WorldWideScience

Sample records for bond dissociation energies

  1. Thermochemistry and bond dissociation energies of ketones.

    Science.gov (United States)

    Hudzik, Jason M; Bozzelli, Joseph W

    2012-06-14

    Ketones are a major class of organic chemicals and solvents, which contribute to hydrocarbon sources in the atmosphere, and are important intermediates in the oxidation and combustion of hydrocarbons and biofuels. Their stability, thermochemical properties, and chemical kinetics are important to understanding their reaction paths and their role as intermediates in combustion processes and in atmospheric chemistry. In this study, enthalpies (ΔH°(f 298)), entropies (S°(T)), heat capacities (C(p)°(T)), and internal rotor potentials are reported for 2-butanone, 3-pentanone, 2-pentanone, 3-methyl-2-butanone, and 2-methyl-3-pentanone, and their radicals corresponding to loss of hydrogen atoms. A detailed evaluation of the carbon-hydrogen bond dissociation energies (C-H BDEs) is also performed for the parent ketones for the first time. Standard enthalpies of formation and bond energies are calculated at the B3LYP/6-31G(d,p), B3LYP/6-311G(2d,2p), CBS-QB3, and G3MP2B3 levels of theory using isodesmic reactions to minimize calculation errors. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) density functional level and are used to determine the entropies and heat capacities. The recommended ideal gas-phase ΔH°(f 298), from the average of the CBS-QB3 and G3MP2B3 levels of theory, as well as the calculated values for entropy and heat capacity are shown to compare well with the available experimental data for the parent ketones. Bond energies for primary, secondary, and tertiary radicals are determined; here, we find the C-H BDEs on carbons in the α position to the ketone group decrease significantly with increasing substitution on these α carbons. Group additivity and hydrogen-bond increment values for these ketone radicals are also determined.

  2. Dissociation Energies of Sulfur-Centered Hydrogen-Bonded Complexes.

    Science.gov (United States)

    Ghosh, Sanat; Bhattacharyya, Surjendu; Wategaonkar, Sanjay

    2015-11-01

    In this work we have determined dissociation energies of O-H···S hydrogen bond in the H2S complexes of various phenol derivatives using 2-color-2-photon photofragmentation spectroscopy in combination with zero kinetic energy photoelectron (ZEKE-PE) spectroscopy. This is the first report of direct determination of dissociation energy of O-H···S hydrogen bond. The ZEKE-PE spectra of the complexes revealed a long progression in the intermolecular stretching mode with significant anharmonicity. Using the anharmonicity information and experimentally determined dissociation energy, we also validated Birge-Sponer (B-S) extrapolation method, which is an approximate method to estimate dissociation energy. Experimentally determined dissociation energies were compared with a variety of ab initio calculations. One of the important findings is that ωB97X-D functional, which is a dispersion corrected DFT functional, was able to predict the dissociation energies in both the cationic as well as the ground electronic state very well for almost every case.

  3. Accurate bond dissociation energies (D 0) for FHF- isotopologues

    Science.gov (United States)

    Stein, Christopher; Oswald, Rainer; Sebald, Peter; Botschwina, Peter; Stoll, Hermann; Peterson, Kirk A.

    2013-09-01

    Accurate bond dissociation energies (D 0) are determined for three isotopologues of the bifluoride ion (FHF-). While the zero-point vibrational contributions are taken from our previous work (P. Sebald, A. Bargholz, R. Oswald, C. Stein, P. Botschwina, J. Phys. Chem. A, DOI: 10.1021/jp3123677), the equilibrium dissociation energy (D e ) of the reaction ? was obtained by a composite method including frozen-core (fc) CCSD(T) calculations with basis sets up to cardinal number n = 7 followed by extrapolation to the complete basis set limit. Smaller terms beyond fc-CCSD(T) cancel each other almost completely. The D 0 values of FHF-, FDF-, and FTF- are predicted to be 15,176, 15,191, and 15,198 cm-1, respectively, with an uncertainty of ca. 15 cm-1.

  4. The dissociative bond.

    Science.gov (United States)

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  5. Influence of charge and coordination number on bond dissociation energies, distances, and vibrational frequencies for the phosphorus-phosphorus bond.

    Science.gov (United States)

    Chitnis, Saurabh S; Whalen, J Marc; Burford, Neil

    2014-09-01

    We report a comprehensive and systematic experimental and computational assessment of the P-P bond in prototypical molecules that represent a rare series of known compounds. The data presented complement the existing solid-state structural data and previous computational studies to provide a thorough thermodynamic and electronic understanding of the P-P bond. Comparison of homolytic and heterolytic bond dissociation for tricoordinate-tricoordinate, tricoordinate-tetracoordinate, and tetracoordinate-tetracoordinate P-P bonds in frameworks 1-6 provides fundamental insights into covalent bonding. For all types of P-P bond discussed, homolytic dissociation is favored over heterolytic dissociation, although the distinction is small for 2(1+) and 6(1+). The presence of a single cationic charge in a molecule substantially strengthens the P-P bond (relative to analogous neutral frameworks) such that it is comparable with the C-C bond in alkanes. Nevertheless, P-P distances are remarkably independent of molecular charge or coordination number, and trends in values of d(PC) and νsymm(PC) imply that a molecular cationic charge is distributed over the alkyl substituents. In the gas phase, the diphosphonium dication 3(2+) has similar energy to two [PMe3](+) radical cations, so that it is the lattice enthalpy of 3[OTf]2 in the solid-state that enables isolation, highlighting that values from gas-phase calculations are poor guides for synthetic planning for ionic compounds. There are no relationships or correlations between bond lengths, strengths, and vibrational frequencies.

  6. Theoretical study of the C-H bond dissociation energy of acetylene

    Science.gov (United States)

    Taylor, Peter R.; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1990-01-01

    The authors present a theoretical study of the convergence of the C-H bond dissociation energy (D sub o) of acetylene with respect to both the one- and n-particle spaces. Their best estimate for D sub o of 130.1 plus or minus 1.0 kcal/mole is slightly below previous theoretical estimates, but substantially above the value determined using Stark anticrossing spectroscopy that is asserted to be an upper bound.

  7. The evaluation of bond dissociation energies for NO2 scission in nitro compounds using density functional

    Institute of Scientific and Technical Information of China (English)

    Shao Ju-Xiang; Cheng Xin-Lu; Ynag Xiang-Dong; He Bi

    2006-01-01

    By using the density functional theory (B3LYP) and four highly accurate complete basis set (CBS-Q, CBS-QB3, CBS-Lq, and CBS-4M) ab initio methods, the X(C, N, O)-NO2 bond dissociation energies (BDEs) for ChsNO2, C2H3NO2) C2H5NO2, HONO2, CH3ONO2, C2H5ONO2, NH2NO2 (CH3)2NNO2 are computed. By comparing the computed BDEs and experimental results, it is found that the B3LYP method is unable to predict satisfactorily the results of bond dissociation energy (BDE); however, all four CBS models are generally able to give reliable predication of the X(C, N, O)-NO2 BDEs for these nitro compounds. Moreover, the CBS-4M calculation is the least computationally demanding among the four CBS methods considered. Therefore, we recommend CBS-4M method as a reliable method of computing the BDEs for this nitro compound system.

  8. Heterolytic and Homolytic N-NO Bond Dissociation Energies of N-Nitroso-benzenesulfonylmethylamines in Acetonitrile

    Institute of Scientific and Technical Information of China (English)

    HAO Wei-Fang; Tang Hui; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Great interests have been accumulated in recent years in the chemistry and biochemistry of nitric oxide (NO) since the remarkable discoveries of its key roles in a wide range of human physiological processes. To elucidate the mechanistic details of NO migration from its donor to its acceptor, it is necessary to determine the Y-NO bind energy that registers the thermodynamic driving force for NO release and capture. In this paper the heterolytic and homolytic N-NO bond dissociation energies [ i. e., △Hhet(N-NO) and △Hhomo(N-NO)] for ten N-nitroso-p-substituted-benzensulfonyl methylamines in acetonitrile are offered, which were obtained from titration calorimetry and thermodynamic cycles, respectively (Scheme 1).

  9. Quantum chemical calculations of bond dissociation energies for COOH scission and electronic structure in some acids

    Institute of Scientific and Technical Information of China (English)

    Zeng Hui; Zhao Jun; Xiao Xun

    2013-01-01

    Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies (BDEs) for 15 acids.These compounds are studied by utilizing the hybrid density functional theory (DFT) (B3LYP,B3PW91,B3P86,PBE1PBE) and the complete basis set (CBS-Q) method in conjunction with the 6-31 lG** basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work.Comparisons between the computational results and the experimental values reveal that CBS-Q method,which can produce reasonable BDEs for some systems in our previous work,seems unable to predict accurate BDEs here.However,the B3P86 calculated results accord very well with the experimental values,within an average absolute error of 2.3 kcal/mol.Thus,B3P86 method is suitable for computing the reliable BDEs of C-COOH bond for carboxylic acid compounds.In addition,the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of studied compounds are estimated,based on which the relative thermal stabilities of the studied acids are also discussed.

  10. C-H and N-H bond dissociation energies of small aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Barckholtz, C.; Barckholtz, T.A.; Hadad, C.M.

    1999-01-27

    A survey of computational methods was undertaken to calculate the homolytic bond dissociation energies (BDEs) of the C-H and N-H bonds in monocyclic aromatic molecules that are representative of the functionalities present in coal. These include six-membered rings (benzene, pyridine, pyridazine, pyrimidine, pyrazine) and five-membered rings (furan, thiophene, pyrrole, oxazole). By comparison of the calculated C-H BDEs with the available experimental values for these aromatic molecules, the B3LYP/6-31G(d) level of theory was selected to calculate the BDEs of polycyclic aromatic hydrocarbons (PAHs), including carbonaceous PAHs (naphthalene, anthracene, pyrene, coronene) and heteroatomic PAHs (benzofuran, benzothiophene, indole, benzoxazole, quinoline, isoquinoline, dibenzofuran, carbazole). The cleavage of a C-H or a N-H bond generates a {sigma} radical that is, in general, localized at the site from which the hydrogen atom was removed. However, delocalization of the unpaired electron results in {approximately} 7 kcal {center{underscore}dot} mol{sup {minus}1} stabilization of the radical with respect to the formation of phenyl when the C-H bond is adjacent to a nitrogen atom in the azabenzenes. Radicals from five-membered rings are {approximately} 6 kcal {center{underscore}dot} mol{sup {minus}1} less stable than those formed from six-membered rings due to both localization of the spin density and geometric factors. The location of the heteroatoms in the aromatic ring affects the C-H bond strengths more significantly than does the size of the aromatic network. Therefore, in general, the monocyclic aromatic molecules can be used to predict the C-H BDE of the large PAHs within 1 kcal {center{underscore}dot} mol{sup {minus}1}.

  11. PCM study of the solvent and substituent effects on bond dissociation energies of the C=NO bond

    Science.gov (United States)

    Li, Xiao-Hong; Tang, Zheng-Xin; Yang, Xiang-Dong

    Quantum chemical calculations are used to estimate the equilibrium C=NO bond dissociation energies (BDEs) for eight X=NO molecule (X = CCl3, C6F5, CH3, CH3CH2, iC3H7, tC4H9, CH2CHCH2, and C6H5CH2). These compounds are studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86) methods together with 6-31G** and 6-311G** basis sets and the complete basis set (CBS-QB3) method. The obtained results are compared with the available experimental results. It is demonstrated that B3P86/6-31G** and CBS-QB3 methods are accurate for computing the reliable BDEs for the X=NO molecule. Considering the inevitably computational cost of CBS-QB3 method and the reliability of the B3P86 calculations, B3P86 method with 6-31G** basis set may be more suitable to calculate the BDEs of the C=NO bond. The solvent effects on the BDEs of the C=NO bond are analyzed and it is shown that the C=NO BDEs in a vacuum computed by using B3PW91/6-311G** method are the closest to the computed values in acetontrile and the average solvent effect is 1.48 kcal/mol. Subsequently, the substituent effects of the BDEs of the C=NO bond are further analyzed and it is found that electron denoting group stabilizes the radical and as a result BDE decreases; whereas electron withdrawing group stabilizes the group state of the molecule and thus increases the BDE from the parent molecule.

  12. Trends in bond dissociation energies of alcohols and aldehydes computed with multireference averaged coupled-pair functional theory.

    Science.gov (United States)

    Oyeyemi, Victor B; Keith, John A; Carter, Emily A

    2014-05-01

    As part of our ongoing investigation of the combustion chemistry of oxygenated molecules using multireference correlated wave function methods, we report bond dissociation energies (BDEs) in C1-C4 alcohols (from methanol to the four isomers of butanol) and C1-C4 aldehydes (from methanal to butanal). The BDEs are calculated with a multireference averaged coupled-pair functional-based scheme. We compare these multireference BDEs with those derived from experiment and single-reference methods. Trends in BDEs for the alcohols and aldehydes are rationalized by considering geometry relaxations of dissociated radical fragments, resonance stabilization, and hyperconjugation. Lastly, we discuss the conjectured association between bond strengths and rates of hydrogen abstraction by hydroxyl radicals. In general, abstraction reaction rates are higher at sites where the C-H bond energies are lower (and vice versa). However, comparison with available rate data shows this inverse relationship between bond strengths and abstraction rates does not hold at all temperatures.

  13. Theoretical Study of the N-NO2 Bond Dissociation Energies for Energetic Materials with Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    LI Xiao-Hong; TANG Zheng-Xin; Abraham F.Jalbout; ZHANG Xian-Zhou; CHENG Xin-Lu

    2008-01-01

    The N-NO2 bond dissociation energies (BDEs) for 7 energetic materials were computed by means of accurate density functional theory (B3LYP, B3PW91 and B3P86) with 6-31G** and 6-311G** basis sets. By comparing the computed energies and experimental results, we find that the B3P86/6-311G** method can give good results of BDE, which has the mean absolute deviation of 1.30 kcal/mol. In addition, substituent effects were also taken into account. It is noted that the Hammett constants of substituent groups are related to the BDEs of the N-NO2 bond and the bond dissociation energies of the energetic materials studied decrease when increasing the number of NO2 group.

  14. The solvent and substituent effects on bond dissociation energies of NO-donor molecules containing the N-NO bond

    Indian Academy of Sciences (India)

    Li Xiao-Hong; Li Wei-Bin; Zhang Xian-Zhou

    2010-07-01

    Quantum chemical calculations are used to estimate the equilibrium N-NO bond dissociation energies (BDEs) for 15 NO-donor molecules in acetonitrile. These compounds are studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86) methods together with 6-31G∗∗ basis set. The basis set superposition error (BSSE) and zero-point vibrational energy (ZPVE) are considered. The results are compared with the available experimental results. It is demonstrated that B3LYP/6-31G** is accurate to compute the reliable BDEs for the NO-donor molecules. The solvent effects on the N-NO BDEs are analysed and the result shows that the N-NO BDEs in a vacuum computed by B3P86/6-31G∗∗ method are the closest to the computed values in acetontrile and the average solvent effect is 0.78 kcal/mol. Subsequently, the substituent effects on the N-NO BDEs are further analysed and it is found that electron donating group stabilizes the radical and as a result BDE decreases; whereas electron withdrawing group stabilizes the ground state of the molecule and thus increases the BDE.

  15. 1, 4-Pyrone Effects on O-H Bond Dissociation Energies of Catechols in Flavonoids: A Density Functional Theory Study

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Through B3LYP/6-31G** calculations, the 1, 4-pyrone effects on O-H bond dissociation energies (BDEs) of catechols in rings A or B of flavonoids were investigated. For the catechol in ring A, although 1, 4-pyrone enlarged the conjugation system, its electron-withdrawing property increased the O-H BDE 3 ( 4.184 kJ/mol compared with that of catechol. However, for the catechol in ring B, 1, 4-pyrone was poorly conjugated with the moiety, and therefore, had little effect on the O-H BDE.

  16. Bond-specific dissociation following excitation energy transfer for distance constraint determination in the gas phase.

    Science.gov (United States)

    Hendricks, Nathan G; Lareau, Nichole M; Stow, Sarah M; McLean, John A; Julian, Ryan R

    2014-09-24

    Herein, we report chemistry that enables excitation energy transfer (EET) to be accurately measured via action spectroscopy on gaseous ions in an ion trap. It is demonstrated that EET between tryptophan or tyrosine and a disulfide bond leads to excited state, homolytic fragmentation of the disulfide bond. This phenomenon exhibits a tight distance dependence, which is consistent with Dexter exchange transfer. The extent of fragmentation of the disulfide bond can be used to determine the distance between the chromophore and disulfide bond. The chemistry is well suited for the examination of protein structure in the gas phase because native amino acids can serve as the donor/acceptor moieties. Furthermore, both tyrosine and tryptophan exhibit unique action spectra, meaning that the identity of the donating chromophore can be easily determined in addition to the distance between donor/acceptor. Application of the method to the Trpcage miniprotein reveals distance constraints that are consistent with a native-like fold for the +2 charge state in the gas phase. This structure is stabilized by several salt bridges, which have also been observed to be important previously in proteins that retain native-like structures in the gas phase. The ability of this method to measure specific distance constraints, potentially at numerous positions if combined with site-directed mutagenesis, significantly enhances our ability to examine protein structure in the gas phase.

  17. Assessment of Performance of G3B3 and CBS-QB3 Methods in Calculation of Bond Dissociation Energies

    Institute of Scientific and Technical Information of China (English)

    亓秀娟; 封勇; 刘磊; 郭庆祥

    2005-01-01

    The performance of the newly developed G3B3 and CBS-QB3 methods in calculating absolute bond dissociation energy (BDE) was assessed. It was found that these two methods could predict the BDE with an accuracy of about 8.4 kJ/mol and therefore, they exlfibited similar performance as the standard G3 and CBS-Q methods. On the other hand, it was demonstrated that the B3LYP method significantly underestimated the absolute BDE by 16.7—20.9 kJ/mol. This finding was valuable and timely because many researchers could use this relatively cheap method in studying radical reactions. Finally, 38 compounds were showed for which the theoretical BDE seriously deviated from the experimental data.

  18. Density Functional Method Studies of X-H (X=C, N, O, Si, P, S) Bond Dissociation Energies

    Institute of Scientific and Technical Information of China (English)

    FU Yao; DONG Xiao-Yu; WANG Yi-Min; LIU Lei; GUO Qing-Xiang

    2005-01-01

    The performances of the density functional theory (DFT) methods in calculating X-H bond dissociation energies (BDE, X=C, N, O, Si, P, S) were evaluated. It was found that most DFT methods including B3LYP, B3PW91,G96LYP, PBE1PBE and BH&HLYP significantly underestimated the X-H BDE by as much as 13-24 kJ/mol.The underestimation is not due to the use of finite basis set, because the DFT methods still significantly underestimate the X-H BDE with the complete basis set. Therefore, these DFT methods can not be used to calculate the BDE directly. Nevertheless, the B3P86 method shows very small underestimation for the X-H BDE. Further analysis suggests that there be no advantage for using the restricted open-shell DFT methods. The unrestricted DFT methods actually perform slightly better than the restricted open-shell DFT methods in most cases. Finally, it was found that the underestimation by the DFT methods was largely systematic. The use of the calibrated UDFT/6-311+ + G(d, p) method was recommended to calculate the X-H BDE.

  19. Diffusion Monte Carlo Study of Bond Dissociation Energies for BH2,B(OH)2, BCl2, and BCl

    Institute of Scientific and Technical Information of China (English)

    Hui-ran Li; Xin-lu Cheng; Hong Zhang

    2012-01-01

    On basis of bond dissociation energies (BDEs) for BH2,B(OH)2,BCl2,and BCl,the diffusion Monte Carlo (DMC) method is applied to explore the BDEs of HB-H,HOB-OH,ClB-Cl,and B-Cl.The effect of the choice of orbitals,as well as the backflow transformation,is studied.The Slater-Jastrow DMC algorithm gives BDEs of 359.1±0.12 kJ/mol for HB-H,410.5±0.50 kJ/mol for HOB-OH,357.8±1.46 kJ/mol for ClB-Cl,and 504.5±0.96 kJ/mol for B-Cl using B3PW91 orbitals and similar BDEs when B3LYP orbitals are used.DMC with backflow corrections (BF-DMC) gives a HB-H BDE of 369.9±0.12 kJ/mol which isclose to one of the available experimental value (375.8 kJ/mol).In the case of HOB-OH BDE,the BF-DMC calculation is 446.0±1.84 kJ/mol that is closer to the experimental BDE.The BF-DMC BDE for ClB-Cl is 343.2±2.34 kJ/mol and the BF-DMC B-Cl BDE is 523.3±0.33 kJ/mol,which are close to the experimental BDEs,341.9 and 530.0 kJ/mol,respectively.

  20. Trends in Homolytic Bond Dissociation Energies of Five- and Six-Coordinate Hydrides of Group 9 Transition Metals: Co, Rh, Ir.

    Science.gov (United States)

    Glezakou, Vassiliki-Alexandra; Rousseau, Roger; Elbert, Stephen T; Franz, James A

    2017-03-09

    The homolytic bond dissociation energies of a series of five- and six-coordinate mono- and dihydride complexes of the type HM(diphosphine)2 and [H2M(diphosphine)2](+) (where M = Co, Rh, and Ir) are calculated and compared with experimental values. This work probes the relationship between the homolytic bond dissociation energies (HMBDEs) of these complexes in these two different coordination environments and formal oxidation states. The results of these calculations and previous experimental observations suggest that for M = Rh the HMBDE of the five-coordinate HM(diphosphine)2 species are 0-2 kcal/mol larger than the HMBDE of the corresponding six-coordinate [H2M(diphosphine)2](+) species. For M = Ir the bond energies of the five- and six-coordinate complexes are nearly the same and for M = Co the six-coordinate species are 1-5 kcal/mol less than the corresponding five-coordinate species. Simplified models of large and complicated ligands seem to capture the essential trends and give very good estimates of these thermodynamic properties compared with experimentally available data that are difficult to obtain.

  1. Dissociation Energies of Diatomic Molecules

    Institute of Scientific and Technical Information of China (English)

    FAN Qun-Chao; SUN Wei-Guo

    2008-01-01

    Molecular dissociation energies of 10 electronic states of alkali molecules of KH, 7LID, 7LiH, 6LiH, NaK, NaLi and NaRb are studied using the highest three accurate vibrational energies of each electronic state, and an improved parameter-free analytical formula which is obtained starting from the LeRoy-Bernstein vibrational energy expression near the dissociation limit. The results show that as long as the highest three vibrational energies are accurate, the current analytical formula will give accurate theoretical dissociation energies Detheory, which are in excellent agreement with the experimental dissociation energies Dexpte.

  2. Dispersion-correcting potentials can significantly improve the bond dissociation enthalpies and noncovalent binding energies predicted by density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    DiLabio, Gino A., E-mail: Gino.DiLabio@nrc.ca [National Institute for Nanotechnology, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9 (Canada); Department of Chemistry, University of British Columbia, Okanagan, 3333 University Way, Kelowna, British Columbia V1V 1V7 (Canada); Koleini, Mohammad [National Institute for Nanotechnology, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9 (Canada); Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4 (Canada)

    2014-05-14

    Dispersion-correcting potentials (DCPs) are atom-centered Gaussian functions that are applied in a manner that is similar to effective core potentials. Previous work on DCPs has focussed on their use as a simple means of improving the ability of conventional density-functional theory methods to predict the binding energies of noncovalently bonded molecular dimers. We show in this work that DCPs developed for use with the LC-ωPBE functional along with 6-31+G(2d,2p) basis sets are capable of simultaneously improving predicted noncovalent binding energies of van der Waals dimer complexes and covalent bond dissociation enthalpies in molecules. Specifically, the DCPs developed herein for the C, H, N, and O atoms provide binding energies for a set of 66 noncovalently bonded molecular dimers (the “S66” set) with a mean absolute error (MAE) of 0.21 kcal/mol, which represents an improvement of more than a factor of 10 over unadorned LC-ωPBE/6-31+G(2d,2p) and almost a factor of two improvement over LC-ωPBE/6-31+G(2d,2p) used in conjunction with the “D3” pairwise dispersion energy corrections. In addition, the DCPs reduce the MAE of calculated X-H and X-Y (X,Y = C, H, N, O) bond dissociation enthalpies for a set of 40 species from 3.2 kcal/mol obtained with unadorned LC-ωPBE/6-31+G(2d,2p) to 1.6 kcal/mol. Our findings demonstrate that broad improvements to the performance of DFT methods may be achievable through the use of DCPs.

  3. Theoretical study of GeH sub n , AsH sub n , and SeH sub n : Bond dissociation energies

    Energy Technology Data Exchange (ETDEWEB)

    Binning, R.C. Jr. (Department of Chemistry and Physics, Carlow College, Pittsburgh, Pennsylvania 15213 (USA)); Curtiss, L.A. (Chemical Technology Division/Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439-4837 (USA))

    1990-02-01

    {ital Ab} {ital initio} molecular orbital theory (Moller--Plesset perturbation theory to fourth order and new basis sets developed for Ge, As, and Se) is used to calculate the atomization energies of GeH{sub {ital n}}({ital n}=1--4), AsH{sub {ital n}}({ital n}=1--3), and SeH{sub {ital n}}({ital n}=1--2). Good agreement is found with the experimental bond dissociation energies of these hydrides derived from recent photoionization studies. The theoretical energies are combined with experimental data on the isolated atoms to determine ideal enthalpies of formation at 0 K for these hydrides, which are expected to have an accuracy of about {plus minus}3 kcal/mol ({plus minus}0.15 eV).

  4. The Cr+-D2 cation complex: Accurate experimental dissociation energy, intermolecular bond length, and vibrational parameters

    Science.gov (United States)

    Dryza, V.; Bieske, E. J.

    2009-10-01

    The infrared spectrum of the T-shaped C52r+-D2 complex is measured over the 2742-2820 cm-1 range by detecting Cr+ photofragments. The main band, due to the D-D stretch excitation, is shifted at 215 cm-1 to lower energy from the Q01 transition of the free D2 molecule and displays clearly resolved rovibrational transitions. Observation of a photodissociation onset for the N'=8 rotational level is used to infer that the dissociation energy of Cr+-D2, with respect to ground-state Cr+ and D2 fragments, lies between 2839.7 and 2856.9 cm-1. Perturbations to the upper state levels are presumed to arise from interactions with quasibound combination levels involving the intermolecular stretch and bend vibrational modes. A vibrationally averaged Cr+⋯D2 separation of 2.023 Å and an estimate of 394 cm-1 for the intermolecular harmonic stretching frequency are derived from the measured rotational constants.

  5. The Cr(+)-D(2) cation complex: Accurate experimental dissociation energy, intermolecular bond length, and vibrational parameters.

    Science.gov (United States)

    Dryza, V; Bieske, E J

    2009-10-28

    The infrared spectrum of the T-shaped (52)Cr(+)-D(2) complex is measured over the 2742-2820 cm(-1) range by detecting Cr(+) photofragments. The main band, due to the D-D stretch excitation, is shifted at 215 cm(-1) to lower energy from the Q(0) (1) transition of the free D(2) molecule and displays clearly resolved rovibrational transitions. Observation of a photodissociation onset for the N(')=8 rotational level is used to infer that the dissociation energy of Cr(+)-D(2), with respect to ground-state Cr(+) and D(2) fragments, lies between 2839.7 and 2856.9 cm(-1). Perturbations to the upper state levels are presumed to arise from interactions with quasibound combination levels involving the intermolecular stretch and bend vibrational modes. A vibrationally averaged Cr(+)...D(2) separation of 2.023 A and an estimate of 394 cm(-1) for the intermolecular harmonic stretching frequency are derived from the measured rotational constants.

  6. Excitation energies with linear response density matrix functional theory along the dissociation coordinate of an electron-pair bond in N-electron systems.

    Science.gov (United States)

    van Meer, R; Gritsenko, O V; Baerends, E J

    2014-01-14

    Time dependent density matrix functional theory in its adiabatic linear response formulation delivers exact excitation energies ωα and oscillator strengths fα for two-electron systems if extended to the so-called phase including natural orbital (PINO) theory. The Löwdin-Shull expression for the energy of two-electron systems in terms of the natural orbitals and their phases affords in this case an exact phase-including natural orbital functional (PILS), which is non-primitive (contains other than just J and K integrals). In this paper, the extension of the PILS functional to N-electron systems is investigated. With the example of an elementary primitive NO functional (BBC1) it is shown that current density matrix functional theory ground state functionals, which were designed to produce decent approximations to the total energy, fail to deliver a qualitatively correct structure of the (inverse) response function, due to essential deficiencies in the reconstruction of the two-body reduced density matrix (2RDM). We now deduce essential features of an N-electron functional from a wavefunction Ansatz: The extension of the two-electron Löwdin-Shull wavefunction to the N-electron case informs about the phase information. In this paper, applications of this extended Löwdin-Shull (ELS) functional are considered for the simplest case, ELS(1): one (dissociating) two-electron bond in the field of occupied (including core) orbitals. ELS(1) produces high quality ωα(R) curves along the bond dissociation coordinate R for the molecules LiH, Li2, and BH with the two outer valence electrons correlated. All of these results indicate that response properties are much more sensitive to deficiencies in the reconstruction of the 2RDM than the ground state energy, since derivatives of the functional with respect to both the NOs and the occupation numbers need to be accurate.

  7. Excitation energies with linear response density matrix functional theory along the dissociation coordinate of an electron-pair bond in N-electron systems

    Energy Technology Data Exchange (ETDEWEB)

    Meer, R. van; Gritsenko, O. V. [Faculty of Exact Sciences, Theoretical Chemistry, VU University, Amsterdam (Netherlands); WCU Program, Dep. of Chemistry, Pohang Univ. of Science and Techn., Pohang (Korea, Republic of); Baerends, E. J. [Faculty of Exact Sciences, Theoretical Chemistry, VU University, Amsterdam (Netherlands); WCU Program, Dep. of Chemistry, Pohang Univ. of Science and Techn., Pohang (Korea, Republic of); Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

    2014-01-14

    Time dependent density matrix functional theory in its adiabatic linear response formulation delivers exact excitation energies ω{sub α} and oscillator strengths f{sub α} for two-electron systems if extended to the so-called phase including natural orbital (PINO) theory. The Löwdin-Shull expression for the energy of two-electron systems in terms of the natural orbitals and their phases affords in this case an exact phase-including natural orbital functional (PILS), which is non-primitive (contains other than just J and K integrals). In this paper, the extension of the PILS functional to N-electron systems is investigated. With the example of an elementary primitive NO functional (BBC1) it is shown that current density matrix functional theory ground state functionals, which were designed to produce decent approximations to the total energy, fail to deliver a qualitatively correct structure of the (inverse) response function, due to essential deficiencies in the reconstruction of the two-body reduced density matrix (2RDM). We now deduce essential features of an N-electron functional from a wavefunction Ansatz: The extension of the two-electron Löwdin-Shull wavefunction to the N-electron case informs about the phase information. In this paper, applications of this extended Löwdin-Shull (ELS) functional are considered for the simplest case, ELS(1): one (dissociating) two-electron bond in the field of occupied (including core) orbitals. ELS(1) produces high quality ω{sub α}(R) curves along the bond dissociation coordinate R for the molecules LiH, Li{sub 2}, and BH with the two outer valence electrons correlated. All of these results indicate that response properties are much more sensitive to deficiencies in the reconstruction of the 2RDM than the ground state energy, since derivatives of the functional with respect to both the NOs and the occupation numbers need to be accurate.

  8. Influence of steric and intramolecular inductive effects on the variable trends in R-X (R=Alkyl) bond dissociation energy

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The question "why are the variation trends of R-X bond dissociation energy different?" is answered. The R-X bond dissociation energy (BDE) may be influenced by three main factors: the C-X intrinsic bond energy, the 1,3 geminal repulsion, and the intramolecular charge-induced dipole. In the presence of atom X, the variation trend of BDE in R-X (R= Me, Et, i-Pr, t-Bu) is dominated by two factors, the 1,3 geminal repulsion and the intramolecular charge-induced dipole. The former decreases the R-X BDE, and the latter either increases or decreases the R-X BDE. For the series of R-X with the R-C bond (such as R-Me, R-CH == CH2, R-C≡CH, and R-CN), the 1,3 geminal repulsion decreases the R-X BDE, and the variation trends of R-C BDE decrease from Me to t-Bu. As regards the series of R-X (such as R-H, R-BH2, and R-SiH2) in which the electronegativity of atom X is smaller than that of the carbon atom, the above two factors decrease the R-X BDE, and the variation trends of the R-X BDE decrease from Me to t-Bu. As to the series of R-X (such as R-F, R-OH, R-Cl, R-Br, R-I, and R-NH2) in which the electronegativity of atom X is larger than that of the carbon atom, the 1,3 geminal repulsion decreases the R-X BDE, while the intramolecular charge-induced dipole increases the R-X BDE. In this case, the variation trends of R-X BDE depend on the competition of the two factors. As a result, some of them (e. g., R-F, R-OH) increase from Me to t-Bu, some (e. g., R-I) decrease from Me to t-Bu, and some (e. g., R-Br) change very little.

  9. Influence of steric and intramolecular inductive effects on the variable trends in R-X (R=Alkyl) bond dissociation energy

    Institute of Scientific and Technical Information of China (English)

    CAO ChenZhong

    2009-01-01

    The question "why are the variation trends of R-X bond dissociation energy different?" is answered.The R-X bond dissociation energy (BDE) may be influenced by three main factors:the C-X intrinsic bond energy,the 1,3 geminal repulsion,and the intramolecular charge-induced dipole.In the presence of atom X,the variation trend of BDE in R-X (R=Me,Et,i-Pr,t-Bu) is dominated by two factors,the 1,3 geminal repulsion and the intramolecular charge-induced dipole.The former decreases the R-X BDE,and the latter either increases or decreases the R-X BDE.For the series of R-X with the R-C bond (such as R-Me,R-CH-CH2,R-C-CH,and R-CN),the 1,3 geminal repulsion decreases the R-X BDE,and the variation trends of R-C BDE decrease from Me to t-Bu.As regards the series of R-X (such as R-H,R-BH2,and R-SiH2) in which the electronegativity of atom X is smaller than that of the carbon atom,the above two factors decrease the R-X BDE,and the variation trends of the R-X BDE decrease from Me to t-Bu.As to the series of R-X (such as R-F,R-OH,R-CI,R-Br,R-I,and R-NH2) in which the electronegativity of atom X is larger than that of the carbon atom,the 1,3 geminal repulsion decreases the R-X BDE,while the intramolecular charge-induced dipole increases the R-X BDE.In this case,the variation trends of R-X BDE depend on the competition of the two factors.As a result,some of them (e.g.,R-F,R-OH) increase from Me to t-Bu,some (e.g.,R-I) decrease from Me to t-Bu,and some (e.g.,R-Br) change very little.

  10. Effect of substituents on the strength of N-X (X = H, F, and Cl) bond dissociation energies: a high-level quantum chemical study.

    Science.gov (United States)

    O'Reilly, Robert J; Karton, Amir; Radom, Leo

    2011-06-02

    The effect of substituents on the strength of N-X (X = H, F, and Cl) bonds has been investigated using the high-level W2w thermochemical protocol. The substituents have been selected to be representative of the key functional groups that are likely to be of biological, synthetic, or industrial importance for these systems. We interpreted the effects through the calculation of relative N-X bond dissociation energies (BDE) or radical stabilization energies (RSE(NX)). The BDE and RSE(NX) values depend on stabilizing/destabilizing effects in both the reactant molecule and the product radical of the dissociation reactions. To assist us in the analysis of the substituent effects, a number of additional thermochemical quantities have been introduced, including molecule stabilization energies (MSE(NX)). We find that the RSE(NH) values are (a) increased by electron-donating alkyl substituents or the vinyl substituent, (b) increased in imines, and (c) decreased by electron-withdrawing substituents such as CF(3) and carbonyl moieties or through protonation. A different picture emerges when considering the RSE(NF) and RSE(NCl) values because of the electronegativities of the halogen atoms. The RSE(NX)s differ from the RSE(NH) values by an amount related to the stabilization of the N-halogenated molecules and given by MSE(NX). We find that substituents that stabilize/destabilize the radicals also tend to stabilize/destabilize the N-halogenated molecules. As a result, N-F- and N-Cl-containing molecules that include alkyl substituents or correspond to imines are generally associated with RSE(NF) and RSE(NCl) values that are less positive or more negative than the corresponding RSE(NH). In contrast, N-F- and N-Cl-containing molecules that include electron-withdrawing substituents or are protonated are generally associated with RSE(NF) and RSE(NCl) values that are more positive or less negative than the corresponding RSE(NH).

  11. Communication: The highest frequency hydrogen bond vibration and an experimental value for the dissociation energy of formic acid dimer

    DEFF Research Database (Denmark)

    Kollipost, F.; Larsen, René Wugt; Domanskaya, A.V.

    2012-01-01

    . Comparison to earlier studies at room temperature reveals the large influence of thermal excitation on the band maximum. Together with three Bu combination states involving hydrogen bond fundamentals and with recent progress for the Raman-active modes, this brings into reach an accurate statistical...

  12. Three methods to measure RH bond energies

    Energy Technology Data Exchange (ETDEWEB)

    Berkowitz, J. [Argonne National Lab., IL (United States); Ellison, G.B. [Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry; Gutman, D. [Catholic Univ. of America, Washington, DC (United States). Dept. of Chemistry

    1993-03-21

    In this paper the authors compare and contrast three powerful methods for experimentally measuring bond energies in polyatomic molecules. The methods are: radical kinetics; gas phase acidity cycles; and photoionization mass spectroscopy. The knowledge of the values of bond energies are a basic piece of information to a chemist. Chemical reactions involve the making and breaking of chemical bonds. It has been shown that comparable bonds in polyatomic molecules, compared to the same bonds in radicals, can be significantly different. These bond energies can be measured in terms of bond dissociation energies.

  13. Thermochemical properties and bond dissociation energies of C3-C5 cycloalkyl hydroperoxides and peroxy radicals: cycloalkyl radical + (3)O2 reaction thermochemistry.

    Science.gov (United States)

    Auzmendi-Murua, Itsaso; Bozzelli, Joseph W

    2012-07-19

    Cyclic aliphatic hydrocarbons are major components in modern fuels; they can be present in the reactants, and they can be formed during the gas-phase oxidation processes. In combustion and thermal oxidation processes, these cyclics will form radicals that react with (3)O(2) to form peroxy radicals. In this study, density functional theory and higher level ab initio calculations are used to calculate thermochemical properties and bond dissociation energies of 3-5-membered cycloalkanes, corresponding hydroperoxides, hydroperoxycycloalkyl radicals, and cycloalkyl radicals that occur in these reaction systems. Geometries, vibration frequencies, and thermochemical properties, ΔH(f 298)°, are calculated with the B3LYP/6-31 g(d,p), B3LYP/6-31 g(2d,2p), composite CBS-QB3, and G3MP2B3 methods. Standard enthalpies of formation at 298 K are evaluated using isodesmic reaction schemes with several work reactions for each species. Group additivity contributions are developed, and application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities, S°(T) and C(p)°(T) (5 K ≤ T ≤ 5000), are determined using geometric parameters and frequencies from the B3LYP/6-31 g(d,p) calculations.

  14. Thermochemistry of C7H16 to C10H22 alkane isomers: primary, secondary, and tertiary C-H bond dissociation energies and effects of branching.

    Science.gov (United States)

    Hudzik, Jason M; Bozzelli, Joseph W; Simmie, John M

    2014-10-09

    Standard enthalpies of formation (ΔH°f 298) of methyl, ethyl, primary and secondary propyl, and n-butyl radicals are evaluated and used in work reactions to determine internal consistency. They are then used to calculate the enthalpy of formation for the tert-butyl radical. Other thermochemical properties including standard entropies (S°(T)), heat capacities (Cp(T)), and carbon-hydrogen bond dissociation energies (C-H BDEs) are reported for n-pentane, n-heptane, 2-methylhexane, 2,3-dimethylpentane, and several branched higher carbon number alkanes and their radicals. ΔH°f 298 and C-H BDEs are calculated using isodesmic work reactions at the B3LYP (6-31G(d,p) and 6-311G(2d,2p) basis sets), CBS-QB3, CBS-APNO, and G3MP2B3 levels of theory. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level for contributions to entropy and heat capacities. Enthalpy calculations for these hydrocarbon radical species are shown to have consistency with the CBS-QB3 and CBS-APNO methods using all work reactions. Our recommended ideal gas phase ΔH°f 298 values are from the average of all CBS-QB3, CBS-APNO, and for G3MP2B3, only where the reference and target radical are identical types, and are compared with literature values. Calculated values show agreement between the composite calculation methods and the different work reactions. Secondary and tertiary C-H bonds in the more highly branched alkanes are shown to have bond energies that are several kcal mol(-1) lower than the BDEs in corresponding smaller molecules often used as reference species. Entropies and heat capacities are calculated and compared to literature values (when available) when all internal rotors are considered.

  15. Thermochemical Properties and Bond Dissociation Energies for Fluorinated Methanol, CH3-xFxOH, and Fluorinated Methyl Hydroperoxides, CH3-xFxOOH: Group Additivity.

    Science.gov (United States)

    Wang, Heng; Bozzelli, Joseph W

    2016-09-08

    Oxygenated fluorocarbons are routinely found in sampling of environmental soils and waters as a result of the widespread use of fluoro and chlorofluoro carbons as heat transfer fluids, inert materials, polymers, fire retardants and solvents; the influence of these chemicals on the environment is a growing concern. The thermochemical properties of these species are needed for understanding their stability and reactions in the environment and in thermal process. Structures and thermochemical properties on the mono- to trifluoromethanol, CH3-xFxOH, and fluoromethyl hydroperoxide, CH3-xFxOOH (1 ≤ x ≤ 3), are determined by CBS-QB3, CBS-APNO, and G4 calculations. Entropy, S°298, and heat capacities, Cp(T)'s (300 ≤ T/K ≤ 1500) from vibration, translation, and external rotation contributions are calculated on the basis of the vibration frequencies and structures obtained from the B3LYP/6-31+G(d,p) density functional method. Potential barriers for the internal rotations are also calculated from this method and used to calculate hindered rotor contributions to S°298 and Cp(T)'s using direct integration over energy levels of the internal rotational potentials. Standard enthalpies of formation, ΔfH°298 (units in kcal mol(-1)) are CH2FOOH (-83.7), CHF2OOH (-138.1), CF3OOH (-193.6), CH2FOO(•) (-44.9), CHF2OO(•) (-99.6), CF3OO(•) (-153.8), CH2FOH (-101.9), CHF2OH (-161.6), CF3OH (-218.1), CH2FO(•) (-49.1), CHF2O(•) (-97.8), CF3O(•) (-150.5), CH2F(•) (-7.6), CHF2(•) (-58.8), and CF3(•) (-112.6). Bond dissociation energies for the R-OOH, RO-OH, ROO-H, R-OO(•), RO-O(•), R-OH, RO-H, R-O(•), and R-H bonds are determined and compared with methyl hydroperoxide to observe the trends from added fluoro substitutions. Enthalpy of formation for the fluoro-hydrocarbon oxygen groups C/F/H2/O, C/F2/H/O, C/F3/O, are derived from the above fluorinated methanol and fluorinated hydroperoxide species for use in Benson's Group Additivity. It was determined that

  16. Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond

    Science.gov (United States)

    Rožman, Marko

    2016-01-01

    Glycosphingolipid fragmentation behavior was investigated by combining results from analysis of a series of negative ion tandem mass spectra and molecular modeling. Fragmentation patterns extracted from 75 tandem mass spectra of mainly acidic glycosphingolipid species (gangliosides) suggest prominent cleavage of the glycosidic bonds with retention of the glycosidic oxygen atom by the species formed from the reducing end (B and Y ion formation). Dominant product ions arise from dissociation of sialic acids glycosidic bonds whereas product ions resulting from cleavage of other glycosidic bonds are less abundant. Potential energy surfaces and unimolecular reaction rates of several low-energy fragmentation pathways leading to cleavage of glycosidic bonds were estimated in order to explain observed dissociation patterns. Glycosidic bond cleavage in both neutral (unsubstituted glycosyl group) and acidic glycosphingolipids was the outcome of the charge-directed intramolecular nucleophilic substitution (SN2) mechanism. According to the suggested mechanism, the nucleophile in a form of carboxylate or oxyanion attacks the carbon at position one of the sugar ring, simultaneously breaking the glycosidic bond and yielding an epoxide. For gangliosides, unimolecular reaction rates suggest that dominant product ions related to the cleavage of sialic acid glycosidic bonds are formed via direct dissociation channels. On the other hand, low abundant product ions related to the dissociation of other glycosidic bonds are more likely to be the result of sequential dissociation. Although results from this study mainly contribute to the understanding of glycosphingolipid fragmentation chemistry, some mechanistic findings regarding cleavage of the glycosidic bond may be applicable to other glycoconjugates.

  17. Predicting Bond Dissociation Energies of Transition-Metal Compounds by Multiconfiguration Pair-Density Functional Theory and Second-Order Perturbation Theory Based on Correlated Participating Orbitals and Separated Pairs.

    Science.gov (United States)

    Bao, Junwei Lucas; Odoh, Samuel O; Gagliardi, Laura; Truhlar, Donald G

    2017-02-14

    We study the performance of multiconfiguration pair-density functional theory (MC-PDFT) and multireference perturbation theory for the computation of the bond dissociation energies in 12 transition-metal-containing diatomic molecules and three small transition-metal-containing polyatomic molecules and in two transition-metal dimers. The first step is a multiconfiguration self-consistent-field calculation, for which two choices must be made: (i) the active space and (ii) its partition into subspaces, if the generalized active space formulation is used. In the present work, the active space is chosen systematically by using three correlated-participating-orbitals (CPO) schemes, and the partition is chosen by using the separated-pair (SP) approximation. Our calculations show that MC-PDFT generally has similar accuracy to CASPT2, and the active-space dependence of MC-PDFT is not very great for transition-metal-ligand bond dissociation energies. We also find that the SP approximation works very well, and in particular SP with the fully translated BLYP functional SP-ftBLYP is more accurate than CASPT2. SP greatly reduces the number of configuration state functions relative to CASSCF. For the cases of FeO and NiO with extended-CPO active space, for which complete active space calculations are unaffordable, SP calculations are not only affordable but also of satisfactory accuracy. All of the MC-PDFT results are significantly better than the corresponding results with broken-symmetry spin-unrestricted Kohn-Sham density functional theory. Finally we test a perturbation theory method based on the SP reference and find that it performs slightly worse than CASPT2 calculations, and for most cases of the nominal-CPO active space, the approximate SP perturbation theory calculations are less accurate than the much less expensive SP-PDFT calculations.

  18. Mechanical switching and coupling between two dissociation pathways in a P-selectin adhesion bond

    Science.gov (United States)

    Evans, Evan; Leung, Andrew; Heinrich, Volkmar; Zhu, Cheng

    2004-08-01

    Many biomolecular bonds exhibit a mechanical strength that increases in proportion to the logarithm of the rate of force application. Consistent with exponential decrease in bond lifetime under rising force, this kinetically limited failure reflects dissociation along a single thermodynamic pathway impeded by a sharp free energy barrier. Using a sensitive force probe to test the leukocyte adhesion bond P-selectin glycoprotein ligand 1 (PSGL-1)-P-selectin, we observed a linear increase of bond strength with each 10-fold increase in the rate of force application from 300 to 30,000 pN/sec, implying a single pathway for failure. However, the strength and lifetime of PSGL-1-P-selectin bonds dropped anomalously when loaded below 300 pN/sec, demonstrating unexpectedly faster dissociation and a possible second pathway for failure. Remarkably, if first loaded by a "jump" in force to 20-30 pN, the bonds became strong when subjected to a force ramp as slow as 30 pN/sec and exhibited the same single-pathway kinetics under all force rates. Applied in this way, a new "jump/ramp" mode of force spectroscopy was used to show that the PSGL-1-P-selectin bond behaves as a mechanochemical switch where force history selects between two dissociation pathways with markedly different properties. Furthermore, replacing PSGL-1 by variants of its 19-aa N terminus and by the crucial tetrasaccharide sialyl LewisX produces dramatic changes in the failure kinetics, suggesting a structural basis for the two pathways. The two-pathway switch seems to provide a mechanism for the "catch bond" response observed recently with PSGL-1-P-selectin bonds subjected to small-constant forces.

  19. Homolytic Bond Dissociation Enthalpies of C C and C-H Bonds in Highly Crowded Alkanes

    Institute of Scientific and Technical Information of China (English)

    ZHU Chen; RUI Lei; FU Yao

    2008-01-01

    The homolytic C-C and C--H bond dissociation enthalpyies (BDE) of highly crowded alkanes were calcu- lated by using an ONIOM-G3B3 method. Geometric parameters such as bond length, bond angle and molecular volume were carefully investigated, as most of the acyclic alkanes in this study were not yet synthesized. These pa-rameters reflect the influence of steric effect on BDE. Good correlations were found between the rapid decrease of BDE and the increase of molecular volumes. The correlations can be applied to the prediction of the possible exis-tence of many highly strained compounds.

  20. Yukawa-dissociation and the deuteron binding energy

    Energy Technology Data Exchange (ETDEWEB)

    Jacobsen, T.

    1997-05-01

    It is shown that energy must be conserved by the dissociation of an elementary particle. The energy deficit by a dissociation behaves as a basic concept. The binding energy of the deuteron is reproduced. 4 refs.

  1. Birge-Sponer Estimation of the C-H Bond Dissociation Energy in Chloroform Using Infrared, Near-Infrared, and Visible Absorption Spectroscopy: An Experiment in Physical Chemistry

    Science.gov (United States)

    Myrick, M. L.; Greer, A. E.; Nieuwland, A. A.; Priore, R. J.; Scaffidi, J.; Andreatta, Danielle; Colavita, Paula

    2008-01-01

    The fundamental and overtone vibrational absorption spectroscopy of the C-H unit in CHCl[subscript 3] is measured for transitions from the v = 0 energy level to v = 1 through v = 5 energy levels. The energies of the transitions exhibit a linearly-decreasing spacing between adjacent vibrational levels as the vibrational quantum number increases.…

  2. High-level ab initio predictions for the ionization energy, bond dissociation energies, and heats of formation of nickel carbide (NiC) and its cation (NiC+).

    Science.gov (United States)

    Lau, Kai-Chung; Chang, Yih Chung; Shi, Xiaoyu; Ng, C Y

    2010-09-21

    The ionization energy (IE) of NiC and the 0 K bond dissociation energies (D(0)) and heats of formation at 0 K (ΔH(o)(f0)) and 298 K (ΔH(o)(f298)) for NiC and NiC(+) are predicted by the wavefunction based CCSDTQ(Full)/CBS approach and the multireference configuration interaction (MRCI) method with Davidson correction (MRCI+Q). The CCSDTQ(Full)/CBS calculations presented here involve the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations along with the zero-point vibrational energy (ZPVE), high-order correlation, core-valence electronic (CV), spin-orbit coupling (SO), and scalar relativistic effect (SR) corrections. The present calculations provide the correct symmetry predictions for the ground states of NiC and NiC(+) to be (1)∑(+) and (2)∑(+), respectively. The CCSDTQ(Full)/CBS IE(NiC)=8.356 eV is found to compare favorably with the experimental IE value of 8.372 05±0.000 06 eV. The predicted IE(NiC) value at the MRCI+Q/cc-pwCV5Z level, including the ZPVE, SO, and SR effects is 8.00 eV, which is 0.37 eV lower than the experimental value. This work together with the previous experimental and theoretical investigations supports the conclusion that the CCSDTQ(Full)/CBS method is capable of providing reliable IE predictions for 3d-transition metal carbides, such as FeC and NiC. Furthermore, the CCSDTQ(Full)/CBS calculations give the prediction of D(0)(Ni-C)-D(0)(Ni(+)-C)=0.688 eV, which is also consistent with the experimental determination of 0.732 21±0.000 06 eV, whereas the MRCI+Q calculations (with relativistic and CV effects) predict a significantly lower value of 0.39 eV for D(0)(Ni-C)-D(0)(Ni(+)-C). The analysis of the correction terms shows that the CV and valence-valence electronic correlations beyond CCSD(T) wavefunction and the relativistic effect make significant contributions to the calculated thermochemical properties of NiC/NiC(+). For the experimental D(0) and ΔH(o)(f0) values of

  3. Combustion Pathways of the Alkylated Heteroaromatics: Bond Dissociation Enthalpies and Alkyl Group Fragmentations

    Science.gov (United States)

    Hayes, Carrigan J.; Hadad, Christopher M.

    2009-04-01

    The bond dissociation enthalpies (BDEs) of the alkyl groups of the alkyl-substituted heterocycles have been studied and compiled using DFT methodology, with the intent of modeling the larger heterocyclic functionalities found in coal. DFT results were calibrated against CBS-QB3 calculations, and qualitative trends were reproduced between these methods. Loss of hydrogen at the benzylic position provided the most favorable route to radical formation, for both the azabenzenes and five-membered heterocycles. The ethyl derivatives had lower BDE values than the methyl derivatives due to increased stabilization of the corresponding radicals. Calculated spin densities correlated well with bond dissociation enthalpies for these compounds, while geometric effects were minimal with respect to the heterocycles themselves. Temperature effects on the bond dissociation enthalpies were minor, ranging by about 5 kcal/mol from 298 to 2000 K; the free energies of reaction dropped significantly over the same range due to entropic effects. Monocyclic heteroaromatic rings were seen to replicate the chemistry of multicyclic heteroaromatic systems.

  4. The Breathing Orbital Valence Bond Method in Diffusion Monte Carlo: C-H Bond Dissociation ofAcetylene

    Energy Technology Data Exchange (ETDEWEB)

    Domin, D.; Braida, Benoit; Lester Jr., William A.

    2008-05-30

    This study explores the use of breathing orbital valence bond (BOVB) trial wave functions for diffusion Monte Carlo (DMC). The approach is applied to the computation of the carbon-hydrogen (C-H) bond dissociation energy (BDE) of acetylene. DMC with BOVB trial wave functions yields a C-H BDE of 132.4 {+-} 0.9 kcal/mol, which is in excellent accord with the recommended experimental value of 132.8 {+-} 0.7 kcal/mol. These values are to be compared with DMC results obtained with single determinant trial wave functions, using Hartree-Fock orbitals (137.5 {+-} 0.5 kcal/mol) and local spin density (LDA) Kohn-Sham orbitals (135.6 {+-} 0.5 kcal/mol).

  5. A Redetermination of the Dissociation Energy of MgO(+)

    Science.gov (United States)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry

    1994-01-01

    In 1986, we reported a dissociation energy (D(sub 0) of 2.31 eV for the X(sup 2)Pi ground state of MgO(+). This value was determined by computing the dissociation energy to the Mg(2+) + O(-) limit and adjusting the value to the Mg(+) + O limit using the experimental Ionization Potential (IP) of Mg(+) and the Electron Affinity (EA) of O. The success of this method relies on the assumption that there is little covalent contribution to the bonding. The very small (0.04 eV) correlation contribution to the binding energy was taken as corroboration for the validity of this approach. Our earlier theoretical value was estimated to be accurate to at least 0.2 eV. It is in excellent agreement with the subsequent value of 2.30 +/- 0.13 eV determined by Freiser and co-workers from photodissociation experiments. It is also consistent with the upper (less than 3.1 eV) and lower (greater than 1.1 eV) bounds determined by Rowe obtained by studying the reactions of Mg(+) with 03 and NO2. However, it is inconsistent with an upper bound of 1.7 eV reported by Kappes and Staley based on their failure to observe MgO(+) in the reaction of Mg(+) with N2O. The picture became somewhat clouded, however, by the recent guided-ion beam mass spectrometric studies of Dalleska and Armentrout. Their initial analysis of the reaction data for Mg(+) + O2 lead to a bond dissociation energy of 2.92 +/- 0.25 eV, which is considerably larger than the value of 2.47 +/- 0.06 eV deduced from their studies of the Mg(+)+NO2 reaction.

  6. Accurate studies on dissociation energies of diatomic molecules

    Institute of Scientific and Technical Information of China (English)

    SUN; WeiGuo; FAN; QunChao

    2007-01-01

    The molecular dissociation energies of some electronic states of hydride and N2 molecules were studied using a parameter-free analytical formula suggested in this study and the algebraic method (AM) proposed recently. The results show that the accurate AM dissociation energies DeAM agree excellently with experimental dissociation energies Deexpt, and that the dissociation energy of an electronic state such as the 23△g state of 7Li2 whose experimental value is not available can be predicted using the new formula.

  7. Computational Study of Bond Dissociation Enthalpies for Lignin Model Compounds. Substituent Effects in Phenethyl Phenyl Ethers

    Energy Technology Data Exchange (ETDEWEB)

    Beste, Ariana [ORNL; Buchanan III, A C [ORNL

    2009-01-01

    Lignin is an abundant natural resource that is a potential source of valuable chemicals. Improved understanding of the pyrolysis of lignin occurs through the study of model compounds for which phenethyl phenyl ether (PhCH2CH2OPh, PPE) is the simplest example representing the dominant -O-4 ether linkage. The initial step in the thermal decomposition of PPE is the homolytic cleavage of the oxygen-carbon bond. The rate of this key step will depend on the bond dissociation enthalpy, which in turn will depend on the nature and location of relevant substituents. We used modern density functional methods to calculate the oxygen-carbon bond dissociation enthalpies for PPE and several oxygen substituted derivatives. Since carbon-carbon bond cleavage in PPE could be a competitive initial reaction under high temperature pyrolysis conditions, we also calculated substituent effects on these bond dissociation enthalpies. We found that the oxygen-carbon bond dissociation enthalpy is substantially lowered by oxygen substituents situated at the phenyl ring adjacent to the ether oxygen. On the other hand, the carbon-carbon bond dissociation enthalpy shows little variation with different substitution patterns on either phenyl ring.

  8. The bond length and bond energy of gaseous CrW.

    Science.gov (United States)

    Matthew, Daniel J; Oh, Sang Hoon; Sevy, Andrew; Morse, Michael D

    2016-06-07

    Supersonically cooled CrW was studied using resonant two-photon ionization spectroscopy. The vibronically resolved spectrum was recorded over the region 21 100 to 23 400 cm(-1), showing a very large number of bands. Seventeen of these bands, across three different isotopologues, were rotationally resolved and analyzed. All were found to arise from the ground (1)Σ(+) state of the molecule and to terminate on states with Ω' = 0. The average r0 bond length across the three isotopic forms was determined to be 1.8814(4) Å. A predissociation threshold was observed in this dense manifold of vibronic states at 23 127(10) cm(-1), indicating a bond dissociation energy of D0(CrW) = 2.867(1) eV. Using the multiple bonding radius determined for atomic Cr in previous work, the multiple bonding radius for tungsten was calculated to be 1.037 Å. Comparisons are made between CrW and the previously investigated group 6 diatomic metals, Cr2, CrMo, and Mo2, and to previous computational studies of this molecule. It is also found that the accurately known bond dissociation energies of group 5/6 metal diatomics Cr2, V2, CrW, NbCr, VNb, Mo2, and Nb2 display a qualitative linear dependence on the sum of the d-orbital radial expectation values, r; this relationship allows the bond dissociation energies of other molecules of this type to be estimated.

  9. Selectivity of peptide bond dissociation on excitation of a core electron: Effects of a phenyl group

    Science.gov (United States)

    Tsai, Cheng-Cheng; Chen, Jien-Lian; Hu, Wei-Ping; Lin, Yi-Shiue; Lin, Huei-Ru; Lee, Tsai-Yun; Lee, Yuan T.; Ni, Chi-Kung; Liu, Chen-Lin

    2016-09-01

    The selective dissociation of a peptide bond upon excitation of a core electron in acetanilide and N-benzylacetamide was investigated. The total-ion-yield near-edge X-ray absorption fine structure spectra were recorded and compared with the predictions from time-dependent density functional theory. The branching ratios for the dissociation of a peptide bond are observed as 16-34% which is quite significant. This study explores the core-excitation, the X-ray photodissociation pathways, and the theoretical explanation of the NEXAFS spectra of organic molecules containing both a peptide bond and a phenyl group.

  10. Bond dissociation mechanism of ethanol during carbon nanotube synthesis via alcohol catalytic CVD technique: Ab initio molecular dynamics simulation

    Science.gov (United States)

    Oguri, Tomoya; Shimamura, Kohei; Shibuta, Yasushi; Shimojo, Fuyuki; Yamaguchi, Shu

    2014-03-01

    Dissociation of ethanol on a nickel cluster is investigated by ab initio molecular dynamics simulation to reveal the bond dissociation mechanism of carbon source molecules during carbon nanotube synthesis. C-C bonds in only CHxCO fragments are dissociated on the nickel cluster, whereas there is no preferential structure among the fragments for C-O bond dissociation. The dissociation preference is uncorrelated with the bond dissociation energy of corresponding bonds in freestanding molecules but is correlated with the energy difference between fragment molecules before and after dissociation on the nickel surface. Moreover, carbon-chain formation occurs after C-C bond dissociation in a continuous simulation. What determines the chirality of CNTs? What happens at the dissociation stage of carbon source molecules? Regarding the former question, many researchers have pointed out the good epitaxial relationship between a graphite network and a close-packed facet (i.e., fcc(1 1 1) or hcp(0 0 0 1)) of transition metals [17-19]. Therefore, the correlation between the chirality of CNTs and the angle of the step edge on metal (or metal carbide) surfaces has been closely investigated [20-22]. In association with this geometric matching, the epitaxial growth of graphene on Cu(1 1 1) and Ni(1 1 1) surfaces has recently been achieved via CCVD technique [23-25], which is a promising technique for the synthesis of large-area and monolayer graphene.Regarding the latter question, it is empirically known that the yield and quality of CNT products strongly depend on the choice of carbon source molecules and additives. For example, it is well known that the use of ethanol as carbon source molecules yields a large amount of SWNTs without amorphous carbons (called the alcohol CCVD (ACCVD) technique) compared with the CCVD process using hydrocarbons [4]. Moreover, the addition of a small amount of water dramatically enhances the activity and lifetime of the catalytic metal (called the

  11. Force modulating dynamic disorder: A physical model of catch-slip bond transitions in receptor-ligand forced dissociation experiments

    Science.gov (United States)

    Liu, Fei; Ou-Yang, Zhong-Can

    2006-11-01

    Recent experiments found that some adhesive receptor-ligand complexes have counterintuitive catch-slip transition behaviors: the mean lifetimes of these complexes first increase (catch) with initial application of a small external force, and then decrease (slip) when the force is beyond some threshold. In this work we suggest that the forced dissociation of these complexes might be a typical rate process with dynamic disorder. The one-dimensional force modulating Agmon-Hopfield model is used to describe the transitions in the single-bond P-selectin glycoprotein ligand 1-P-selectin forced dissociation experiments, which were respectively performed in the constant force [Marshall , Nature (Landon) 423, 190 (2003)] and the ramping force [Evans , Proc. Natl. Acad. Sci. U.S.A 98, 11281 (2004)] modes. We find that, an external force can not only accelerate the bond dissociation, but also modulate the complex from the lower-energy barrier to the higher one; the catch-slip bond transition can arise from a particular energy barrier shape. The agreement between our calculation and the experimental data is satisfactory.

  12. Zero-Point Energy Constraint for Unimolecular Dissociation Reactions. Giving Trajectories Multiple Chances To Dissociate Correctly.

    Science.gov (United States)

    Paul, Amit K; Hase, William L

    2016-01-28

    A zero-point energy (ZPE) constraint model is proposed for classical trajectory simulations of unimolecular decomposition and applied to CH4* → H + CH3 decomposition. With this model trajectories are not allowed to dissociate unless they have ZPE in the CH3 product. If not, they are returned to the CH4* region of phase space and, if necessary, given additional opportunities to dissociate with ZPE. The lifetime for dissociation of an individual trajectory is the time it takes to dissociate with ZPE in CH3, including multiple possible returns to CH4*. With this ZPE constraint the dissociation of CH4* is exponential in time as expected for intrinsic RRKM dynamics and the resulting rate constant is in good agreement with the harmonic quantum value of RRKM theory. In contrast, a model that discards trajectories without ZPE in the reaction products gives a CH4* → H + CH3 rate constant that agrees with the classical and not quantum RRKM value. The rate constant for the purely classical simulation indicates that anharmonicity may be important and the rate constant from the ZPE constrained classical trajectory simulation may not represent the complete anharmonicity of the RRKM quantum dynamics. The ZPE constraint model proposed here is compared with previous models for restricting ZPE flow in intramolecular dynamics, and connecting product and reactant/product quantum energy levels in chemical dynamics simulations.

  13. Coupling of disulfide bond and distal histidine dissociation in human ferrous cytoglobin regulates ligand binding.

    Science.gov (United States)

    Beckerson, Penny; Reeder, Brandon J; Wilson, Michael T

    2015-02-13

    Earlier kinetics studies on cytoglobin did not assign functional properties to specific structural forms. Here, we used defined monomeric and dimeric forms and cysteine mutants to show that an intramolecular disulfide bond (C38-C83) alters the dissociation rate constant of the intrinsic histidine (H81) (∼1000 fold), thus controlling binding of extrinsic ligands. Through time-resolved spectra we have unequivocally assigned CO binding to hexa- and penta-coordinate forms and have made direct measurement of histidine rebinding following photolysis. We present a model that describes how the cysteine redox state of the monomer controls histidine dissociation rate constants and hence extrinsic ligand binding.

  14. Choice of Bond Dissociation Enthalpies on which to Base the Stabilization Energies of Simple Radicals: DH(R-H)is Preferred because DH(R-Me) is Perturbed by Changes in Chain Branching

    Energy Technology Data Exchange (ETDEWEB)

    Poutsma, Marvin L [ORNL

    2008-01-01

    The relative stabilization energies of radicals, SE(R ), along the simple series methyl/ethyl/i-propyl/t-butyl are known to vary in spread and even direction dependent on which dissociation enthalpies, DH(R-X), they are based on. Using a highly electronegative X is recognized as unwise, but it is not clear whether a choice of X = Me or X = R might not be preferred over the almost universal use of R = H. The enthalpies of isomerization of C4 radical pairs that vary only in the substitution pattern at the radical center but not in carbon skeleton illustrate that R = H is indeed the better choice. Comparisons in the context of recent predictive models for alkane and radical stability indicate that, while relative DH(R-H) values highlight the desired difference in substitution pattern at the radical center, relative DH(R-Me) values are perturbed by differences in skeletal branching or protobranching which are well-known to affect thermochemistry. As a result, SE(R ) values derived from relative DH(R-Me) values are consistently too small. The same pattern is illustrated for prim, sec, and tert allylic and benzylic radicals (larger SE(R )) and for the parent vinyl, phenyl, and ethynyl radicals (negative SE(R )).

  15. A theoretical study on C-COOH homolytic bond dissociation enthalpies.

    Science.gov (United States)

    Shi, Jing; Huang, Xiong-Yi; Wang, Jun-Peng; Li, Run

    2010-06-01

    The knowledge of C-COOH homolytic bond dissociation enthalpies (BDEs) is of great importance in understanding various chemical and biochemical processes involving the decarboxylation reaction. In the present study, the density functional theory (DFT method), B3P86/6-311++G(2df,2p)//B3LYP/6-31+G(d), is found to be reliable to predict the C-COOH BDE of various structurally unrelated carboxylic acids. The mean absolute deviation (MAD) and root-mean-square deviation (rmsd) of this optimal method are equal to 2.0 and 2.5 kcal/mol, respectively. With the authorized theoretical protocol in hand, an extensive C-COOH BDE scale containing over 100 carboxylic acids has been established. The availability of this body of data enabled a detailed investigation of remote substituent effect on four types of carboxylic acids, including para-substituted benzoic acid, beta-substituted cis-propenoic acid, beta-substituted trans-propenoic acid, and substituted propiolic acid. Also with the C-COOH BDE data obtained in this work, an excellent linear relationship has been found between the C-COOH BDE of carboxylic acids and the C-H BDE of their hydrocarbon analogues. After comparing the energy barrier of the Pd-catalyzed decarboxylation reaction (DeltaG(decarboxylation)++) with the related C-COOH BDE, a negative correlation between the DeltaG(decarboxylation)++ and the C-COOH BDE was found.

  16. On the viability of heterolytic peptide N-C(α) bond cleavage in electron capture and transfer dissociation mass spectrometry.

    Science.gov (United States)

    Wodrich, Matthew D; Zhurov, Konstantin O; Corminboeuf, Clémence; Tsybin, Yury O

    2014-03-20

    While frequently employed as an experimental technique, the mechanistic picture surrounding the gas-phase dissociation of peptides carrying multiple positive charges during electron capture and electron transfer dissociation tandem mass spectrometry remains incomplete. Despite this mechanistic uncertainty, most proposals agree that the peptide backbone N-Cα bond located to the C-terminal (right) side of an aminoketyl radical formed in a peptide backbone during the electron capture process is homolytically cleaved. Recently, we introduced the "enol" mechanism, which proposes that a backbone N-Cα bond located to the N-terminal (left) side of an aminoketyl radical is cleaved heterolytically. Here, we further validate this mechanism using replica-exchange molecular dynamics to create unbiased representative sets of low-energy conformers for several model tryptic peptide systems (H-Alax-Lys-OH(2+), x = 3-5). Transition state barrier enthalpies for the cleavage of N-Cα bonds proceeding via the homolytic (right-side) and heterolytic (left-side) pathways, determined by density functional computations, identify the preferred cleavage route for each conformer. These findings support our original hypothesis that heterolytic N-Cα cleavage can exist in a competitive balance with homolytic cleavages, independent of the relative energy of the precursor dication species. Smaller peptide systems see decreased heterolytic N-Cα cleavage probabilities, likely resulting from an insufficient hydrogen-bonding network needed to stabilize and ultimately annihilate the transition state zwitterion. This observation may explain the early dismissal of left-side cleavage pathways based on computational studies employing small model systems.

  17. Theoretical determination of the alkali-metal superoxide bond energies

    Science.gov (United States)

    Partridge, Harry; Bauschlicher, Charles W., Jr.; Sodupe, Mariona; Langhoff, Stephen R.

    1992-01-01

    The bond dissociation energies for the alkali-metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional level. Our computed D0 values are 61.4, 37.2, 40.6, and 38.4 kcal/mol for LiO2, NaO2, KO2, and RbO2, respectively. These values, which are expected to be lower bounds and accurate to 2 kcal/mol, agree well with some of the older flame data, but rule out several recent experimental measurements.

  18. Sequential bond energies and structures of the Cr+·(N2), n =1−4

    Indian Academy of Sciences (India)

    Jamal N Dawoud

    2014-11-01

    DFT calculations, with an effective core potential for the chromium ion and large polarized basis set functions have been used to calculate the sequential bond dissociation energies of the Cr+·(N2) (n = 1—4) complexes. A linear configuration was obtained for the Cr+·N2 and Cr+·(N2)2 complexes with sequential bond dissociation energies of 14.6 and 16.4 kcal mol-1, respectively. For the Cr+·(N2)3 and Cr+·(N2)4 complexes, distorted trigonal pyramidal and tetrahedral geometries were optimized with sequential bond dissociation energies of 6.5 and 5.5 kcal mol-1, respectively. - back-donation in side-on approach of the Cr+·N2 leads to the formation of a tilted structure with the Cr+ ion in central position. The di-ligated complex exhibits the strongest bond dissociation energy among these four Cr+·(N2) (n = 1—4) complexes since it has the largest Cr+—N bond order.

  19. Molecular dissociation in presence of catalysts: Interpreting bond breaking as a quantum dynamical phase transition

    CERN Document Server

    Ruderman, A; Santos, E; Pastawski, H M

    2015-01-01

    In this work we show that the molecular chemical bond formation and dissociation in presence of the d-band of a metal catalyst can be described as a Quantum Dynamical Phase Transition (QDPT). This agree with DFT calculations that predict sudden jumps in some observables as the molecule breaks. According to our model this phenomenon emerges because the catalyst provides for a non- Hermitian Hamiltonian. We show that when the molecule approaches the surface, as occurs in the Heyrovsky reaction of H 2, the bonding H 2 orbital has a smooth crossover into a bonding molecular orbital built with the closest H orbital and the surface metal d-states. The same occurs for the antibonding state. Meanwhile, two resonances appear within the continuous spectrum of the d- band which are associated with bonding and antibonding orbitals between the furthest H atom and the d-states at the second metallic layer. These move towards the band center where they collapse into a pure metallic resonance and an almost isolated H orbital...

  20. Accurate studies on the full vibrational energy spectra and molecular dissociation energies for some electronic states of N2 molecule

    Institute of Scientific and Technical Information of China (English)

    REN; Weiyi; SUN; Weiguo; HOU; Shilin; FENG; Hao

    2005-01-01

    It is usually very difficult to directly obtain molecular dissociation energy De and all accurate high-lying vibrational energies for most diatomic electronic states using modern experimental techniques or quantum theories, and it is also very difficult to give accurate analytical expression for diatomic molecular dissociation energy. This study proposes a new analytical formula for obtaining accurate molecular dissociation energy based on the LeRoy and Bernstein's energy expression in dissociation limit. A set of full vibrational energy spectra for some electronic states of N2 molecule are studied using the algebraic method (AM) suggested recently, and the corresponding accurate molecular dissociation energies are evaluated using the proposed new formula and high-lying AM vibrational energies. The results show that the AM spectra and the new theoretical dissociation energies agree excellently with experimental data, and thereby providing a new physical approach to generating accurate dissociation energies for electronic states of diatomic molecules.

  1. Bond-Energy and Surface-Energy Calculations in Metals

    Science.gov (United States)

    Eberhart, James G.; Horner, Steve

    2010-01-01

    A simple technique appropriate for introductory materials science courses is outlined for the calculation of bond energies in metals from lattice energies. The approach is applied to body-centered cubic (bcc), face-centered cubic (fcc), and hexagonal-closest-packed (hcp) metals. The strength of these bonds is tabulated for a variety metals and is…

  2. Collision Induced Dissociation and Energy Transfer in Molecular Hydroge

    Science.gov (United States)

    Mandy, Margot E.

    2006-06-01

    Molecular hydrogen is a significant constituent in giant molecular clouds in the interstellar medium. Shocks in these clouds are associated with star formation. The cooling of the shocks is governed by competition of collisional energy transfer and dissociation with radiative cooling by quadrupole emission. Thus a detailed understanding of collisional behaviour of molecular hydrogen is needed. Work in this group has examined energy transfer and dissociation in molecular energy transfer as the result of collisions with H, D, He, and H2. Using quasiclassical trajectories and chemically accurate ab initio potentials state-to-state rate coefficients have been determined. The uncertainties of the cross sections are propagated rigourously to give uncertainties of the rate coefficients and the rate coefficients are parameterized as a function of temperature. Comparisons with quantum calculations are discussed and the proposed website is described.This work was supported by a grant from the Natural Sciences and Engineering Research Council of Canada. The calculations were carried out using the high performance computing facility jointly supported by the Canadian Foundation for Innovation, the British Columbia Knowledge Development Fund, and Silicon Graphics at the University of Northern British Columbia.

  3. Synthesis, XRD crystal structure, spectroscopic characterization (FT-IR, 1H and 13C NMR), DFT studies, chemical reactivity and bond dissociation energy studies using molecular dynamics simulations and evaluation of antimicrobial and antioxidant activities of a novel chalcone derivative, (E)-1-(4-bromophenyl)-3-(4-iodophenyl)prop-2-en-1-one

    Science.gov (United States)

    Zainuri, D. Alwani; Arshad, Suhana; Khalib, N. Che; Razak, I. Abdul; Pillai, Renjith Raveendran; Sulaiman, S. Fariza; Hashim, N. Shafiqah; Ooi, K. Leong; Armaković, Stevan; Armaković, Sanja J.; Panicker, C. Yohannan; Van Alsenoy, C.

    2017-01-01

    In the present study, the title compound named as (E)-1-(4-bromophenyl)-3-(4-iodophenyl)prop-2-en-1-one was synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system with P21/c space group with the unit cell parameters of a = 16.147 (2) Å, b = 14.270 (2) Å, c = 5.9058 (9) Å, β = 92.577 (3)° and Z = 4. The molecular geometry obtained from X-Ray structure determination was optimized by Density Functional Theory (DFT) using B3LYP/6-31G+(d, p)/Lanl2dz(f) method in the ground state. The IR spectrum was recorded and interpreted in details with the aid of Density Functional Theory (DFT) calculations and Potential Energy Distribution (PED) analysis. In order to investigate local reactivity properties of the title molecule, we have conducted DFT calculations of average local ionization energy surface and Fukui functions which were mapped to the electron density surface. In order to predict the open air stability and possible degradation properties, within DFT approach, we have also calculated bond dissociation energies. 1H and 13C NMR spectra were recorded and chemical shifts were calculated theoretically and compared with the experimental values. In addition, in vitro antimicrobial results show that the title compound has great potential of antibacterial activity against Staphylococcus aureus, Staphylococcus epidermidis and Micrococcus luteus bacteria and antifungal activity against Candida albicans in comparison to some reported chalcone derivatives. Antioxidant studies revealed the highest metal chelating activity of this compound.

  4. A DFT Study of R-X Bond Dissociation Enthalpies of Relevance to the Initiation Process of Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Gillies, Malcolm Bjørn; Matyjaszewski, Krzysztof; Norrby, Per-Ola;

    2003-01-01

    DFT calculations at the B3P86/6-31G** level have been carried out to derive the bond dissociation energies (BDE) and free energies for a number of R-X systems (X ) Cl, Br, I, N3, and S2-CNMe2) that have been or can potentially be used as initiators for atom transfer radical polymerization (ATRP...... with the equilibrium constants that have been determined from ATRP polymerization rates and from model studies of activation-deactivation-termination processes in the absence of monomer. These comparisons reveal the effectiveness of the DFT-computed BDEs for predicting polymerization rates for new monomers in ATRP...

  5. Mechanisms of Peptide Fragmentation from Time-and Energy-Resolved Surface-Induced Dissociation Studies: Dissociation of Angiotensin Analogs

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, Julia; Bailey, Thomas H.; Futrell, Jean H.

    2006-03-01

    Energetics and mechanism of dissociation of singly protonated angiotensin III (RVYIHPF) and its analogs RVYIFPF, RVYIYPF, RVYIHAF, and RVYIHDF was studied using surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for studying ion activation by collisions with surfaces. The energetics and dynamics of peptide fragmentation were deduced by modeling the time- and energy-resolved survival curves for each precursor ion using an RRKM based approach developed in our laboratory. Fragmentation mechanisms were inferred from comparison of time- and energy-resolved fragmentation efficiency curves (TFECs) of different fragment ions followed by RRKM modeling of dissociation of angiotensin III into six major families of fragment ions. Detailed modeling demonstrated that dissociation of these peptides is dominated by loss of ammonia from the precursor ion and characterized by a high energy barrier of 1.6 eV. Loss of NH3 and subsequent rearrangement of the MH-NH3 ion results in proton mobilization and release of ca. 30 kcal/mol into internal excitation of the MH-NH3 ion. The resulting highly excited ion accesses a variety of non-specific dissociation pathways with very high rate constants. Fast fragmentation of excited MH-NH3 ion forms a variety of abundant bn-NH3 and an-NH3 fragment ions. Abundant XH and HX internal fragments are also formed, reflecting the stability of histidine-containing diketopiperazine structures.

  6. Mechanisms of peptide fragmentation from time- and energy-resolved surface-induced dissociation studies: Dissociation of angiotensin analogs

    Science.gov (United States)

    Laskin, Julia; Bailey, Thomas H.; Futrell, Jean H.

    2006-03-01

    Energetics and mechanism of dissociation of singly protonated angiotensin III (RVYIHPF) and its analogs RVYIFPF, RVYIYPF, RVYIHAF and RVYIHDF was studied using surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for studying ion activation by collisions with surfaces. The energetics and dynamics of peptide fragmentation were deduced by modeling the time- and energy-resolved survival curves for each precursor ion using an RRKM-based approach developed in our laboratory. Fragmentation mechanisms were inferred from comparison of time- and energy-resolved fragmentation efficiency curves (TFECs) of different fragment ions followed by RRKM modeling of dissociation of angiotensin III into six major families of fragment ions. Detailed modeling demonstrated that dissociation of these peptides is dominated by loss of ammonia from the precursor ion and characterized by a high-energy barrier of 1.6 eV. Loss of NH3 and subsequent rearrangement of the MH+-NH3 ion results in proton mobilization and release of ca. 30 kcal/mol into internal excitation of the MH+-NH3 ion. The resulting highly excited ion accesses a variety of non-specific dissociation pathways with very high rate constants. Fast fragmentation of excited MH+-NH3 ion forms a variety of abundant bn-NH3 and an-NH3 fragment ions. Abundant XH and HX internal fragments are also formed, reflecting the stability of histidine-containing diketopiperazine structures.

  7. Resonant structure of low-energy H3+ dissociative recombination

    CERN Document Server

    Petrignani, Annemieke; Berg, Max H; Bing, Dennis; Buhr, Henrik; Greene, Chris H; Grieser, Manfred; Hoffmann, Jens; Jordon-Thaden, Brandon; Kokoouline, Viatcheslav; Krantz, Claude; Kreckel, Holger; Mendes, Mario B; Novotny, Oldrich; Novotny, Steffen; Orlov, Dmitry A; Repnow, Roland; Sorg, Tobias; Stuetzel, Julia; Wolf, Andreas

    2010-01-01

    New high-resolution dissociative recombination rate coefficients of rotationally cool and hot H3+ in the vibrational ground state have been measured with a 22-pole trap setup and a Penning ion source, respectively, at the ion storage ring TSR. The experimental results are compared with theoretical calculations to explore the dependence of the rate coefficient on ion temperature and to study the contributions of different symmetries to probe the rich predicted resonance spectrum. The break-up energy was investigated by fragment imaging to derive internal temperatures of the stored parent ions under differing experimental conditions. A systematic experimental assessment of heating effects is performed which, together with a survey of other recent storage-ring data, suggests that the present rotationally cool rate-coefficient measurement was performed at 380^{+50}_{-130} K and that this is the lowest rotational temperature so far realized in storage-ring rate-coefficient measurements on H3+. This partially suppo...

  8. The thermodynamics and kinetics of phosphoester bond formation, use, and dissociation in biology, with the example of polyphosphate in platelet activation, trasience, and mineralization.

    Science.gov (United States)

    Omelon, S. J.

    2014-12-01

    Mitochondria condense orthophosphates (Pi), forming phosphoester bonds for ATP production that is important to life. This represents an exchange of energy from dissociated carbohydrate bonds to phosophoester bonds. These bonds are available to phosphorylate organic compounds or hydrolyze to Pi, driving many biochemical processes. The benthic bacteria T. namibiensis 1 and Beggiatoa 2 condense Pi into phosphate polymers in oxygenated environments. These polyphosphates (polyPs) are stored until the environment becomes anoxic, when these bacteria retrieve the energy from polyP dissociation into Pi3. Dissociated Pi is released outside of the bacteria, where it precipitates as apatite.The Gibbs free energy of polyP phosphoester bond hydrolysis is negative, however, the kinetics are slow4. Diatoms contain a polyP pool that is stable until after death, after which the polyPs hydrolyze and form apatite5. The roles of polyP in eukaryotic organism biochemistry continue to be discovered. PolyPs have a range of biochemical roles, such as bioavailable P-storage, stress adaptation, and blood clotting6. PolyP-containing granules are released from anuclear platelets to activate factor V7 and factor XII in the blood clotting process due to their polyanionic charge8. Platelets have a lifespan of approximately 8 days, after which they undergo apoptosis9. Data will be presented that demonstrate the bioactive, thermodynamically unstable polyP pool within older platelets in vitro can spontaneously hydrolyze and form phosphate minerals. This process is likely avoided by platelet digestion in the spleen and liver, possibly recycling platelet polyPs with their phosphoester bond energy for other biochemical roles. 1 Schulz HN et al. Science (2005) 307: 416-4182 Brüchert V et al. Geochim Cosmochim Acta (2003) 67: 4505-45183 Goldhammer T et al. Nat Geosci (2010) 3: 557-5614 de Jager H-J et al. J Phys Chem A (1988) 102: 2838-28415 Diaz, J et al. Science (2008) 320: 652-6556 Mason KD et al

  9. Bond Energies in Models of the Schrock Metathesis Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Vasiliu, Monica; Li, Shenggang; Arduengo, Anthony J.; Dixon, David A.

    2011-06-23

    Heats of formation, adiabatic and diabatic bond dissociation energies (BDEs) of the model Schrock-type metal complexes M(NH)(CRR)(OH)₂ (M = Cr, Mo, W; CRR = CH₂, CHF, CF₂) and MO₂(OH)₂ compounds, and Brønsted acidities and fluoride affinities for the M(NH)(CH₂)(OH) ₂ transition metal complexes are predicted using high level CCSD(T) calculations. The metallacycle intermediates formed by reaction of C₂H4 with M(NH)-(CH₂)(OH)2 and MO₂(OH)₂ are investigated at the same level of theory. Additional corrections were added to the complete basis set limit to obtain near chemical accuracy ((1 kcal/mol). A comparison between adiabatic and diabatic BDEs is made and provides an explanation of trends in the BDEs. Electronegative groups bonded on the carbenic carbon lead to less stable Schrock-type complexes as the adiabatic BDEs ofMdCF₂ andMdCHF bonds are much lower than theMdCH₂ bonds. The Cr compounds have smaller BDEs than theWorMo complexes and should be less stable. Different M(NH)(OH)₂(C₃H₆) and MO(OH)₂(OC₂H4) metallacycle intermediates are investigated, and the lowest-energy metallacycles have a square pyramidal geometry. The results show that consideration of the singlet_triplet splitting in the carbene in the initial catalyst as well as in the metal product formed by the retro [2+2] cycloaddition is a critical component in the design of an effective olefin metathesis catalyst in terms of the parent catalyst and the groups being transferred.

  10. The binding energy and bonding in dialane.

    Science.gov (United States)

    Goebbert, Daniel J; Hernandez, Heriberto; Francisco, Joseph S; Wenthold, Paul G

    2005-08-24

    The binding energy of dialane, Al2H6, has been measured using mass spectrometric techniques to be 33 +/- 5 kcal/mol. This represents the first measurement of the thermochemical properties of dialane, which has only recently been observed in low-temperature matricies. High-level quantum mechanical calculations give a binding energy in agreement with the measured value. Experimental and quantum mechanical calculations show that dialane is chemically similar to diborane, B2H6, even though the bonding for these two systems shows significant differences.

  11. Dissociation constants of weak acids from ab initio molecular dynamics using metadynamics: influence of the inductive effect and hydrogen bonding on pKa values.

    Science.gov (United States)

    Tummanapelli, Anil Kumar; Vasudevan, Sukumaran

    2014-11-26

    The theoretical estimation of the dissociation constant, or pKa, of weak acids continues to be a challenging field. Here, we show that ab initio Car-Parrinello molecular dynamics simulations in conjunction with metadynamics calculations of the free-energy profile of the dissociation reaction provide reasonable estimates of the pKa value. Water molecules, sufficient to complete the three hydration shells surrounding the acid molecule, were included explicitly in the computation procedure. The free-energy profiles exhibit two distinct minima corresponding to the dissociated and neutral states of the acid, and the difference in their values provides the estimate for pKa. We show for a series of organic acids that CPMD simulations in conjunction with metadynamics can provide reasonable estimates of pKa values. The acids investigated were aliphatic carboxylic acids, chlorine-substituted carboxylic acids, cis- and trans-butenedioic acid, and the isomers of hydroxybenzoic acid. These systems were chosen to highlight that the procedure could correctly account for the influence of the inductive effect as well as hydrogen bonding on pKa values of weak organic acids. In both situations, the CPMD metadynamics procedure faithfully reproduces the experimentally observed trend and the magnitudes of the pKa values.

  12. Strength of hydrogen bond network takes crucial roles in the dissociation process of inhibitors from the HIV-1 protease binding pocket.

    Directory of Open Access Journals (Sweden)

    Dechang Li

    Full Text Available To understand the underlying mechanisms of significant differences in dissociation rate constant among different inhibitors for HIV-1 protease, we performed steered molecular dynamics (SMD simulations to analyze the entire dissociation processes of inhibitors from the binding pocket of protease at atomistic details. We found that the strength of hydrogen bond network between inhibitor and the protease takes crucial roles in the dissociation process. We showed that the hydrogen bond network in the cyclic urea inhibitors AHA001/XK263 is less stable than that of the approved inhibitor ABT538 because of their large differences in the structures of the networks. In the cyclic urea inhibitor bound complex, the hydrogen bonds often distribute at the flap tips and the active site. In contrast, there are additional accessorial hydrogen bonds formed at the lateral sides of the flaps and the active site in the ABT538 bound complex, which take crucial roles in stabilizing the hydrogen bond network. In addition, the water molecule W301 also plays important roles in stabilizing the hydrogen bond network through its flexible movement by acting as a collision buffer and helping the rebinding of hydrogen bonds at the flap tips. Because of its high stability, the hydrogen bond network of ABT538 complex can work together with the hydrophobic clusters to resist the dissociation, resulting in much lower dissociation rate constant than those of cyclic urea inhibitor complexes. This study may provide useful guidelines for design of novel potent inhibitors with optimized interactions.

  13. Strength of hydrogen bond network takes crucial roles in the dissociation process of inhibitors from the HIV-1 protease binding pocket.

    Science.gov (United States)

    Li, Dechang; Ji, Baohua; Hwang, Keh-Chih; Huang, Yonggang

    2011-01-01

    To understand the underlying mechanisms of significant differences in dissociation rate constant among different inhibitors for HIV-1 protease, we performed steered molecular dynamics (SMD) simulations to analyze the entire dissociation processes of inhibitors from the binding pocket of protease at atomistic details. We found that the strength of hydrogen bond network between inhibitor and the protease takes crucial roles in the dissociation process. We showed that the hydrogen bond network in the cyclic urea inhibitors AHA001/XK263 is less stable than that of the approved inhibitor ABT538 because of their large differences in the structures of the networks. In the cyclic urea inhibitor bound complex, the hydrogen bonds often distribute at the flap tips and the active site. In contrast, there are additional accessorial hydrogen bonds formed at the lateral sides of the flaps and the active site in the ABT538 bound complex, which take crucial roles in stabilizing the hydrogen bond network. In addition, the water molecule W301 also plays important roles in stabilizing the hydrogen bond network through its flexible movement by acting as a collision buffer and helping the rebinding of hydrogen bonds at the flap tips. Because of its high stability, the hydrogen bond network of ABT538 complex can work together with the hydrophobic clusters to resist the dissociation, resulting in much lower dissociation rate constant than those of cyclic urea inhibitor complexes. This study may provide useful guidelines for design of novel potent inhibitors with optimized interactions.

  14. Dissociation of CO induced by He2+ ions : I. Fragmentation and kinetic energy release spectra

    NARCIS (Netherlands)

    Bliek, FW; de Jong, MC; Hoekstra, R; Morgenstern, R

    1997-01-01

    The dissociation of COq+ ions (q less than or equal to 3) produced in collisions of keV amu(-1) He2+ ions with CO has been studied by time-of-flight measurements. Both singles and coincidence time-of-flight techniques have been used to determine the kinetic energy release of the dissociating CO mole

  15. Precision measurements of ionization and dissociation energies by extrapolation of Rydberg series: from H2 to larger molecules.

    Science.gov (United States)

    Sprecher, D; Beyer, M; Merkt, F

    2013-01-01

    Recent experiments are reviewed which have led to the determination of the ionization and dissociation energies of molecular hydrogen with a precision of 0.0007 cm(-)1 (8 mJ/mol or 20 MHz) using a procedure based on high-resolution spectroscopic measurements of high Rydberg states and the extrapolation of the Rydberg series to the ionization thresholds. Molecular hydrogen, with only two protons and two electrons, is the simplest molecule with which all aspects of a chemical bond, including electron correlation effects, can be studied. Highly precise values of its ionization and dissociation energies provide stringent tests of the precision of molecular quantum mechanics and of quantum-electrodynamics calculations in molecules. The comparison of experimental and theoretical values for these quantities enable one to quantify the contributions to a chemical bond that are neglected when making the Born-Oppenheimer approximation, i.e. adiabatic, nonadiabatic, relativistic, and radiative corrections. Ionization energies of a broad range of molecules can now be determined experimentally with high accuracy (i.e. about 0.01 cm(-1)). Calculations at similar accuracies are extremely challenging for systems containing more than two electrons. The combination of precision measurements of molecular ionization energies with highly accurateab initio calculations has the potential to provide, in future, fully reliable sets of thermochemical quantities for gas-phase reactions.

  16. Electron-nuclear energy sharing in above-threshold multiphoton dissociative ionization of H2.

    Science.gov (United States)

    Wu, J; Kunitski, M; Pitzer, M; Trinter, F; Schmidt, L Ph H; Jahnke, T; Magrakvelidze, M; Madsen, C B; Madsen, L B; Thumm, U; Dörner, R

    2013-07-12

    We report experimental observation of the energy sharing between electron and nuclei in above-threshold multiphoton dissociative ionization of H2 by strong laser fields. The absorbed photon energy is shared between the ejected electron and nuclei in a correlated fashion, resulting in multiple diagonal lines in their joint energy spectrum governed by the energy conservation of all fragment particles.

  17. Electron-Nuclear Energy Sharing in Above-Threshold Multiphoton Dissociative Ionization of H2

    DEFF Research Database (Denmark)

    Wu, J.; Kunitski, M.; Pitzer, M.

    2013-01-01

    We report experimental observation of the energy sharing between electron and nuclei in above-threshold multiphoton dissociative ionization of H2 by strong laser fields. The absorbed photon energy is shared between the ejected electron and nuclei in a correlated fashion, resulting in multiple...... diagonal lines in their joint energy spectrum governed by the energy conservation of all fragment particles....

  18. Distinct dissociation kinetics between ion pairs: Solvent-coordinate free-energy landscape analysis

    Science.gov (United States)

    Yonetani, Yoshiteru

    2015-07-01

    Different ion pairs exhibit different dissociation kinetics; however, while the nature of this process is vital for understanding various molecular systems, the underlying mechanism remains unclear. In this study, to examine the origin of different kinetic rate constants for this process, molecular dynamics simulations were conducted for LiCl, NaCl, KCl, and CsCl in water. The results showed substantial differences in dissociation rate constant, following the trend kLiCl constants arose predominantly from the variation in solvent-state distribution between the ion pairs. The formation of a water-bridging configuration, in which the water molecule binds to an anion and a cation simultaneously, was identified as a key step in this process: water-bridge formation lowers the related dissociation free-energy barrier, thereby increasing the probability of ion-pair dissociation. Consequently, a higher probability of water-bridge formation leads to a higher ion-pair dissociation rate.

  19. Accurate studies of dissociation energies and vibrational energies on alkali metals

    Institute of Scientific and Technical Information of China (English)

    Liu Xiu-Ying; Sun Wei-Guo; Fan Qun-Chao

    2008-01-01

    This paper studies full vibrational spectra {Ev} and molecular dissociation energies De by using conventional least-squares (LS) fitting and an algebraic method (AM) proposed recently for 10 diatomic electronic states of 7Li2, Na2, NaK and NaLi molecules based on some known experimental vibrational energies in a subset [Eexptv] respectively. Studies show that: (1) although both the full AM spectrum {EAMv} and the LS spectrum {ELSv} can reproduce the known experimental energies in [Eexptv], the {EAMv} is superior to the {Els} in that the high-lying AM vibrational energies which may not be available experimentally have better or much better accuracy than those LS counterparts in {ELSv}, and so is the AM dissociation energy DAMe; (2) the main source of the errors in the data obtained by using the LS fitting is that the fitting which is just a pure mathematical process does not use any physical criteria that must be satisfied by the full vibrational spectrum, while the AM method does. This study suggests that when fitting or solving a physical equation using a set of source data, it is important not only to apply a proper mathematical tool, but also to use correct physical criteria which measure the physical properties of the data, kick out those data having bigger errors, and impose conditional convergence on the numerical process.

  20. Accurate studies of dissociation energies and vibrational energies on alkali metals

    Science.gov (United States)

    Liu, Xiu-Ying; Sun, Wei-Guo; Fan, Qun-Chao

    2008-06-01

    This paper studies full vibrational spectra {Ev} and molecular dissociation energies De by using conventional least-squares (LS) fitting and an algebraic method (AM) proposed recently for 10 diatomic electronic states of 7Li2, Na2, NaK and NaLi molecules based on some known experimental vibrational energies in a subset [Evexpt] respectively. Studies show that: (1) although both the full AM spectrum {EvAM} and the LS spectrum {EvLS} can reproduce the known experimental energies in [Evexpt], the {EvAM} is superior to the {EvLS} in that the high-lying AM vibrational energies which may not be available experimentally have better or much better accuracy than those LS counterparts in {EvLS}, and so is the AM dissociation energy DeAM; (2) the main source of the errors in the data obtained by using the LS fitting is that the fitting which is just a pure mathematical process does not use any physical criteria that must be satisfied by the full vibrational spectrum, while the AM method does. This study suggests that when fitting or solving a physical equation using a set of source data, it is important not only to apply a proper mathematical tool, but also to use correct physical criteria which measure the physical properties of the data, kick out those data having bigger errors, and impose conditional convergence on the numerical process.

  1. Direct molecular simulation of nitrogen dissociation based on an ab initio potential energy surface

    Energy Technology Data Exchange (ETDEWEB)

    Valentini, Paolo, E-mail: vale0142@umn.edu; Schwartzentruber, Thomas E., E-mail: schwart@aem.umn.edu; Bender, Jason D., E-mail: jbender73@gmail.com; Nompelis, Ioannis, E-mail: nompelis@umn.edu; Candler, Graham V., E-mail: candler@umn.edu [Department of Aerospace Engineering and Mechanics, College of Science and Engineering, University of Minnesota, Minneapolis, Minnesota 55455 (United States)

    2015-08-15

    The direct molecular simulation (DMS) approach is used to predict the internal energy relaxation and dissociation dynamics of high-temperature nitrogen. An ab initio potential energy surface (PES) is used to calculate the dynamics of two interacting nitrogen molecules by providing forces between the four atoms. In the near-equilibrium limit, it is shown that DMS reproduces the results obtained from well-established quasiclassical trajectory (QCT) analysis, verifying the validity of the approach. DMS is used to predict the vibrational relaxation time constant for N{sub 2}–N{sub 2} collisions and its temperature dependence, which are in close agreement with existing experiments and theory. Using both QCT and DMS with the same PES, we find that dissociation significantly depletes the upper vibrational energy levels. As a result, across a wide temperature range, the dissociation rate is found to be approximately 4–5 times lower compared to the rates computed using QCT with Boltzmann energy distributions. DMS calculations predict a quasi-steady-state distribution of rotational and vibrational energies in which the rate of depletion of high-energy states due to dissociation is balanced by their rate of repopulation due to collisional processes. The DMS approach simulates the evolution of internal energy distributions and their coupling to dissociation without the need to precompute rates or cross sections for all possible energy transitions. These benchmark results could be used to develop new computational fluid dynamics models for high-enthalpy flow applications.

  2. Accurate bond energies of biodiesel methyl esters from multireference averaged coupled-pair functional calculations.

    Science.gov (United States)

    Oyeyemi, Victor B; Keith, John A; Carter, Emily A

    2014-09-04

    Accurate bond dissociation energies (BDEs) are important for characterizing combustion chemistry, particularly the initial stages of pyrolysis. Here we contribute to evaluating the thermochemistry of biodiesel methyl ester molecules using ab initio BDEs derived from a multireference averaged coupled-pair functional (MRACPF2)-based scheme. Having previously validated this approach for hydrocarbons and a variety of oxygenates, herein we provide further validation for bonds within carboxylic acids and methyl esters, finding our scheme predicts BDEs within chemical accuracy (i.e., within 1 kcal/mol) for these molecules. Insights into BDE trends with ester size are then analyzed for methyl formate through methyl crotonate. We find that the carbonyl group in the ester moiety has only a local effect on BDEs. C═C double bonds in ester alkyl chains are found to increase the strengths of bonds adjacent to the double bond. An important exception are bonds beta to C═C or C═O bonds, which produce allylic-like radicals upon dissociation. The observed trends arise from different degrees of geometric relaxation and resonance stabilization in the radicals produced. We also compute BDEs in various small alkanes and alkenes as models for the long hydrocarbon chain of actual biodiesel methyl esters. We again show that allylic bonds in the alkenes are much weaker than those in the small methyl esters, indicating that hydrogen abstractions are more likely at the allylic site and even more likely at bis-allylic sites of alkyl chains due to more electrons involved in π-resonance in the latter. Lastly, we use the BDEs in small surrogates to estimate heretofore unknown BDEs in large methyl esters of biodiesel fuels.

  3. PM6 study of free radical scavenging mechanisms of flavonoids: why does O-H bond dissociation enthalpy effectively represent free radical scavenging activity?

    Science.gov (United States)

    Amić, Dragan; Stepanić, Višnja; Lučić, Bono; Marković, Zoran; Dimitrić Marković, Jasmina M

    2013-06-01

    It is well known that the bond dissociation enthalpy (BDE) of the O-H group is related to the hydrogen atom transfer (HAT) mechanism of free radical scavenging that is preferred in gas-phase and non-polar solvents. The present work shows that the BDE may also be related to radical scavenging processes taking place in polar solvents, i.e., single electron transfer followed by proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET). This is so because the total energy requirements related to the SET-PT [sum of the ionization potential (IP) and proton dissociation enthalpy (PDE)] and the SPLET [sum of the proton affinity (PA) and electron transfer enthalpy (ETE)] are perfectly correlated with the BDE. This could explain why the published data for polyphenolic antioxidant activity measured by various assays are better correlated with the BDE than with other reaction enthalpies involved in radical scavenging mechanisms, i.e., the IP, PDE, PA and ETE. The BDE is fairly well able to rank flavonoids as antioxidants in any medium, but to conclude which radical scavenging mechanism represents the most probable reaction pathway from the thermodynamic point of view, the IP and PA (ETE) should also be considered. This is exemplified in the case of the radical scavenging activity of 25 flavonoids.

  4. Elucidation of hydroxyl groups-antioxidant relationship in mono- and dihydroxyflavones based on O-H bond dissociation enthalpies.

    Science.gov (United States)

    Treesuwan, Witcha; Suramitr, Songwut; Hannongbua, Supa

    2015-06-01

    Radical scavenging potential is the key to anti-oxidation of hydroxyflavones which generally found in fruits and vegetables. The objective of this work was to investigate the influence of hydroxyl group on the O-H bond dissociation enthalpies (BDE) from a series of mono- and dihydroxyflavones. Calculation at the B3LYP/6-31G(d,p) level reveals the important roles of an additional one hydroxyl group to boost the BDE of hydroxyflavones that were a stabilization of the generated radicals through attractive H-bond interactions, an ortho- and para-dihydroxyl effect, and a presence of the 3-OH in dihydroxyflavones. On the other hand, the meta-dihydroxyl effect and range-hydroxyl effect especially associated with the either 5-OH or 8-OH promoted greater BDE. Results did not only confirm that dihydroxyflavones had lower BDE than monohydroxyflavones but also suggest the selective potent hydroxyflavone molecules that are the 6'-hydroxyflavone (for monohydroxyflavone) and the 5',6'-, 7,8- and 3',4'-dihydroxyflavone which the corresponding radical preferable generated at C6'-O•, C8-O• and C4'-O•, respectively. Electron distribution was limited only over the two connected rings of hydroxyflavones while the expansion distribution into C-ring could be enhanced if the radical was formed especially for the 2',3'- and 5',6'dihydroxyflavone radicals. The delocalized bonds were strengthened after radical was generated. However the 5-O• in 5,6-dihydroxyflavone and the 3-O• in 3,6'-dihydroxyflavone increased the bond order at C4-O11 which might interrupt the conjugated delocalized bonds at the keto group.

  5. Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide

    Science.gov (United States)

    Scott, Carl D.; Smalley, Richard E.

    2003-01-01

    The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

  6. Dynamical potential approach to dissociation of H-C bond in HCO highly excited vibration

    Institute of Scientific and Technical Information of China (English)

    Fang Chao; Wu Guo-Zhen

    2009-01-01

    The highly excited vibrational levels of HCO in the electronic ground state, X1A', are employed to determine the coefficients of an algebraic Hamiltonian, by which the dynamical potential is derived and shown to be very useful for interpreting thc intramolecular vibrational relaxation (IVR) which operates via the HCO bending motion. The IVR inhibits the dissociation of H atom and enhances the stochastic degree of dynamical character. This approach is from a global viewpoint on a series of levels classified by the polyad number which is a constant of motion in a certain dynamical domain. In this way, the seemingly complicated level structure shows very regular picture, dynamically.

  7. Methanol Oxidative Dehydrogenation on Oxide Catalysts: Molecular and Dissociative Routes and Hydrogen Addition Energies as Descriptors of Reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Deshlahra, Prashant; Iglesia, Enrique

    2014-11-13

    The oxidative dehydrogenation (ODH) of alkanols on oxide catalysts is generally described as involving H-abstraction from alkoxy species formed via O–H dissociation. Kinetic and isotopic data cannot discern between such routes and those involving kinetically-relevant H-abstraction from undissociated alkanols. Here, we combine such experiments with theoretical estimates of activation energies and entropies to show that the latter molecular routes prevail over dissociative routes for methanol reactions on polyoxometalate (POM) clusters at all practical reaction temperatures. The stability of the late transition states that mediate H-abstraction depend predominantly on the stability of the O–H bond formed, making H-addition energies (HAE) accurate and single-valued descriptors of reactivity. Density functional theory-derived activation energies depend linearly on HAE values at each O-atom location on clusters with a range of composition (H3PMo12, H4SiMo12, H3PW12, H4PV1Mo11, and H4PV1W11); both barriers and HAE values reflect the lowest unoccupied molecular orbital energy of metal centers that accept the electron and the protonation energy of O-atoms that accept the proton involved in the H-atom transfer. Bridging O-atoms form O–H bonds that are stronger than those of terminal atoms and therefore exhibit more negative HAE values and higher ODH reactivity on all POM clusters. For each cluster composition, ODH turnover rates reflect the reactivity-averaged HAE of all accessible O-atoms, which can be evaluated for each cluster composition to provide a rigorous and accurate predictor of ODH reactivity for catalysts with known structure. These relations together with oxidation reactivity measurements can then be used to estimate HAE values and to infer plausible structures for catalysts with uncertain active site structures.

  8. Free energy calculations on Transthyretin dissociation and ligand binding from Molecular Dynamics Simulations

    DEFF Research Database (Denmark)

    Sørensen, Jesper; Hamelberg, Donald; McCammon, J. Andrew

    experimental results have helped to explain this aberrant behavior of TTR, however, structural insights of the amyloidgenic process are still lacking. Therefore, we have used all-atom molecular dynamics simulation and free energy calculations to study the initial phase of this process. We have calculated...... the free energy changes of the initial tetramer dissociation under different conditions and in the presence of thyroxine....

  9. Mechanically enforced bond dissociation reports synergistic influence of Mn2+ and Mg2+ on the interaction between integrin α7β1 and invasin

    DEFF Research Database (Denmark)

    Ligezowska, Agnieszka; Boye, Kristian; Eble, Johannes A.;

    2011-01-01

    sites overrides the increase in binding strength of individual beads. We show that this is due to a very strong dependence of bond affinity on divalent ions. Our study illustrates the importance of divalent ions for the regulation of force transmission by integrin ligand bonds on the molecular level......Integrins require the divalent ions magnesium and manganese for ligand recognition. Here we mechanically enforced bond dissociation to explore the influence of these ions on the mechanical strength of the specific bond between α7β1 integrin and its pathologically relevant ligand invasin. Upon...

  10. Dissociative scattering of hyperthermal energy CF3+ ions from modified surfaces.

    Science.gov (United States)

    Rezayat, Talayeh; Shukla, Anil

    2007-02-28

    Dissociative scattering of CF3+ ions in collision with a self-assembled monolayer surface of fluorinated alkyl thiol on a gold 111 crystal has been studied at low ion kinetic energies (from 29 to 159 eV) using a custom built tandem mass spectrometer with a rotatable second stage energy analyzer and mass spectrometer detectors. Energy and intensity distributions of the scattered fragment ions were measured as a function of the fragment ion mass and scattering angle. Inelastically scattered CF3+ ions were not observed even at the lowest energy studied here. All fragment ions, CF2+, CF+, F+, and C+, were observed at all energies studied with the relative intensity of the highest energy pathway, C+, increasing and that of the lowest energy pathway, CF2+, decreasing with collision energy. Also, the dissociation efficiency of CF3+ decreased significantly as the collision energy was increased to 159 eV. Energy distributions of all fragment ions from the alkyl thiol surface showed two distinct components, one corresponding to the loss of nearly all of the kinetic energy and scattered over a broad angular range while the other corresponding to smaller kinetic energy losses and scattered closer to the surface parallel. The latter process is due to delayed dissociation of collisionally excited ions after they have passed the collision region as excited parent ions. A similar study performed at 74 eV using a LiF coated surface on a titanium substrate resulted only in one process for all fragment ions; corresponding to the delayed dissociation process. The intensity maxima for these fragmentation processes were shifted farther away from the surface parallel compared to the thiol surface. A new mechanism is proposed for the delayed dissociation process as proceeding via projectile ions' neutralization to long-lived highly excited Rydberg state(s), reionization by the potential field between the collision region and entrance to the energy analyzer, and subsequent dissociation

  11. Bonding energy of Sylgard on fused quartz: an experimental investigation

    Science.gov (United States)

    Liu, C.; Yeager, J. D.; Ramos, K. J.

    2015-02-01

    The bonding energy between the polymer Sylgard and fused quartz is determined experimentally using a miniature bulge test combined with three-dimensional digital image correlation (3D-DIC). Based on the experimental observation, Mindlin plate theory is used to compute the bonding energy (adhesive energy or surface energy) between the Sylgard and the fused quartz. The experimental results demonstrate that the combination of the miniature bulge test and the 3D-DIC provides a viable tool to directly measure interfacial and bonding properties.

  12. Studies on dissociation energies of diatomic molecules using vibrational spectroscopic constants

    Institute of Scientific and Technical Information of China (English)

    HOU; Shilin(侯世林); SUN; Weiguo(孙卫国)

    2003-01-01

    New analytical expression and numerical approach are suggested to calculate dissociation energies De of diatomic molecular states using an extreme value method (EVM). Studies on some electronic states of OH, BH, N2, Br2, ClF and CO molecules show that the accuracy of the EVM dissociation energies depends on the number of correct vibrational constants used in the calculations. The convergence qualities of De are suggested to be an alternative physical criterion to measure the qualities of the various sets of vibrational constants from different literature for the same diatomic state.

  13. Dissociation energy of diatomic molecules -comment on the work of Kaur and Mahajan

    Science.gov (United States)

    Chandra, Suresh

    2001-04-01

    When observed spectrum of a diatomic molecule is expressed in terms of the Dunham coefficients Y00, Y10, Y20, Y01, and Y11 only, dissociation energy of the molecule is given by Y00 + Y102/(-4 Y20). Kaur and Mahajan [1] have used the Dunham coefficients Y10, Y20, Y01, and Y11, for 15 vibrational states of 12 diatomic molecules (Y00 is zero for the cases accounted for), but their dissociation energy cannot be reproduced by the expression Y102/(-4 Y20). Probable reason for the discrepancy has been discussed.

  14. Dissociation energy of diatomic molecules – comment on the work of Kaur and Mahajan

    Indian Academy of Sciences (India)

    Suresh Chandra

    2001-04-01

    When observed spectrum of a diatomic molecule is expressed in terms of the Dunham coefficients 00, 10, 20, 01, and 11 only, dissociation energy of the molecule is given by 00 + $^{2}_{10}$/(-420). Kaur and Mahajan [1] have used the Dunham coefficients 10, 20, 01, and 11, for 15 vibrational states of 12 diatomic molecules (00 is zero for the cases accounted for), but their dissociation energy cannot be reproduced by the expression $^{2}_{10}$/(-420). Probable reason for the discrepancy has been discussed.

  15. Polarization and dissociation of a high energy photon-excited state in conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiao-xue, E-mail: sps_lixx@ujn.edu.cn

    2015-02-20

    We use the tight-binding Su–Schrieffer–Heeger model for the one-dimensional conjugated polymers to explore the static polarization behavior of a high energy photon-excited state under the electric field. An obvious reverse polarization is obtained although the electric field is weak. With the increase of field strength, the degree of polarization increases first and then decreases. When the electric field is strong enough, the excited state is dissociated into the polaron pair. In addition, the effects of electron–electron interaction and interchain coupling are also discussed. The results indicate that the electron–electron interaction could weaken the reverse polarization of the high energy photon-excited state, which tends to be dissociated into a high-energy exciton and a pair of solitons with the including of interchain coupling. - Highlights: • We explore the polarization of a high energy photon-excited state in polymers. • An obvious reverse polarization under the moderate electric field is obtained. • High energy photon-excited state is dissociated into polaron pair at strong field. • Increasing electron–electron interaction will weaken the reverse polarization. • Interchain coupling induces dissociation into high-energy exciton and solitons.

  16. Determination of bond energies by mass spectrometry. Some transition metal carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Michels, G.D.

    1979-01-01

    Two groups of transition metal carbonyls have been studied, M(CO)/sub 6/ and M(CO)/sub 5/CS complexes of the Group VIB metals and M/sub 2/(CO)/sub 10/ complexes of the Group VIIB metals. Results for the hexacarbonyl complexes indicate that the measured fragmentation energies are in error by 0.25 +- 0.02 eV per CO produced. This is attributed to excitation of CO to the first vibrational state. Least-squares dissociation energies calculated from corrected data for M(CO)/sub 5/CS complexes indicate that the M--CS bond is 3 to 4 times stronger than the M--CO bonds. Substitution of CS for CO in going from M(CO)/sub 6/ to M(CO)/sub 5/CS weakens the remaining M--CO bonds by an average of 0.2 eV. Previously unreported MnTc(CO)/sub 10/ and TcRe(CO)/sub 10/ are prepared by halide substitution of Tc(CO)/sub 5/Br and Re(CO)/sub 5/Br with Mn(CO)/sub 5//sup -/ and Tc(CO)/sub 5//sup -/, respectively. In the positive ion, metal and mixed-metal decacarbonyls are considered as (CO)/sub 5/M/sup +/--M(CO)/sub 5/ complexes possessing five strong and five weak M--CO bonds. For Mn/sub 2/(CO)/sub 10/ and Re/sub 2/(CO)/sub 10/, M/sup +/--M dissociation energies are 3.0 +- 0.1 and 4.0 +- 0.3 eV, respectively. These energies are 2.5 times greater than those reported for homolytic cleavage to M(CO)/sub 5//sup +/ and M(CO)/sub 5/.

  17. Bonding Energy and Growth Habit of Lithium Niobate Single Crystals

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    On the basis of crystallographic structure of lithium niobate (LN), the bonding energy was quantitatively calculated by the bond valence sum model, which was employed to investigate the crystal growth. A possible relationship between the crystal growth habit and chemical bonding energy of LN crystals are found. It is found that the higher the bond energy, the slower the growth rate, and the more important the plane. The analytical results indicate that (012) plane is the most influential face for the LN crystal growth, which consists well with the standard card (JCPDS Card: 20-0631) and our previous experimental observation. The current work shows that the chemical bond analysis of LN crystals allows us to predict its growth habit and thus to obtain the expected morphology during the spontaneous growth.

  18. A Rough Energy Landscape to Describe Surface-Linked Antibody and Antigen Bond Formation

    Science.gov (United States)

    Limozin, Laurent; Bongrand, Pierre; Robert, Philippe

    2016-01-01

    Antibodies and B cell receptors often bind their antigen at cell-cell interface while both molecular species are surface-bound, which impacts bond kinetics and function. Despite the description of complex energy landscapes for dissociation kinetics which may also result in significantly different association kinetics, surface-bound molecule (2D) association kinetics usually remain described by an on-rate due to crossing of a single free energy barrier, and few experimental works have measured association kinetics under conditions implying force and two-dimensional relative ligand-receptor motion. We use a new laminar flow chamber to measure 2D bond formation with systematic variation of the distribution of encounter durations between antigen and antibody, in a range from 0.1 to 10 ms. Under physiologically relevant forces, 2D association is 100-fold slower than 3D association as studied by surface plasmon resonance assays. Supported by brownian dynamics simulations, our results show that a minimal encounter duration is required for 2D association; an energy landscape featuring a rough initial part might be a reasonable way of accounting for this. By systematically varying the temperature of our experiments, we evaluate roughness at 2kBT, in the range of previously proposed rough parts of landscapes models during dissociation. PMID:27731375

  19. Force-dependent bond dissociation govern rolling of HL-60 cells through E-selectin.

    Science.gov (United States)

    Li, Quhuan; Fang, Ying; Ding, Xiaoru; Wu, Jianhua

    2012-08-15

    E-selectin-mediated rolling on vascular surface of circulating leukocyte on vascular surface is a key initial event during inflammatory response and lymphocyte homing. This event depends not only on the specific interactions of adhesive molecules but also on the hemodynamics of blood flow. Little is still understood about whether wall shear stress or shear rate regulates the rolling. With flow chamber techniques, we here measured the effects of transport, shear stress and cell deformation on rolling of both unfixed and fixed HL-60 cells on E-selectin either in the absence or in the presence of 3% Ficoll in medium at various wall shear stresses from 0.05 to 0.7 dyn/cm(2). The results demonstrated a triphasic force-dependent rolling, that is, as increasing of force, the rolling would be accelerated firstly, then followed a decelerating phase occurred at the initial shear threshold of about 0.1 dyn/cm(2), and lastly returned to an accelerating process starting at the optimal shear threshold of 0.35 dyn/cm(2) approximately. The catch bond regime was completely reflected to rolling behaviors, such as tether lifetime, cell stop time and rolling velocity, meaning that the dominant factor to govern rolling is force. The initial shear threshold might be the minimum level of wall shear stress to sustain a stationary rolling, and the optimal shear threshold would make rolling to the most stable and regular. These findings strongly elucidate the catch bond mechanism for flow-enhanced rolling through E-selectin since longer bond lifetimes led to slower and stabler rolling.

  20. N+ charge transfer and N+2 dissociation in N2 at swarm energies.

    Science.gov (United States)

    Basurto, E; de Urquijo, J; Cisneros, C; Alvarez, I

    2001-01-01

    This paper reports a drift-tube-mass-spectrometer measurement of the relative abundances of N+ and N+2 in pure nitrogen, over a ratio of electric field to gas density, E/N, from 800 to 7200 Td [1 townsend (Td)=10(-17) V cm(2)]. A proposed charge transfer dissociation scheme between the above two ions and N2 allowed us to obtain spatial rate coefficients for charge transfer and dissociation over the E/N range 800-2800 Td. Using previously measured cross sections for the above processes, and assuming a Maxwellian distribution of ion velocities, we calculated the reaction coefficients, which were found to be in good agreement with our measured values. In particular, the present results support the trend toward fairly high charge transfer cross section values for N+ energies above 10 eV. In the overlap range between 2.4 and 7.2 kTd, our concentration ratio [N(+)/N(+)(2)] is about five times smaller than that measured previously from a diffuse Townsend discharge in which electron impact is involved in addition to N+2 collisional dissociation with N2, but has the same trend. Thus it seems that, besides N+2 dissociation by electron impact, collisional dissociation becomes important at elevated values of E/N. In connection with previous discharge work in nitrogen, the present study may help explain the enhanced cathode yields observed.

  1. Boltzmann rovibrational collisional coarse-grained model for internal energy excitation and dissociation in hypersonic flows.

    Science.gov (United States)

    Munafò, A; Panesi, M; Magin, T E

    2014-02-01

    A Boltzmann rovibrational collisional coarse-grained model is proposed to reduce a detailed kinetic mechanism database developed at NASA Ames Research Center for internal energy transfer and dissociation in N(2)-N interactions. The coarse-grained model is constructed by lumping the rovibrational energy levels of the N(2) molecule into energy bins. The population of the levels within each bin is assumed to follow a Boltzmann distribution at the local translational temperature. Excitation and dissociation rate coefficients for the energy bins are obtained by averaging the elementary rate coefficients. The energy bins are treated as separate species, thus allowing for non-Boltzmann distributions of their populations. The proposed coarse-grained model is applied to the study of nonequilibrium flows behind normal shock waves and within converging-diverging nozzles. In both cases, the flow is assumed inviscid and steady. Computational results are compared with those obtained by direct solution of the master equation for the rovibrational collisional model and a more conventional multitemperature model. It is found that the proposed coarse-grained model is able to accurately resolve the nonequilibrium dynamics of internal energy excitation and dissociation-recombination processes with only 20 energy bins. Furthermore, the proposed coarse-grained model provides a superior description of the nonequilibrium phenomena occurring in shock heated and nozzle flows when compared with the conventional multitemperature models.

  2. The Bond Order of C2 from a Strictly N-Representable Natural Orbital Energy Functional Perspective.

    Science.gov (United States)

    Piris, Mario; Lopez, Xabier; Ugalde, Jesus M

    2016-03-14

    The bond order of the ground electronic state of the carbon dimer has been analyzed in the light of natural orbital functional theory calculations carried out with an approximate, albeit strictly N-representable, energy functional. Three distinct solutions have been found from the Euler equations of the minimization of the energy functional with respect to the natural orbitals and their occupation numbers, which expand upon increasing values of the internuclear coordinate. In the close vicinity of the minimum energy region, two of the solutions compete around a discontinuity point. The former, corresponding to the absolute minimum energy, features two valence natural orbitals of each of the following symmetries, σ, σ*, π and π*, and has three bonding interactions and one antibonding interaction, which is very suggestive of a bond order large than two but smaller than three. The latter, features one σ-σ* linked pair of natural orbitals and three degenerate pseudo-bonding like orbitals, paired each with one triply degenerate pseudo-antibonding orbital, which points to a bond order larger than three. When correlation effects, other than Hartree-Fock for example, between the paired natural orbitals are accounted for, this second solution vanishes yielding a smooth continuous dissociation curve. Comparison of the vibrational energies and electron ionization energies, calculated on this curve, with their corresponding experimental marks, lend further support to a bond order for C2 intermediate between acetylene and ethylene.

  3. Dynamics of N-OH bond dissociation in cyclopentanone and cyclohexanone oxime at 193 nm: laser-induced fluorescence detection of nascent OH (v'', J'').

    Science.gov (United States)

    Kawade, Monali N; Saha, Ankur; Upadhyaya, Hari P; Kumar, Awadhesh; Naik, Prakash D

    2010-12-01

    Cyclohexanone oxime (CHO) and cyclopentanone oxime (CPO) in the vapor phase undergo N-OH bond scission upon excitation at 193 nm to produce OH, which was detected state selectively employing laser-induced fluorescence. The measured energy distribution between fragments for both oximes suggests that in CHO the OH produced is mostly vibrationally cold, with moderate rotational excitation, whereas in CPO the OH fragment is also formed in v'' = 1 (~2%). The rotational population of OH (v'' = 0, J'') from CHO is characterized by a rotational temperature of 1440 ± 80 K, whereas the rotational populations of OH (v'' = 0, J'') and OH (v'' = 1, J'') from CPO are characterized by temperatures of 1360 ± 90 K and 930 ± 170 K, respectively. A high fraction of the available energy is partitioned to the relative translation of the fragments with f(T) values of 0.25 and 0.22 for CHO and CPO, respectively. In the case of CHO, the Λ-doublet states of the nascent OH radical are populated almost equally in lower rotational quantum levels N'', with a preference for Π(+) (A') states for higher N''. However, there is no preference for either of the two spin orbit states Π(3/2) and Π(1/2) of OH. The nascent OH product in CPO is equally distributed in both Λ-doublet states of Π(+) (A') and Π(-) (A'') for all N'', but has a preference for the Π(3/2) spin orbit state. Experimental work in combination with theoretical calculations suggests that both CHO and CPO molecules at 193 nm are excited to the S(2) state, which undergoes nonradiative relaxation to the T(2) state. Subsequently, molecules undergo the N-OH bond dissociation from the T(2) state with an exit barrier to produce OH (v'', J'').

  4. Theoretical investigation on the bond dissociation enthalpies of phenolic compounds extracted from Artocarpus altilis using ONIOM(ROB3LYP/6-311++G(2df,2p):PM6) method

    Science.gov (United States)

    Thong, Nguyen Minh; Duong, Tran; Pham, Linh Thuy; Nam, Pham Cam

    2014-10-01

    Theoretical calculations have been performed to predict the antioxidant property of phenolic compounds extracted from Artocarpus altilis. The Osbnd H bond dissociation enthalpy (BDE), ionization energy (IE), and proton dissociation enthalpy (PDE) of the phenolic compounds have been computed. The ONIOM(ROB3LYP/6-311++G(2df,2p):PM6) method is able to provide reliable evaluation for the BDE(Osbnd H) in phenolic compounds. An important property of antioxidants is determined via the BDE(Osbnd H) of those compounds extracted from A. altilis. Based on the BDE(Osbnd H), compound 12 is considered as a potential antioxidant with the estimated BDE value of 77.3 kcal/mol in the gas phase.

  5. Identification of general linear relationships between activation energies and enthalpy changes for dissociation reactions at surfaces.

    Science.gov (United States)

    Michaelides, Angelos; Liu, Z-P; Zhang, C J; Alavi, Ali; King, David A; Hu, P

    2003-04-02

    The activation energy to reaction is a key quantity that controls catalytic activity. Having used ab inito calculations to determine an extensive and broad ranging set of activation energies and enthalpy changes for surface-catalyzed reactions, we show that linear relationships exist between dissociation activation energies and enthalpy changes. Known in the literature as empirical Brønsted-Evans-Polanyi (BEP) relationships, we identify and discuss the physical origin of their presence in heterogeneous catalysis. The key implication is that merely from knowledge of adsorption energies the barriers to catalytic elementary reaction steps can be estimated.

  6. Dissociation energies of six NO2 isotopologues by laser induced fluorescence spectroscopy and zero point energy of some triatomic molecules.

    Science.gov (United States)

    Michalski, G; Jost, R; Sugny, D; Joyeux, M; Thiemens, M

    2004-10-15

    We have measured the rotationless photodissociation threshold of six isotopologues of NO2 containing 14N, 15N, 16O, and 18O isotopes using laser induced fluorescence detection and jet cooled NO2 (to avoid rotational congestion). For each isotopologue, the spectrum is very dense below the dissociation energy while fluorescence disappears abruptly above it. The six dissociation energies ranged from 25 128.56 cm(-1) for 14N16O2 to 25 171.80 cm(-1) for 15N18O2. The zero point energy for the NO2 isotopologues was determined from experimental vibrational energies, application of the Dunham expansion, and from canonical perturbation theory using several potential energy surfaces. Using the experimentally determined dissociation energies and the calculated zero point energies of the parent NO2 isotopologue and of the NO product(s) we determined that there is a common De = 26 051.17+/-0.70 cm(-1) using the Born-Oppenheimer approximation. The canonical perturbation theory was then used to calculate the zero point energy of all stable isotopologues of SO2, CO2, and O3, which are compared with previous determinations.

  7. Estimating the energy of intramolecular hydrogen bonds in chitosan oligomers

    Science.gov (United States)

    Mikhailov, G. P.; Lazarev, V. V.

    2016-07-01

    The effect the number of chitosan monomer units CTS n ( n = 1-5), the protonation of chitosan dimers, and the interaction between CTS n ( n = 1-3) and acetate ions have on the energy of intramolecular hydrogen bonds is investigated by means of QTAIM analysis and solving the vibrational problem within the cluster-continuum model. It is established that the number of H-bonds in CTS n is 2 n - 1 and the total energy of H-bonds grows by ~20 kJ/mol. It is concluded that the hydrogen bonds between CTS and acetate ions play a major role in the stabilization of polyelectrolyte complexes in dilute acetic acid solutions of CTS.

  8. Molecular dynamical studies of the dissociation of a diatomic molecular crystal. I. Energy exchange in rapid exothermic reactions

    Science.gov (United States)

    Tsai, D. H.; Trevino, S. F.

    1983-08-01

    We discuss the results of a study of the exothermic dissociation of a model diatomic molecular crystal. Our main purpose is to investigate the dynamics of energy transport and energy sharing in this system during the dissociation process. The crystal was prepared in a metastable molecular form, in thermal equilibrium at a low initial temperature and pressure. When we heated the system to a higher temperature, at constant volume, we observed thermally initiated dissociations which progressed rapidly to completion. During the dissociation process, we found that the sharing of the potential energy released by the metastable molecules with the rest of the system, and the sharing of the kinetic energy of the dissociated fragments with the kinetic energy of the molecules in the translational degrees of freedom, were rather efficient. But the intra- and intermolecular exchange of the kinetic energy among the various degrees of freedom, viz., translation-rotation, translation-vibration, and rotation-vibration was inefficient. Dissociation would occur in one of the regions of high local kinetic energy density, after a molecule in that region had acquired sufficient vibrational energy to break apart, and when the ``caging'' effect was favorable to allow the molecule to dissociate. From such a reaction site, and there may be others, the reaction would spread to a neighboring site, and continue this way until all the molecules became dissociated. The induction time showed an approximately logarithmic dependence on the inverse of the temperature of the system after heating. But during the process of rapid dissociation, both the potential energy and the kinetic energy of the system underwent rapid changes, and thermal equilibrium was not reached until the end of the process.

  9. Formation and reshuffling of disulfide bonds in bovine serum albumin demonstrated using tandem mass spectrometry with collision-induced and electron-transfer dissociation.

    Science.gov (United States)

    Rombouts, Ine; Lagrain, Bert; Scherf, Katharina A; Lambrecht, Marlies A; Koehler, Peter; Delcour, Jan A

    2015-07-20

    Thermolysin hydrolyzates of freshly isolated, extensively stored (6 years, 6 °C, dry) and heated (60 min, 90 °C, in excess water) bovine serum albumin (BSA) samples were analyzed with liquid chromatography (LC) electrospray ionization (ESI) tandem mass spectrometry (MS/MS) using alternating electron-transfer dissociation (ETD) and collision-induced dissociation (CID). The positions of disulfide bonds and free thiol groups in the different samples were compared to those deduced from the crystal structure of native BSA. Results revealed non-enzymatic posttranslational modifications of cysteine during isolation, extensive dry storage, and heating. Heat-induced extractability loss of BSA was linked to the impact of protein unfolding on the involvement of specific cysteine residues in intermolecular and intramolecular thiol-disulfide interchange and thiol oxidation reactions. The here developed approach holds promise for exploring disulfide bond formation and reshuffling in various proteins under conditions relevant for chemical, biochemical, pharmaceutical and food processing.

  10. Elementary Steps of Syngas Reactions on Mo2C(001): Adsorption Thermochemistry and Bond Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Medford, Andrew

    2012-02-16

    Density functional theory (DFT) and ab initio thermodynamics are applied in order to investigate the most stable surface and subsurface terminations of Mo{sub 2}C(001) as a function of chemical potential and in the presence of syngas. The Mo-terminated (001) surface is then used as a model surface to evaluate the thermochemistry and energetic barriers for key elementary steps in syngas reactions. Adsorption energy scaling relations and Broensted-Evans-Polanyi relationships are established and used to place Mo{sub 2}C into the context of transition metal surfaces. The results indicate that the surface termination is a complex function of reaction conditions and kinetics. It is predicted that the surface will be covered by either C{sub 2}H{sub 2} or O depending on conditions. Comparisons to transition metals indicate that the Mo-terminated Mo{sub 2}C(001) surface exhibits carbon reactivity similar to transition metals such as Ru and Ir, but is significantly more reactive towards oxygen.

  11. Measurement of bonding energy in an anhydrous nitrogen atmosphere and its application to silicon direct bonding technology

    Science.gov (United States)

    Fournel, F.; Continni, L.; Morales, C.; Da Fonseca, J.; Moriceau, H.; Rieutord, F.; Barthelemy, A.; Radu, I.

    2012-05-01

    Bonding energy represents an important parameter for direct bonding applications as well as for the elaboration of physical mechanisms at bonding interfaces. Measurement of bonding energy using double cantilever beam (DCB) under prescribed displacement is the most used technique thanks to its simplicity. The measurements are typically done in standard atmosphere with relative humidity above 30%. Therefore, the obtained bonding energies are strongly impacted by the water stress corrosion at the bonding interfaces. This paper presents measurements of bonding energies of directly bonded silicon wafers under anhydrous nitrogen conditions in order to prevent the water stress corrosion effect. It is shown that the measurements under anhydrous nitrogen conditions (less than 0.2 ppm of water in nitrogen) lead to high stable debonding lengths under static load and to higher bonding energies compared to the values measured under standard ambient conditions. Moreover, the bonding energies of Si/SiO2 or SiO2/SiO2 bonding interfaces are measured overall the classical post bond annealing temperature range. These new results allow to revisit the reported bonding mechanisms and to highlight physical and chemical phenomena in the absence of stress corrosion effect.

  12. Modeling of dissociation and energy transfer in shock-heated nitrogen flows

    Energy Technology Data Exchange (ETDEWEB)

    Munafò, A., E-mail: munafo@illinois.edu [Department of Aerospace Engineering, University of Illinois at Urbana-Champaign, Talbot Laboratory, 104 S. Wright St., Urbana, Illinois 61801 (United States); NASA Ames Research Center, Moffett Field, California 94035 (United States); Liu, Y., E-mail: yen.liu@nasa.gov [NASA Ames Research Center, Moffett Field, California 94035 (United States); Panesi, M., E-mail: mpanesi@illinois.edu [Department of Aerospace Engineering, University of Illinois at Urbana-Champaign, Talbot Laboratory, 104 S. Wright St., Urbana, Illinois 61801 (United States)

    2015-12-15

    This work addresses the modeling of dissociation and energy transfer processes in shock heated nitrogen flows by means of the maximum entropy linear model and a newly proposed hybrid bin vibrational collisional model. Both models aim at overcoming two of the main limitations of the state of the art non-equilibrium models: (i) the assumption of equilibrium between rotational and translational energy modes of the molecules and (ii) the reliance on the quasi-steady-state distribution for the description of the population of the internal levels. The formulation of the coarse-grained models is based on grouping the energy levels into bins, where the population is assumed to follow a Maxwell-Boltzmann distribution at its own temperature. Different grouping strategies are investigated. Following the maximum entropy principle, the governing equations are obtained by taking the zeroth and first-order moments of the rovibrational master equations. The accuracy of the proposed models is tested against the rovibrational master equation solution for both flow quantities and population distributions. Calculations performed for free-stream velocities ranging from 5 km/s to 10 km/s demonstrate that dissociation can be accurately predicted by using only 2-3 bins. It is also shown that a multi-temperature approach leads to an under-prediction of dissociation, due to the inability of the former to account for the faster excitation of high-lying vibrational states.

  13. Electron Capture Dissociation of Weakly Bound Polypeptide Polycationic Complexes

    DEFF Research Database (Denmark)

    Haselmann, Kim F; Jørgensen, Thomas J D; Budnik, Bogdan A;

    2002-01-01

    We have previously reported that, in electron capture dissociation (ECD), rupture of strong intramolecular bonds in weakly bound supramolecular aggregates can proceed without dissociation of weak intermolecular bonds. This is now illustrated on a series of non-specific peptide-peptide dimers...... as well as specific complexes of modified glycopeptide antibiotics with their target peptide. The weak nature of bonding is substantiated by blackbody infrared dissociation, low-energy collisional excitation and force-field simulations. The results are consistent with a non-ergodic ECD cleavage mechanism....

  14. Enthalpy of Formation and O-H Bond Dissociation Enthalpy of Phenol: Inconsistency between Theory and Experiment.

    Science.gov (United States)

    Dorofeeva, Olga V; Ryzhova, Oxana N

    2016-04-21

    Gas-phase O–H homolytic bond dissociation enthalpy in phenol, DH298°(C6H5O–H), is still disputed, despite a large number of experimental and computational studies. In estimating this value, the experimental enthalpy of formation of phenol, ΔfH298°(C6H5OH, g) = −96.4 ± 0.6 kJ/mol (Cox, J. D. Pure Appl. Chem. 1961, 2, 125−128), is often used assuming high accuracy of the experimental value. In the present work a substantially less negative value of ΔfH298°(C6H5OH, g) = −91.8 ± 2.5 kJ/mol was calculated combining G4 theory with an isodesmic reaction approach. A benchmark quality of this result was achieved by using a large number of reliable reference species in isodesmic reaction calculations. Among these are the most accurate ΔfH298° values currently available from the Active Thermochemical Tables (ATcT) for 36 species (neutral molecules, radicals, and ions), anisole with recently reassessed enthalpy of formation, and 13 substituted phenols. The internal consistency of the calculated ΔfH298°(C6H5OH, g) value with the experimental enthalpies of formation of more than 50 reference species suggests that the reported experimental enthalpy of formation of phenol is in error. Taking into account that the enthalpy of formation of phenol has not been investigated experimentally since 1961, the new measurements would be extremely valuable. Using the accurate enthalpies of formation of C6H5OH and C6H5O• calculated in the present work, we obtained DH298°(C6H5O–H) = 369.6 ± 4.0 kJ/mol. This value is in satisfactory agreement with that determined from the most precise experimental measurement.

  15. Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy

    Energy Technology Data Exchange (ETDEWEB)

    McGrail, B. Peter; Brown, Daryl R.; Thallapally, Praveen K.

    2016-08-02

    Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

  16. The role of proton mobility in determining the energy-resolved vibrational activation/dissociation channels of N-glycopeptide ions.

    Science.gov (United States)

    Kolli, Venkata; Roth, Heidi A; De La Cruz, Gabriela; Fernando, Ganga S; Dodds, Eric D

    2015-10-01

    Site-specific glycoproteomic analysis largely hinges on the use of tandem mass spectrometry (MS/MS) to identify glycopeptides. Experiments of this type are usually aimed at drawing connections between individual oligosaccharide structures and their specific sites of attachment to the polypeptide chain. These determinations inherently require ion dissociation methods capable of interrogating both the monosaccharide and amino acid connectivity of the glycopeptide. Collision-induced dissociation (CID) shows potential to satisfy this requirement, as the vibrational activation/dissociation of protonated N-glycopeptides has been observed to access cleavage of either glycosidic bonds of the glycan or amide bonds of the peptide in an energy-resolved manner. Nevertheless, the relative energy requirement for these fragmentation pathways varies considerably among analytes. This research addresses the influence of proton mobility on the vibrational energy necessary to achieve either glycan or peptide cleavage in a collection of protonated N-glycopeptide ions. While greater proton mobility of the precursor ion was found to correlate with lower energy requirements for precursor ion depletion and appearance of glycosidic fragments, the vibrational energy deposition necessary for appearance of peptide backbone fragments showed no relation to the precursor ion proton mobility. These results are consistent with observations suggesting that peptide fragments arise from an intermediate fragment which is generally of lower proton mobility than the precursor ion. Such findings have potential to facilitate the rational selection of CID conditions which are best suited to provide either glycan or peptide cleavage products in MS/MS based N-glycoproteomic analysis.

  17. Formation and reactivity of a porphyrin iridium hydride in water: acid dissociation constants and equilibrium thermodynamics relevant to Ir-H, Ir-OH, and Ir-CH2- bond dissociation energetics.

    Science.gov (United States)

    Bhagan, Salome; Wayland, Bradford B

    2011-11-01

    Aqueous solutions of group nine metal(III) (M = Co, Rh, Ir) complexes of tetra(3,5-disulfonatomesityl)porphyrin [(TMPS)M(III)] form an equilibrium distribution of aquo and hydroxo complexes ([(TMPS)M(III)(D(2)O)(2-n)(OD)(n)]((7+n)-)). Evaluation of acid dissociation constants for coordinated water show that the extent of proton dissociation from water increases regularly on moving down the group from cobalt to iridium, which is consistent with the expected order of increasing metal-ligand bond strengths. Aqueous (D(2)O) solutions of [(TMPS)Ir(III)(D(2)O)(2)](7-) react with dihydrogen to form an iridium hydride complex ([(TMPS)Ir-D(D(2)O)](8-)) with an acid dissociation constant of 1.8(0.5) × 10(-12) (298 K), which is much smaller than the Rh-D derivative (4.3 (0.4) × 10(-8)), reflecting a stronger Ir-D bond. The iridium hydride complex adds with ethene and acetaldehyde to form organometallic derivatives [(TMPS)Ir-CH(2)CH(2)D(D(2)O)](8-) and [(TMPS)Ir-CH(OD)CH(3)(D(2)O)](8-). Only a six-coordinate carbonyl complex [(TMPS)Ir-D(CO)](8-) is observed for reaction of the Ir-D with CO (P(CO) = 0.2-2.0 atm), which contrasts with the (TMPS)Rh-D analog which reacts with CO to produce an equilibrium with a rhodium formyl complex ([(TMPS)Rh-CDO(D(2)O)](8-)). Reactivity studies and equilibrium thermodynamic measurements were used to discuss the relative M-X bond energetics (M = Rh, Ir; X = H, OH, and CH(2)-) and the thermodynamically favorable oxidative addition of water with the (TMPS)Ir(II) derivatives.

  18. Students' Interdisciplinary Reasoning about "High-Energy Bonds" and ATP

    CERN Document Server

    Dreyfus, Benjamin W; Sawtelle, Vashti; Svoboda, Julia; Turpen, Chandra; Redish, Edward F

    2012-01-01

    Students' sometimes contradictory ideas about ATP (adenosine triphosphate) and the nature of chemical bonds have been studied in the biology and chemistry education literatures, but these topics are rarely part of the introductory physics curriculum. We present qualitative data from an introductory physics course for undergraduate biology majors that seeks to build greater interdisciplinary coherence and therefore includes these topics. In these data, students grapple with the apparent contradiction between the energy released when the phosphate bond in ATP is broken and the idea that an energy input is required to break a bond. We see that students' perceptions of how each scientific discipline bounds the system of interest can influence how they justify their reasoning about a topic that crosses disciplines. This has consequences for a vision of interdisciplinary education that respects disciplinary perspectives while bringing them into interaction in ways that demonstrate consistency amongst the perspectiv...

  19. An improved potential energy surface and multi-temperature quasiclassical trajectory calculations of N2 + N2 dissociation reactions.

    Science.gov (United States)

    Bender, Jason D; Valentini, Paolo; Nompelis, Ioannis; Paukku, Yuliya; Varga, Zoltan; Truhlar, Donald G; Schwartzentruber, Thomas; Candler, Graham V

    2015-08-01

    Accurate modeling of high-temperature hypersonic flows in the atmosphere requires consideration of collision-induced dissociation of molecular species and energy transfer between the translational and internal modes of the gas molecules. Here, we describe a study of the N2 + N2⟶N2 + 2N and N2 + N2⟶4N nitrogen dissociation reactions using the quasiclassical trajectory (QCT) method. The simulations used a new potential energy surface for the N4 system; the surface is an improved version of one that was presented previously. In the QCT calculations, initial conditions were determined based on a two-temperature model that approximately separates the translational-rotational temperature from the vibrational temperature of the N2 diatoms. Five values from 8000 K to 30,000 K were considered for each of the two temperatures. Over 2.4 × 10(9) trajectories were calculated. We present results for ensemble-averaged dissociation rate constants as functions of the translational-rotational temperature T and the vibrational temperature T(v). The rate constant depends more strongly on T when T(v) is low, and it depends more strongly on T(v) when T is low. Quasibound reactant states contribute significantly to the rate constants, as do exchange processes at higher temperatures. We discuss two sets of runs in detail: an equilibrium test set in which T = T(v) and a nonequilibrium test set in which T(v) test set, high-v and moderately-low-j molecules contribute most significantly to the overall dissociation rate, and this state specificity becomes stronger as the temperature decreases. Dissociating trajectories tend to result in a major loss of vibrational energy and a minor loss of rotational energy. In the nonequilibrium test set, as T(v) decreases while T is fixed, higher-j molecules contribute more significantly to the dissociation rate, dissociating trajectories tend to result in a greater rotational energy loss, and the dissociation probability's dependence on v weakens. In

  20. Dissociative recombination and vibrational excitation of BF+ in low energy electron collisions

    Science.gov (United States)

    Mezei, J. Zs; Colboc, F.; Pop, N.; Ilie, S.; Chakrabarti, K.; Niyonzima, S.; Lepers, M.; Bultel, A.; Dulieu, O.; Motapon, O.; Tennyson, J.; Hassouni, K.; Schneider, I. F.

    2016-10-01

    The latest molecular data—potential energy curves and Rydberg-valence interactions—characterising the super-excited electronic states of BF are reviewed in order to provide the input for the study of their fragmentation dynamics. Starting from this input, the main paths and mechanisms of BF+ dissociative recombination and vibrational excitation are analysed. Their cross sections are computed for the first time using a method based on the multichannel quantum defect theory (MQDT), and Maxwellian rate-coefficients are calculated and displayed in ready-to-be-used format for low temperature plasma kinetics simulations.

  1. Energetics and Dynamics of the Fragmentation Reactions of Protonated Peptides Containing Methionine Sulfoxide or Aspartic Acid via Energy- and Time-Resolved Surface Induced Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Lioe, Hadi; Laskin, Julia; Reid, Gavin E.; O' Hair, Richard Aj

    2007-10-25

    The surface-induced dissociation (SID) of six model peptides containing either methionine sulfoxide or aspartic acid (GAILM(O)GAILR, GAILM(O)GAILK, GAILM(O)GAILA, GAILDGAILR, GAILDGAILK, and GAILDGAILA) have been studied using a specially configured Fourier transform ion-cyclotron resonance mass spectrometer (FT-ICR MS). In particular, we have investigated the energetics and dynamics associated with (i) preferential cleavage of the methionine sulfoxide side chain via the loss of CH3SOH (64Da), and (ii) preferential cleavage of the amide bond C-terminal to aspartic acid. The role of proton mobility on these selective bond cleavage reactions was examined by changing the C-terminal residue of the peptide from arginine (non-mobile proton conditions) to lysine (partially-mobile proton conditions) to alanine (mobile proton conditions). Time- and energy-resolved fragmentation efficiency curves (TFEC) reveals that selective cleavages due to the methionine sulfoxide and aspartic acid residues are characterized by slow fragmentation kinetics. RRKM modeling of the experimental data suggests that the slow kinetics is associated with large negative entropy effects and these may be due to the presence of rearrangements prior to fragmentation. It was found that the Arrhenius pre-exponential factor (A) for peptide fragmentations occurring via selective bond cleavages are 1–2 orders of magnitude lower than non-selective peptide fragmentation reactions, while the dissociation threshold (E0) is relatively invariant. This means that selective bond cleavage is kinetically disfavored compared to non-selective amide bond cleavage. It was also found that the energetics and dynamics for the preferential loss of CH3SOH from peptide ions containing methionine sulfoxide are very similar to selective C-terminal amide bond cleavage at the aspartic acid residue. These results suggest that while preferential cleavage can compete with amide bond cleavage energetically, dynamically, these

  2. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter

    2009-01-01

    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energie

  3. An improved potential energy surface and multi-temperature quasiclassical trajectory calculations of N2 + N2 dissociation reactions

    Science.gov (United States)

    Bender, Jason D.; Valentini, Paolo; Nompelis, Ioannis; Paukku, Yuliya; Varga, Zoltan; Truhlar, Donald G.; Schwartzentruber, Thomas; Candler, Graham V.

    2015-08-01

    Accurate modeling of high-temperature hypersonic flows in the atmosphere requires consideration of collision-induced dissociation of molecular species and energy transfer between the translational and internal modes of the gas molecules. Here, we describe a study of the N2 + N2⟶N2 + 2N and N2 + N2⟶4N nitrogen dissociation reactions using the quasiclassical trajectory (QCT) method. The simulations used a new potential energy surface for the N4 system; the surface is an improved version of one that was presented previously. In the QCT calculations, initial conditions were determined based on a two-temperature model that approximately separates the translational-rotational temperature from the vibrational temperature of the N2 diatoms. Five values from 8000 K to 30 000 K were considered for each of the two temperatures. Over 2.4 × 109 trajectories were calculated. We present results for ensemble-averaged dissociation rate constants as functions of the translational-rotational temperature T and the vibrational temperature Tv. The rate constant depends more strongly on T when Tv is low, and it depends more strongly on Tv when T is low. Quasibound reactant states contribute significantly to the rate constants, as do exchange processes at higher temperatures. We discuss two sets of runs in detail: an equilibrium test set in which T = Tv and a nonequilibrium test set in which Tv rate, and this state specificity becomes stronger as the temperature decreases. Dissociating trajectories tend to result in a major loss of vibrational energy and a minor loss of rotational energy. In the nonequilibrium test set, as Tv decreases while T is fixed, higher-j molecules contribute more significantly to the dissociation rate, dissociating trajectories tend to result in a greater rotational energy loss, and the dissociation probability's dependence on v weakens. In this way, as Tv decreases, rotational energy appears to compensate for the decline in average vibrational energy in

  4. Free energy barrier for dissociation of the guanosine monophosphate anion in water

    Science.gov (United States)

    Cornetta, Lucas M.; Coutinho, Kaline; Canuto, Sylvio; Varella, Márcio T. do N.

    2016-08-01

    We report free energy barriers for the ground-state dissociation of the guanosine nucleotide anion in solution, employing implicit and explicit solvation models. The latter was based on the Free Energy Perturbation technique and Monte Carlo simulations. For the lowest-energy structure, both solvation models indicate a solvent-induced transition from a dipole-bound state in the gas phase to a π∗ valence state in solution. The free barrier estimates obtained from explicit and implicit solvation are in fair agreement with each other, although significantly overestimated in comparison to a previously reported explicit solvation model based on ab initio molecular dynamics simulations. Accounting for corrections related to the different DFT functionals used in the present and previous studies significantly improves the agreement. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  5. Stepwise Ti-Cl, Ti-CH3, and Ti-C6H5 bond dissociation enthalpies in bis(pentamethylcyclopentadienyl)titanium complexes

    NARCIS (Netherlands)

    Dias, Alberto R.; Salema, Margarida S.; Martinho Simões, Jose A.; Pattiasina, Johannes W.; Teuben, Jan H.

    1988-01-01

    Reaction-solution calorimetric studies involving the complexes Ti[η5-C5(CH3)5]2(CH3)2, Ti[η5-C5(CH3)5]2(CH3), Ti[η5-C5(CH3)5]2(C6H5), Ti[η5-C5(CH3)5]2Cl2, and Ti[η5-C5(CH3)5]2Cl, have enabled derivation of titanium-carbon and titanium-chlorine stepwise bond dissociation enthalpies in these species.

  6. IR Spectra and Bond Energies Computed Using DFT

    Science.gov (United States)

    Bauschlicher, Charles; Andrews, Lester; Arnold, James (Technical Monitor)

    2000-01-01

    The combination of density functional theory (DFT) frequencies and infrared (IR) intensities and experimental spectra is a very powerful tool in the identification of molecules and ions. The computed and measured isotopic ratios make the identification much more secure than frequencies and intensities alone. This will be illustrated using several examples, such as Mn(CO)n and Mn(CO)n-. The accuracy of DFT metal-ligand bond energies will also be discussed.

  7. Geometrical structures, vibrational frequencies, force constants and dissociation energies of isotopic water molecules (H2O, HDO, D2O, HTO, DTO, and T2O) under dipole electric field

    Institute of Scientific and Technical Information of China (English)

    Shi Shun-Ping; Zhang Quan; Zhang Li; Wang Rong; Zhu Zheng-He; Jiang Gang; Fu Yi-Bei

    2011-01-01

    The dissociation limits of isotopic water molecules are derived for the ground state. The equilibrium geometries,the vibrational frequencies, the force constants and the dissociation energies for the ground states of all isotopic water molecules under the dipole electric fields from -0.05 a.u. to 0.05 a.u. are calculated using B3P86/6-311++G(3df,3pf).The results show that when the dipole electric fields change from -0.05 a.u. to 0.05 a.u., the bond length of H-O increases whereas the bond angle of H-O-H decreases because of the charge transfer induced by the applied dipole electric field. The vibrational frequencies and the force constants of isotopic water molecules change under the influence of the strong external torque. The dissociation energies increase when the dipole electric fields change from -0.05 a.u.to 0.05 a.u. and the increased dissociation energies are in the order of H2O, HDO, HTO, D2O, DTO, and T2O under the same external electric fields.

  8. Simultaneous Glycan-Peptide Characterization Using Hydrophilic Interaction Chromatography and Parallel Fragmentation by CID, Higher Energy Collisional Dissociation, and Electron Transfer Dissociation MS Applied to the N-Linked Glycoproteome of Campylobacter jejuni*

    Science.gov (United States)

    Scott, Nichollas E.; Parker, Benjamin L.; Connolly, Angela M.; Paulech, Jana; Edwards, Alistair V. G.; Crossett, Ben; Falconer, Linda; Kolarich, Daniel; Djordjevic, Steven P.; Højrup, Peter; Packer, Nicolle H.; Larsen, Martin R.; Cordwell, Stuart J.

    2011-01-01

    Campylobacter jejuni is a gastrointestinal pathogen that is able to modify membrane and periplasmic proteins by the N-linked addition of a 7-residue glycan at the strict attachment motif (D/E)XNX(S/T). Strategies for a comprehensive analysis of the targets of glycosylation, however, are hampered by the resistance of the glycan-peptide bond to enzymatic digestion or β-elimination and have previously concentrated on soluble glycoproteins compatible with lectin affinity and gel-based approaches. We developed strategies for enriching C. jejuni HB93-13 glycopeptides using zwitterionic hydrophilic interaction chromatography and examined novel fragmentation, including collision-induced dissociation (CID) and higher energy collisional (C-trap) dissociation (HCD) as well as CID/electron transfer dissociation (ETD) mass spectrometry. CID/HCD enabled the identification of glycan structure and peptide backbone, allowing glycopeptide identification, whereas CID/ETD enabled the elucidation of glycosylation sites by maintaining the glycan-peptide linkage. A total of 130 glycopeptides, representing 75 glycosylation sites, were identified from LC-MS/MS using zwitterionic hydrophilic interaction chromatography coupled to CID/HCD and CID/ETD. CID/HCD provided the majority of the identifications (73 sites) compared with ETD (26 sites). We also examined soluble glycoproteins by soybean agglutinin affinity and two-dimensional electrophoresis and identified a further six glycosylation sites. This study more than doubles the number of confirmed N-linked glycosylation sites in C. jejuni and is the first to utilize HCD fragmentation for glycopeptide identification with intact glycan. We also show that hydrophobic integral membrane proteins are significant targets of glycosylation in this organism. Our data demonstrate that peptide-centric approaches coupled to novel mass spectrometric fragmentation techniques may be suitable for application to eukaryotic glycoproteins for simultaneous

  9. Simultaneous glycan-peptide characterization using hydrophilic interaction chromatography and parallel fragmentation by CID, higher energy collisional dissociation, and electron transfer dissociation MS applied to the N-linked glycoproteome of Campylobacter jejuni.

    Science.gov (United States)

    Scott, Nichollas E; Parker, Benjamin L; Connolly, Angela M; Paulech, Jana; Edwards, Alistair V G; Crossett, Ben; Falconer, Linda; Kolarich, Daniel; Djordjevic, Steven P; Højrup, Peter; Packer, Nicolle H; Larsen, Martin R; Cordwell, Stuart J

    2011-02-01

    Campylobacter jejuni is a gastrointestinal pathogen that is able to modify membrane and periplasmic proteins by the N-linked addition of a 7-residue glycan at the strict attachment motif (D/E)XNX(S/T). Strategies for a comprehensive analysis of the targets of glycosylation, however, are hampered by the resistance of the glycan-peptide bond to enzymatic digestion or β-elimination and have previously concentrated on soluble glycoproteins compatible with lectin affinity and gel-based approaches. We developed strategies for enriching C. jejuni HB93-13 glycopeptides using zwitterionic hydrophilic interaction chromatography and examined novel fragmentation, including collision-induced dissociation (CID) and higher energy collisional (C-trap) dissociation (HCD) as well as CID/electron transfer dissociation (ETD) mass spectrometry. CID/HCD enabled the identification of glycan structure and peptide backbone, allowing glycopeptide identification, whereas CID/ETD enabled the elucidation of glycosylation sites by maintaining the glycan-peptide linkage. A total of 130 glycopeptides, representing 75 glycosylation sites, were identified from LC-MS/MS using zwitterionic hydrophilic interaction chromatography coupled to CID/HCD and CID/ETD. CID/HCD provided the majority of the identifications (73 sites) compared with ETD (26 sites). We also examined soluble glycoproteins by soybean agglutinin affinity and two-dimensional electrophoresis and identified a further six glycosylation sites. This study more than doubles the number of confirmed N-linked glycosylation sites in C. jejuni and is the first to utilize HCD fragmentation for glycopeptide identification with intact glycan. We also show that hydrophobic integral membrane proteins are significant targets of glycosylation in this organism. Our data demonstrate that peptide-centric approaches coupled to novel mass spectrometric fragmentation techniques may be suitable for application to eukaryotic glycoproteins for simultaneous

  10. Effects of density functionals and dispersion interactions on geometries, bond energies and harmonic frequencies of Etbnd UX3 (E = N, P, CH; X = H, F, Cl)

    Science.gov (United States)

    Pandey, Krishna Kumar; Patidar, Pankaj; Patidar, Sunil Kumar; Vishwakarma, Ravi

    2014-12-01

    Quantum-chemical calculations have been performed to evaluate the geometries, bonding nature and harmonic frequencies of the compounds [Etbnd UX3] at DFT, DFT-D3, DFT-D3(BJ) and DFT-dDSc levels using different density functionals BP86, BLYP, PBE, revPBE, PW91, TPSS and M06-L. The stretching frequency of Utbnd N bond in [Ntbnd UF3] calculated with DFT/BLYP closely resembles with the experimental value. The performance of different density functionals for accurate Utbnd N vibrational frequencies follows the order BLYP > revPBE > BP86 > PW91 > TPSS > PBE > M06-L. The BLYP functional gives accurate value of the Utbnd E bond distances. The uranium atom in the studied compounds [Etbnd UX3] is positively charged. Upon going from [Etbnd UF3] to [Etbnd UCl3], the partial Hirshfeld charge on uranium atom decreases because of the lower electronegativity of chlorine compared to flourine. The Gopinathan-Jug bond order for Utbnd E bonds ranges from 2.90 to 3.29. The Utbnd E bond dissociation energies vary with different density functionals as M06-L UX3] are larger than the electrostatic interaction ΔEelstat, which means the Utbnd N bonds in these compound have greater degree of covalent character (in the range 63.8-77.2%). The Usbnd E σ-bonding interaction is the dominant bonding interaction in the nitride and methylidyne complexes while it is weaker in [Ptbnd UX3]. The dispersion energy contributions to the total bond dissociation energies are rather small. Compared to the Grimme's D3(BJ) corrections, the Corminboeuf's dispersion corrections are larger with metaGGA functionals (TPSS, M06-L) while smaller with GGA functionals.

  11. Molecular Dissociation in Presence of a Catalyst II: The bond breaking role of the transition from virtual to localized states

    CERN Document Server

    Ruderman, Andres; Santos, Elizabeth; Pastawski, Horacio Miguel

    2016-01-01

    We address a molecular dissociation mechanism that is known to occur when a H 2 molecule approaches a catalyst with its molecular axis parallel to the surface. It is found that molecular dissociation is a form of quantum dynamical phase transition associated to an ana- lytic discontinuity of quite unusual nature: the molecule is destabilized by the transition from non-physical virtual states into actual local- ized states. Current description complements our recent results for a molecule approaching the catalyst with its molecular axis perpendicu- lar to the surface. Also, such a description can be seen as a further successful implementation of a non-Hermitian Hamiltonian in a well defined model.

  12. Multidimensional Potential Energy Surface for H2 Dissociation over Cu(111)

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Scheffler, Matthias; Jacobsen, Karsten Wedel;

    1994-01-01

    We present ab initio density functional calculations within the generalized gradient approximation for H-2 dissociating over Cu(111). The minimum barrier for dissociation is 0.5 eV and shows large corrugation within the unit cell and a strong dependence on the molecular orientation. Dissociation ...

  13. Fragmentation energetics for angiotensin II and its analogs from time- and energy-resolved surface-induced dissociation studies

    Science.gov (United States)

    Laskin, Julia; Bailey, Thomas H.; Futrell, Jean H.

    2004-05-01

    Surface-induced dissociation (SID) of four model peptides: DRVYIHPF, RVYIHPF, RVYIHAF, and RVYIHDF was studied using a novel Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for SID experiments. The energetics and dynamics of peptide fragmentation were deduced by modeling the time- and energy-resolved survival curves for each precursor ion using an RRKM based approach developed in our laboratory. Accurate dissociation parameters can be obtained from these experiments because collision-energy-resolved SID data are very sensitive to both the energetics and dynamics of dissociation. We found that transition from selective to non-selective fragmentation as ion kinetic energy is increased is associated with a substantial (ca. 0.5 eV) increase in the dissociation energy and a 3-4 orders of magnitude increase in the pre-exponential factor. Dissociation thresholds for angiotensin analogs derived from the experimental data are as follows: 1.62 eV for RVYIHAF and RVYIHPF, 1.14 eV for RVYIHDF and 1.13 eV for DRVYIHPF. Pre-exponential factors of 8.2×1011, 7.2×1012, 3.1×108, and 5.0×107 s-1 were obtained for RVYIHPF, RVYIHAF, RVYIHDF, and DRVYIHPF, respectively. Contribution from shattering to the total decomposition of the precursor ion increases for kinetically hindered fragmentation. The largest contribution is observed for a peptide ion that has the largest negative reaction entropy--DRVYIHPF.

  14. Energy dependence of dissociative J/ψ photoproduction as a signature of gluon saturation at the LHC

    Science.gov (United States)

    Cepila, J.; Contreras, J. G.; Tapia Takaki, J. D.

    2017-03-01

    We have developed a model in which the quantum fluctuations of the proton structure are characterised by hot spots, whose number grows with decreasing Bjorken-x. Our model reproduces the F2 (x ,Q2) data from HERA at the relevant scale, as well as the exclusive and dissociative J / ψ photoproduction data from H1 and ALICE. Our model predicts that for Wγp ≈ 500 GeV, the dissociative J / ψ cross section reaches a maximum and then decreases steeply with energy, which is in qualitatively good agreement to a recent observation that the dissociative J / ψ background in the exclusive J / ψ sample measured in photoproduction by ALICE decreases as energy increases. Our prediction provides a clear signature for gluon saturation at LHC energies.

  15. Energy dependence of dissociative $\\mathrm{J/}\\psi$ photoproduction as a signature of gluon saturation at the LHC

    CERN Document Server

    Cepila, J; Takaki, J D Tapia

    2016-01-01

    We have developed a model in which the quantum fluctuations of the proton structure are characterised by hot spots, whose number grows with decreasing Bjorken-$x$. Our model reproduces the $F_2(x,Q^2)$ data from HERA at the relevant scale, as well as the exclusive and dissociative $\\mathrm{J/}\\psi$ photoproduction data from H1 and ALICE. Our model predicts that for $W_{\\gamma\\mathrm{p}} \\approx 500$ GeV, the dissociative $\\mathrm{J/}\\psi$ cross section reaches a maximum and then decreases steeply with energy, which is in qualitatively good agreement to a recent observation that the dissociative $\\mathrm{J/}\\psi$ background in the exclusive $\\mathrm{J/}\\psi$ sample measured in photoproduction by ALICE decreases as energy increases. Our prediction provides a clear signature for gluon saturation at LHC energies.

  16. The elastic properties, generalized stacking fault energy and dissociated dislocations in MgB2 under different pressure

    KAUST Repository

    Feng, Huifang

    2013-05-31

    The 〈112̄0〉 perfect dislocation in MgB2 is suggested to dissociate into two partial dislocations in an energy favorable way 〈112̄0〉 → 1/2 〈112̄0〉 + SF + 1/2 〈112̄0〉. This dissociation style is a correction of the previous dissociation 〈1000〉 → 1/3 〈11̄00〉 SF + 1/3 〈 2100〉proposed by Zhu et al. to model the partial dislocations and stacking fault observed by transmission electron microscopy. The latter dissociation results in a maximal stacking fault energy rather than a minimal one according to the generalized stacking fault energy calculated from first-principles methods. Furthermore, the elastic constants and anisotropy of MgB2 under different pressure are investigated. The core structures and mobilities of the 〈112̄0〉 dissociated dislocations are studied within the modified Peierls-Nabarro (P-N) dislocation theory. The variational method is used to solve the modified P-N dislocation equation and the Peierls stress is also determined under different pressure. High pressure effects on elastic anisotropy, core structure and Peierls stress are also presented. © 2013 Springer Science+Business Media New York.

  17. Scapulothoracic dissociation: An emerging high-energy trauma in medical literature

    Directory of Open Access Journals (Sweden)

    Andrew McCague

    2012-01-01

    Full Text Available Scapulothoracic dissociation (STD is a devastating consequence of high-energy trauma sustained by the shoulder girdle that can easily result in rapid mortality. Since described by Oreck et al. in 1984, STD has been reported in a handful of journals and individual case series, though is still considered a rare occurrence in the context of shoulder injuries. In this report, we examine the case of a 25-year-old female involved in a high-speed rollover auto accident. Unique to this case was the discovery of a completely transected axillary artery and vein with intracorporeal bleeding and complete avulsion of the ipsilateral brachial plexus requiring immediate ligation of the vessels followed by interval above-elbow-amputation and later glenohumeral disarticulation.

  18. Molecular dissociation in presence of a catalyst: II. The bond breaking role of the transition from virtual to localized states

    Science.gov (United States)

    Ruderman, A.; Dente, A. D.; Santos, E.; Pastawski, H. M.

    2016-08-01

    We address a molecular dissociation mechanism that is known to occur when a H2 molecule approaches a catalyst with its molecular axis parallel to the surface. It is found that molecular dissociation is a form of quantum dynamical phase transition associated to an analytic discontinuity of quite unusual nature: the molecule is destabilized by the transition from non-physical virtual states into actual localized states. Current description complements our recent results for a molecule approaching the catalyst with its molecular axis perpendicular to the surface (Ruderman et al 2015 J. Phys.: Condens. Matter 27 315501). Also, such a description can be seen as a further successful implementation of a non-Hermitian Hamiltonian in a well defined model.

  19. Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes

    KAUST Repository

    Minenkov, Yury

    2015-08-27

    The performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.

  20. Dissociation energies of Ag-RG (RG = Ar, Kr, Xe) and AgO molecules from velocity map imaging studies.

    Science.gov (United States)

    Cooper, Graham A; Kartouzian, Aras; Gentleman, Alexander S; Iskra, Andreas; van Wijk, Robert; Mackenzie, Stuart R

    2015-09-28

    The near ultraviolet photodissociation dynamics of silver atom-rare gas dimers have been studied by velocity map imaging. Ag-RG (RG = Ar, Kr, Xe) species generated by laser ablation are excited in the region of the C ((2)Σ(+))←X ((2)Σ(+)) continuum leading to direct, near-threshold dissociation generating Ag* ((2)P3/2) + RG ((1)S0) products. Images recorded at excitation wavelengths throughout the C ((2)Σ(+))←X ((2)Σ(+)) continuum, coupled with known atomic energy levels, permit determination of the ground X ((2)Σ(+)) state dissociation energies of 85.9 ± 23.4 cm(-1) (Ag-Ar), 149.3 ± 22.4 cm(-1) (Ag-Kr), and 256.3 ± 16.0 cm(-1) (Ag-Xe). Three additional photolysis processes, each yielding Ag atom photoproducts, are observed in the same spectral region. Two of these are markedly enhanced in intensity upon seeding the molecular beam with nitrous oxide, and are assigned to photodissociation of AgO at the two-photon level. These features yield an improved ground state dissociation energy for AgO of 15 965 ± 81 cm(-1), which is in good agreement with high level calculations. The third process results in Ag atom fragments whose kinetic energy shows anomalously weak photon energy dependence and is assigned tentatively to dissociative ionization of the silver dimer Ag2.

  1. Bond length and local energy density property connections for non-transition-metal oxide-bonded interactions.

    Science.gov (United States)

    Gibbs, G V; Spackman, M A; Jayatilaka, D; Rosso, K M; Cox, D F

    2006-11-01

    For a variety of molecules and earth materials, the theoretical local kinetic energy density, G(r(c)), increases and the local potential energy density, V(r(c)), decreases as the M-O bond lengths (M = first- and second-row metal atoms bonded to O) decrease and the electron density, rho(r(c)), accumulates at the bond critical points, r(c). Despite the claim that the local kinetic energy density per electronic charge, G(r(c))/rho(r(c)), classifies bonded interactions as shared interactions when less than unity and closed-shell when greater, the ratio was found to increase from 0.5 to 2.5 au as the local electronic energy density, H(r(c)) = G(r(c)) + V(r(c)), decreases and becomes progressively more negative. The ratio appears to be a measure of the character of a given M-O bonded interaction, the greater the ratio, the larger the value of rho(r(c)), the smaller the coordination number of the M atom and the more shared the bonded interaction. H(r(c))/rho(r(c)) versus G(r(c))/rho(r(c)) scatter diagrams categorize the M-O bonded interactions into domains with the local electronic energy density per electron charge, H(r(c))/rho(r(c)), tending to decrease as the electronegativity differences for the bonded pairs of atoms decrease. The values of G(r(c)) and V(r(c)), estimated with a gradient-corrected electron gas theory expression and the local virial theorem, are in good agreement with theoretical values, particularly for the bonded interactions involving second-row M atoms. The agreement is poorer for shared C-O and N-O bonded interactions.

  2. I. Dissociation free energies in drug-receptor systems via non equilibrium alchemical simulations: theoretical framework

    CERN Document Server

    Procacci, Piero

    2016-01-01

    In this contribution I critically revise the alchemical reversible approach in the context of the statistical mechanics theory of non covalent bonding in drug receptor systems. I show that most of the pitfalls and entanglements for the binding free energies evaluation in computer simulations are rooted in the equilibrium assumption that is implicit in the reversible method. These critical issues can be resolved by using a non-equilibrium variant of the alchemical method in molecular dynamics simulations, relying on the production of many independent trajectories with a continuous dynamical evolution of an externally driven alchemical coordinate, completing the decoupling of the ligand in a matter of few tens of picoseconds rather than nanoseconds. The absolute binding free energy can be recovered from the annihilation work distributions by applying an unbiased unidirectional free energy estimate, on the assumption that any observed work distribution is given by a mixture of normal distributions, whose compone...

  3. PbCNN: A molecule containing Pb≡C bonding

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    In order to predict potential molecules with Pb≡C bonding, we investigated the potential energy sur-face of a tetra-atomic system [PbCN2] at the CCSD(T)//B3LYP level. We found that the linear isomer PbCNN possesses good thermodynamic and kinetic stability. The combined molecular orbital analysis, hydrogenation heat, bond energy and bond dissociation energy all proved that PbCNN is composed of Pb≡ C triple bonding.

  4. PbCNN: A molecule containing Pb≡C bonding

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wen-Bin; SHI Guo-Sheng; DING Yi-Hong; SUN Chia-Chung

    2009-01-01

    In order to predict potential molecules with Pb≡C bonding, we investigated the potential energy sur-face of a tetra-atomic system [PbCN2] at the CCSD(T)//B3LYP level. We found that the linear isomer PbCNN possesses good thermodynamic and kinetic stability. The combined molecular orbital analysis, hydrogenation heat, bond energy and bond dissociation energy all proved that PbCNN is composed of Pb≡C triple bonding.

  5. Reduction in database search space by utilization of amino acid composition information from electron transfer dissociation and higher-energy collisional dissociation mass spectra.

    Science.gov (United States)

    Hansen, Thomas A; Kryuchkov, Fedor; Kjeldsen, Frank

    2012-08-07

    With high-mass accuracy and consecutively obtained electron transfer dissociation (ETD) and higher-energy collisional dissociation (HCD) tandem mass spectrometry (MS/MS), reliable (≥97%) and sensitive fragment ions have been extracted for identification of specific amino acid residues in peptide sequences. The analytical benefit of these specific amino acid composition (AAC) ions is to restrict the database search space and provide identification of peptides with higher confidence and reduced false negative rates. The 6706 uniquely identified peptide sequences determined with a conservative Mascot score of >30 were used to characterize the AAC ions. The loss of amino acid side chains (small neutral losses, SNLs) from the charge reduced peptide radical cations was studied using ETD. Complementary AAC information from HCD spectra was provided by immonium ions. From the ETD/HCD mass spectra, 5162 and 6720 reliable SNLs and immonium ions were successfully extracted, respectively. Automated application of the AAC information during database searching resulted in an average 3.5-fold higher confidence level of peptide identification. In addition, 4% and 28% more peptides were identified above the significance level in a standard and extended search space, respectively.

  6. Identification of lanthionine and lysinoalanine in heat-treated wheat gliadin and bovine serum albumin using tandem mass spectrometry with higher-energy collisional dissociation.

    Science.gov (United States)

    Rombouts, Ine; Lambrecht, Marlies A; Carpentier, Sebastien C; Delcour, Jan A

    2016-04-01

    The present manuscript reports on the identification of various dehydroamino acid-derived bonds and cross-links resulting from thermal treatment (excess water, 240 min, 130 °C) of two model food proteins, bovine serum albumin, and wheat gliadin. S-Carbamidomethylated tryptic and chymotryptic digests of unheated (control) and heated serum albumin and gliadin, respectively, were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-ESI-MS/MS) with higher-energy collisional dissociation (HCD). Heat-induced β-elimination of cystine, serine and threonine, and subsequent Michael addition of cysteine and lysine to dehydroalanine and 3-methyl-dehydroalanine were demonstrated. Lanthionine, lysinoalanine, 3-methyl-lanthionine, and 3-methyl-lysinoalanine were identified. The detection of inter-chain lanthionine in both bovine serum albumin and wheat gliadin suggests the significance of these cross-links for food texture.

  7. Energy-resolved collision-induced dissociation studies of 1,10-phenanthroline complexes of the late first-row divalent transition metal cations: determination of the third sequential binding energies.

    Science.gov (United States)

    Nose, Holliness; Chen, Yu; Rodgers, M T

    2013-05-23

    The third sequential binding energies of the late first-row divalent transition metal cations to 1,10-phenanthroline (Phen) are determined by energy-resolved collision-induced dissociation (CID) techniques using a guided ion beam tandem mass spectrometer. Five late first-row transition metal cations in their +2 oxidation states are examined including: Fe(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+). The kinetic energy dependent CID cross sections for loss of an intact Phen ligand from the M(2+)(Phen)3 complexes are modeled to obtain 0 and 298 K bond dissociation energies (BDEs) after accounting for the effects of the internal energy of the complexes, multiple ion-neutral collisions, and unimolecular decay rates. Electronic structure theory calculations at the B3LYP, BHandHLYP, and M06 levels of theory are employed to determine the structures and theoretical estimates for the first, second, and third sequential BDEs of the M(2+)(Phen)x complexes. B3LYP was found to deliver results that are most consistent with the measured values. Periodic trends in the binding of these complexes are examined and compared to the analogous complexes to the late first-row monovalent transition metal cations, Co(+), Ni(+), Cu(+), and Zn(+), previously investigated.

  8. Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111).

    Science.gov (United States)

    Geweke, Jan; Shirhatti, Pranav R; Rahinov, Igor; Bartels, Christof; Wodtke, Alec M

    2016-08-07

    In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl(v = 0 → 1) and HCl(v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl(v = 2 → 3) channel could not be observed-presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl(v = 0 → 1) excitation probabilities [Q. Ran et al., Phys. Rev. Lett. 98, 237601 (2007)]-50 times smaller than those reported here-were influenced by erroneous assignment of spectroscopic lines used in the data analysis.

  9. Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111)

    Science.gov (United States)

    Geweke, Jan; Shirhatti, Pranav R.; Rahinov, Igor; Bartels, Christof; Wodtke, Alec M.

    2016-08-01

    In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl(v = 0 → 1) and HCl(v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl(v = 2 → 3) channel could not be observed—presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl(v = 0 → 1) excitation probabilities [Q. Ran et al., Phys. Rev. Lett. 98, 237601 (2007)]—50 times smaller than those reported here—were influenced by erroneous assignment of spectroscopic lines used in the data analysis.

  10. Metallic bond effects on mean excitation energies for stopping powers

    Science.gov (United States)

    Wilson, J. W.; Xu, Y. J.

    1982-01-01

    Mean excitation energies for first row metals are evaluated by means of the local plasma approximation. Particle corrections based on Pines' (1953) procedure and the Wigner Seitz (1934) model of the metallic state are included. The agreement with experimental values is remarkably good. In contrast to previous work, the calculations given here estimate shifts in the plasma frequency according to the theory for plane wave states in an extended plasma as calculated by Pines. It is demonstrated that the effects of the metallic bond in lithium and beryllium are quite large and that they appear mainly as a result of collective oscillations in the 'free' electron gas formed from the valence electrons. The usefulness of the plasma frequency shift derived for a degenerate electron gas in predicting the plasma frequency shift within the ion core is considered surprising.

  11. Six-dimensional potential energy surface of the dissociative chemisorption of HCl on Au(111) using neural networks

    Institute of Scientific and Technical Information of China (English)

    LIU TianHui; FU BiNa; ZHANG Dong H

    2014-01-01

    We constructed a six-dimensional potential energy surface(PES)for the dissociative chemisorption of HCl on Au(111)using the neural networks method based on roughly 70000 energies obtained from extensive density functional theory(DFT)calculations.The resulting PES is accurate and smooth,based on the small fitting errors and good agreement between the fitted PES and the direct DFT calculations.Time-dependent wave packet calculations show that the potential energy surface is very well converged with respect to the number of DFT data points,as well as to the fitting process.The dissociation probabilities of HCl initially in the ground rovibrational state from six-dimensional quantum dynamical calculations are quite diferent from the four-dimensional fixed-site calculations,indicating it is essential to perform full-dimensional quantum dynamical studies for the title molecule-surface interaction system.

  12. The effect of translational energy on collision-induced dissociation of highly excited NO 2 on MgO(100)

    Science.gov (United States)

    Arnold, D. W.; Korolik, M.; Wittig, C.; Reisler, H.

    1998-01-01

    Collision-induced dissociation of highly excited NO 2 (i.e., mixed 2B 2/ 2A 1 molecular eigenstates just below D0) impinging on MgO(100) surfaces has been studied as a function of NO 2 internal excitation at an incident translational energy of 4400 cm -1 by using state-selective NO detection. NO internal energy distributions as well as the average energy transferred per activating collision have been obtained. The results, in particular the NO [ 2Π 1/2]/[ 2Π 3/2] population ratios, indicate the presence of exit-channel interactions with the surface that are dependent on collision energy.

  13. Estimation of Intramolecular Hydrogen-bonding Energy via the Substitution Method

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The intramolecular hydrogen-bonding energies for eighteen molecules were calculated based on the substitution method, and compared with those predicted by the cis-trans method.The energy values obtained from two methods are close to each other with a correlation coefficient of 0.96.Furthermore, the hydrogen-bonding energies based on the substitution method are consistent with the geometrical features of intramolecular hydrogen bonds.Both of them demonstrate that the substitution method is capable of providing a good estimation of intramolecular hydrogen-bonding energy.

  14. Calculation of activation energies for hydrogen-atom abstractions by radicals containing carbon triple bonds

    Science.gov (United States)

    Brown, R. L.; Laufer, A. H.

    1981-01-01

    Activation energies are calculated by the bond-energy-bond-order (BEBO) and the bond-strength-bond-length (BSBL) methods for the reactions of C2H radicals with H2, CH4, and C2H6 and for the reactions of CN radicals with H2 and CH4. The BSBL technique accurately predicts the activation energies for these reactions while the BEBO method yields energies averaging 9 kcal higher than those observed. A possible reason for the disagreement is considered.

  15. Dissociation energies of Ag–RG (RG = Ar, Kr, Xe) and AgO molecules from velocity map imaging studies

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, Graham A.; Gentleman, Alexander S.; Iskra, Andreas; Wijk, Robert van; Mackenzie, Stuart R., E-mail: stuart.mackenzie@chem.ox.ac.uk [Physical and Theoretical Chemistry Laboratory, Oxford Chemistry, South Parks Road, Oxford OX1 3QZ (United Kingdom); Kartouzian, Aras [Physical and Theoretical Chemistry Laboratory, Oxford Chemistry, South Parks Road, Oxford OX1 3QZ (United Kingdom); Department of Physical Chemistry, Catalysis Research Center, Technische Universität München, Lichtenbergstr. 4, 85748 Garching (Germany)

    2015-09-28

    The near ultraviolet photodissociation dynamics of silver atom—rare gas dimers have been studied by velocity map imaging. Ag–RG (RG = Ar, Kr, Xe) species generated by laser ablation are excited in the region of the C ({sup 2}Σ{sup +})←X ({sup 2}Σ{sup +}) continuum leading to direct, near-threshold dissociation generating Ag* ({sup 2}P{sub 3/2}) + RG ({sup 1}S{sub 0}) products. Images recorded at excitation wavelengths throughout the C ({sup 2}Σ{sup +})←X ({sup 2}Σ{sup +}) continuum, coupled with known atomic energy levels, permit determination of the ground X ({sup 2}Σ{sup +}) state dissociation energies of 85.9 ± 23.4 cm{sup −1} (Ag–Ar), 149.3 ± 22.4 cm{sup −1} (Ag–Kr), and 256.3 ± 16.0 cm{sup −1} (Ag–Xe). Three additional photolysis processes, each yielding Ag atom photoproducts, are observed in the same spectral region. Two of these are markedly enhanced in intensity upon seeding the molecular beam with nitrous oxide, and are assigned to photodissociation of AgO at the two-photon level. These features yield an improved ground state dissociation energy for AgO of 15 965 ± 81 cm{sup −1}, which is in good agreement with high level calculations. The third process results in Ag atom fragments whose kinetic energy shows anomalously weak photon energy dependence and is assigned tentatively to dissociative ionization of the silver dimer Ag{sub 2}.

  16. Theoretical Electron Density Distributions for Fe- and Cu-Sulfide Earth Materials: A Connection between Bond Length, Bond Critical Point Properties, Local Energy Densities, and Bonded Interactions

    Energy Technology Data Exchange (ETDEWEB)

    Gibbs, Gerald V.; Cox, David F.; Rosso, Kevin M.; Ross, Nancy L.; Downs, R. T.; Spackman, M. A.

    2007-03-01

    Bond critical point and local energy density properties together with net atomic charges were calculated for theoretical electron density distributions, F(r), generated for a variety of Fe and Cu metal-sulfide materials with high- and low-spin Fe atoms in octahedral coordination and high-spin Fe atoms in tetrahedral coordination. The electron density, F(rc), the Laplacian, 32F(rc), the local kinetic energy, G(rc), and the oxidation state of Fe increase as the local potential energy density, V(rc), the Fe-S bond lengths, and the coordination numbers of the Fe atoms decrease. The properties of the bonded interactions for the octahedrally coordinated low-spin Fe atoms for pyrite and marcasite are distinct from those for high-spin Fe atoms for troilite, smythite, and greigite. The Fe-S bond lengths are shorter and the values of F(rc) and 32F(rc) are larger for pyrite and marcasite, indicating that the accumulation and local concentration of F(r) in the internuclear region are greater than those involving the longer, high-spin Fe-S bonded interactions. The net atomic charges and the bonded radii calculated for the Fe and S atoms in pyrite and marcasite are also smaller than those for sulfides with high-spin octahedrally coordinated Fe atoms. Collectively, the Fe-S interactions are indicated to be intermediate in character with the low-spin Fe-S interactions having greater shared character than the highspin interactions. The bond lengths observed for chalcopyrite together with the calculated bond critical point properties are consistent with the formula Cu+Fe3+S2. The bond length is shorter and the F(rc) value is larger for the FeS4 tetrahedron displayed by metastable greigite than those displayed by chalcopyrite and cubanite, consistent with a proposal that the Fe atom in greigite is tetravalent. S-S bond paths exist between each of the surface S atoms of adjacent slabs of FeS6 octahedra comprising the layer sulfide smythite, suggesting that the neutral Fe3S4 slabs are

  17. An isomer-specific high-energy collision-induced dissociation MS/MS database for forensic applications: a proof-of-concept on chemical warfare agent markers.

    Science.gov (United States)

    Subramaniam, Raja; Östin, Anders; Nygren, Yvonne; Juhlin, Lars; Nilsson, Calle; Åstot, Crister

    2011-09-01

    Spectra database search has become the most popular technique for the identification of unknown chemicals, minimizing the need for authentic reference chemicals. In the present study, an isomer-specific high-energy collision-induced dissociation (CID) MS/MS spectra database of 12 isomeric O-hexyl methylphosphonic acids (degradation markers of nerve agents) was created. Phosphonate anions were produced by the electrospray ionization of phosphonic acids or negative-ion chemical ionization of their fluorinated derivatives and were analysed in a hybrid magnetic-sector-time-of-flight tandem mass spectrometer. A centre-of-mass energy (E(com)) of 65 eV led to an optimal sequential carbon-carbon bond breakage, which was interpreted in terms of charge remote fragmentation. The proposed mechanism is discussed in comparison with the routinely used low-energy CID MS/MS. Even-mass (odd-electron) charge remote fragmentation ion series were diagnostic of the O-alkyl chain structure and can be used to interpret unknown spectra. Together with the odd-mass ion series, they formed highly reproducible, isomer-specific spectra that gave significantly higher database matches and probability factors (by 1.5 times) than did the EI MS spectra of the trimethylsilyl derivatives of the same isomers. In addition, ionization by negative-ion chemical ionization and electrospray ionization resulted in similar spectra, which further highlights the general potential of the high-energy CID MS/MS technique.

  18. Performance of an integrated approach for prediction of bond dissociation enthalpies of phenols extracted from ginger and tea

    Science.gov (United States)

    Nam, Pham Cam; Chandra, Asit K.; Nguyen, Minh Tho

    2013-01-01

    Integration of the (RO)B3LYP/6-311++G(2df,2p) with the PM6 method into a two-layer ONIOM is found to produce reasonably accurate BDE(O-H)s of phenolic compounds. The chosen ONIOM model contains only two atoms of the breaking bond as the core zone and is able to provide reliable evaluation for BDE(O-H) for phenols and tocopherol. Deviation of calculated values from experiment is ±(1-2) kcal/mol. BDE(O-H) of several curcuminoids and flavanoids extracted from ginger and tea are computed using the proposed model. The BDE(O-H) values of enol curcumin and epigallocatechin gallate are predicted to be 83.3 ± 2.0 and 76.0 ± 2.0 kcal/mol, respectively.

  19. Dissociation energies of AgRG (RG = Ar, Kr, Xe) and AgO molecules from velocity map imaging studies

    CERN Document Server

    Cooper, Graham A; Gentleman, Alexander S; Iskra, Andreas; van Wijk, Robert; Mackenzie, Stuart R

    2015-01-01

    The near ultraviolet photodissociation dynamics of silver atom rare gas dimers have been studied by velocity map imaging. AgRG (RG = Ar, Kr, Xe) species generated by laser ablation are excited in the region of the C <- X continuum leading to direct, near threshold dissociation generating Ag* (2P3/2) + RG (1S0) products. Images recorded at excitation wavelengths throughout the C <- X continuum, coupled with known atomic energy levels, permit determination of the ground X (2SIGMA+) state dissociation energies of 85.9 +/- 23.4 cm-1 (AgAr), 149.3 +/- 22.4 cm-1 (AgKr) and 256.3 +/- 16.0 cm-1 (AgXe). Three additional photolysis processes, each yielding Ag atom photoproducts, are observed in the same spectral region. Two of these are markedly enhanced in intensity upon seeding the molecular beam with nitrous oxide, and are assigned to photodissociation of AgO at the two photon level. These features yield an improved ground state dissociation energy for AgO of 15965 +/- 81 cm-1, which is in good agreement with ...

  20. Evaluation of the Rh(II)-Rh(II) bond dissociation enthalpy for [(TMTAA)Rh]2 by 1H NMR T2 measurements: application in determining the Rh-C(O)- BDE in [(TMTAA)Rh]2C═O.

    Science.gov (United States)

    Imler, Gregory H; Zdilla, Michael J; Wayland, Bradford B

    2013-10-07

    Toluene solutions of the rhodium(II) dimer of dibenzotetramethylaza[14]annulene ([(TMTAA)Rh]2; (1)) manifest an increase in the line widths for the singlet methine and methyl (1)H NMR resonances with increasing temperature that result from the rate of dissociation of the diamagnetic Rh(II)-Rh(II) bonded dimer (1) dissociating into paramagnetic Rh(II) monomers (TMTAA) Rh (2). Temperature dependence of the rates of Rh(II)-Rh(II) dissociation give the activation parameters for bond homolysis ΔH(‡)(app) = 24(1) kcal mol(-1) and ΔS(‡)(app) = 10 (1) cal K(-1) mol(-1) and an estimate for the Rh(II)-Rh(II) bond dissociation enthalpy (BDE) of 22 kcal mol(-1). Thermodynamic values for reaction of 1 with CO to form (TMTAA)Rh-C(O)-Rh(TMTAA) (3) ΔH1° = -14 (1) kcal mol(-1), ΔS1°= -30(3) cal K(-1) mol(-1)) were used in deriving a (TMTAA)Rh-C(O)- BDE of 53 kcal mol(-1).

  1. Interstellar Isomers: The Importance of Bonding Energy Differences

    CERN Document Server

    Remijan, A J; Lovas, F J; Plusquellic, D F; Jewell, P R; Remijan, Anthony J.

    2005-01-01

    We present strong detections of methyl cyanide, vinyl cyanide, ethyl cyanide and cyanodiacetylene molecules with the Green Bank Telescope (GBT) toward the Sgr B2(N) molecular cloud. Attempts to detect the corresponding isocyanide isomers were only successful in the case of methyl isocyanide for its J(K)=1(0)-0(0) transition, which is the first interstellar report of this line. To determine the spatial distribution of methyl isocyanide, we used archival Berkeley-Illinois-Maryland Association (BIMA) array data for the J(K)=4(K)-3(K) (K=0-3) transitions but no emission was detected. From ab initio calculations, the bonding energy difference between the cyanide and isocyanide molecules is >8500 cm^-1 (>12,000 K). That we detect methyl isocyanide emission with a single antenna (Gaussian beamsize(Omega_B)=1723 arcsec^2) but not with an interferometer (Omega_B=192 arcsec^2), strongly suggests that methyl isocyanide has a widespread spatial distribution toward the Sgr B2(N) region. Thus, large-scale, non-thermal proc...

  2. Structures, energies and bonding in neutral and charged Li microclusters.

    Science.gov (United States)

    Yepes, Diana; Kirk, Steven Robert; Jenkins, Samantha; Restrepo, Albeiro

    2012-09-01

    Structural and chemical properties of charged and neutral Lithium microclusters are investigated for [Formula: see text]. A total of 18 quantum conformational spaces are randomly walked to produce candidate structures for local minima. Very rich potential energy surfaces are produced, with the largest structural complexity predicted for anionic clusters. Analysis of the electron charge distributions using the quantum theory of atoms in molecules (QTAIM) predicts major stabilizing roles of Non-nuclear attractors (NNAs) via NNA···Li interactions with virtually no direct Li···Li interactions, except in the least stable configurations. A transition in behavior for clusters containing more than seven nuclei is observed by using the recently introduced quantum topology to determine in a quantum mechanically consistent fashion the number of spatial dimensions each cluster has. We experiment with a novel scheme for extracting persistent structural motifs with increase in cluster size. The new structural motifs correlate well with the energetic stability, particularly in highlighting the least stable structures. Quantifying the degree of covalent character in Lithium bonding independently agrees with the observation in the transition in cluster behavior for lithium clusters containing more than seven nuclei. Good correlation with available experimental data is obtained for all properties reported in this work.

  3. Vibrational and Electronic Energy Transfer and Dissociation of Diatomic Molecules by Electron Collisions

    Science.gov (United States)

    Huo, Winifred M.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    At high altitudes and velocities equal to or greater than the geosynchronous return velocity (10 kilometers per second), the shock layer of a hypersonic flight will be in thermochemical nonequilibrium and partially ionized. The amount of ionization is determined by the velocity. For a trans atmospheric flight of 10 kilometers per second and at an altitude of 80 kilometers, a maximum of 1% ionization is expected. At a velocity of 12 - 17 kilometer per second, such as a Mars return mission, up to 30% of the atoms and molecules in the flow field will be ionized. Under those circumstances, electrons play an important role in determining the internal states of atoms and molecules in the flow field and hence the amount of radiative heat load and the distance it takes for the flow field to re-establish equilibrium. Electron collisions provide an effective means of transferring energy even when the electron number density is as low as 1%. Because the mass of an electron is 12,760 times smaller than the reduced mass of N2, its average speed, and hence its average collision frequency, is more than 100 times larger. Even in the slightly ionized regime with only 1% electrons, the frequency of electron-molecule collisions is equal to or larger than that of molecule-molecule collisions, an important consideration in the low density part of the atmosphere. Three electron-molecule collision processes relevant to hypersonic flows will be considered: (1) vibrational excitation/de-excitation of a diatomic molecule by electron impact, (2) electronic excitation/de-excitation, and (3) dissociative recombination in electron-diatomic ion collisions. A review of available data, both theory and experiment, will be given. Particular attention will be paid to tailoring the molecular physics to the condition of hypersonic flows. For example, the high rotational temperatures in a hypersonic flow field means that most experimental data carried out under room temperatures are not applicable. Also

  4. Energy- and Time-Dependent Branching to Competing Paths in Coupled Unimolecular Dissociations of Chlorotoluene Radical Cations

    Energy Technology Data Exchange (ETDEWEB)

    Seo, Jongcheol; Shin, Seung Koo [Pohang Univ. of Science and Technology, Pohang (Korea, Republic of); Kim, Seung Joon [Hannam Univ., Daejeon (Korea, Republic of)

    2014-03-15

    The energy- and time-dependent branching to the competing dissociation paths are studied by theory for coupled unimolecular dissociations of the o-, m-, and p-chlorotoluene radical cations to C{sub 7}H{sub 7}{sup +} (benzylium and tropylium). There are four different paths to C{sub 7}H{sub 7}{sup +}, three to the benzylium ion and one to the tropylium ion, and all of them are coupled together. The branching to the multiple paths leads to the multiexponential decay of reactant with the branching ratio depending on both internal energy and time. To gain insights into the multipath branching, we study the detailed kinetics as a function of time and internal energy on the basis of ab inito/RRKM calculations. The number of reaction steps to C{sub 7}H{sub 7}{sup +} is counted for each path. Of the three isomers, the meta mostly goes through the coupling, whereas the para proceeds with little or no coupling. In the beginning, some reactants with high internal energy decay fast to the benzylium ion without any coupling and others rearrange to the other isomers. Later on all three isomers dissociate to the products via long-lived intermediates. Thus, the reactant shows a multiexponential decay and the branching ratio varies with time as the average internal energy decreases with time. The reciprocal of the effective lifetime is taken as the rate constant. The resulting rate-energy curves are in line with experiments. The present results suggest that the coupling between the stable isomers is thermodynamically controlled, whereas the branching to the product is kinetically controlled.

  5. Dissociative scattering of low-energy SiF{sub 3}{sup +} and SiF{sup +} ions (5-200 eV) on Cu(100) surface

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Hiroyuki; Baba, Yuji; Sasaki, T.A. [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1997-03-01

    Dissociative scattering of molecular SiF{sub 3}{sup +} and SiF{sup +} ions from a Cu(100) single crystal surface has been investigated in the incident energy range from 5 eV to 200 eV with a scattering angle of 77deg. The scattered ion intensity of dissociative ions and parent molecular ions were measured as a function of incident ion energy. The observed data show that onset energies of dissociation for SiF{sub 3}{sup +} and SiF{sup +} ions are 30 eV and 40 eV, respectively. The obtained threshold energies are consistent with a impulsive collision model where the dissociation of incident ion is caused by vibrational excitation during collision. (author)

  6. Ab initio calculation of accurate dissociation energy,potential energy curve and dipole moment function for the A1∑+ state 7LiH molecule

    Institute of Scientific and Technical Information of China (English)

    Shi De-Heng; Liu Yu-Fang; Sun Jin-Feng; Yang Xiang-Dong; Zhu Zun-Lue

    2006-01-01

    The reasonable dissociation limit of the A1∑+ state 7LiH molecule is obtained. The accurate dissociation energy and the equilibrium geometry of this state are calculated using a symmetry-adapted-cluster configuration-interaction method in complete active space for the first time. The whole potential energy curve and the dipole moment function for the A1∑+ state are calculated over a wide internuclear separation range from about 0.1 to 1.4 nm. The calculated equilibrium geometry and dissociation energy of this potential energy curve are of Re=0.2487 nm and De=1.064 eV,respectively. The unusual negative values of the anharmonicity constant and the vibration-rotational coupling constant are of wexe=-4.7158cm-1 and αe=-0.08649cm-1, respectively. The vertical excitation energy from the ground to the A1∑+ state is calculated and the value is of 3.613eV at 0.15875nm (the equilibrium position of the ground state).The highly anomalous shape of this potential energy curve, which is exceptionally flat over a wide radial range around the equilibrium position, is discussed in detail. The harmonic frequency value of 502.47cm-1 about this state is approximately estimated. Careful comparison of the theoretical determinations with those obtained by previous theories about the A1∑+ state dissociation energy clearly shows that the present calculations are much closer to the experiments than previous theories, thus represents an improvement.

  7. Ab initio calculations of accurate dissociation energy and analytic potential energy function for the second excited state B1П of 7LiH

    Institute of Scientific and Technical Information of China (English)

    Shi De-Heng; Liu Yu-Fang; Sun Jin-Feng; Zhu Zun-Lùe; Yang Xiang-Dong

    2006-01-01

    The reasonable dissociation limit of the second excited singlet state B1П of 7LiH molecule is obtained. The obtained over the internuclear distance ranging from about 0.10 nm to 0.54 nm, and has a least-square fit to the analytic compared with previous theoretical results. The equilibrium internuclear distance obtained by geometry optimization is found to be quite different from that obtained by single-point energy scanning under the same calculation condition.comparison of the theoretical calculations of dissociation energies, equilibrium interatomic distances and the analytic potential energy function with those obtained by previous theoretical results clearly shows that the present work is more theories.

  8. Evaluation of the individual hydrogen bonding energies in N-methylacetamide chains

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The individual hydrogen bonding energies in N-methylacetamide chains were evaluated at the MP2/6-31+G** level including BSSE correction and at the B3LYP/6-311++G(3df,2pd) level including BSSE and van der Waals correction.The calculation results indicate that compared with MP2 results,B3LYP calculations without van der Waals correction underestimate the individual hydrogen bonding energies about 5.4 kJ m ol-1 for both the terminal and central hydrogen bonds,whereas B3LYP calculations with van der Waals correction produce almost the same individual hydrogen bonding energies as MP2 does for those terminal hydrogen bonds,but still underestimate the individual hydrogen bonding energies about 2.5 kJ mol-1 for the hydrogen bonds near the center.Our calculation results show that the individual hydrogen bonding energy becomes more negative (more attractive) as the chain becomes longer and that the hydrogen bonds close to the interior of the chain are stronger than those near the ends.The weakest individual hydrogen bonding energy is about-29.0 kJ m ol-1 found in the dimer,whereas with the growth of the N-methylacetamide chain the individual hydrogen bonding energy was estimated to be as large as-62.5 kJ mol-1 found in the N-methylacetamide decamer,showing that there is a significant hydrogen bond cooperative effect in N-methylacetamide chains.The natural bond orbital analysis indicates that a stronger hydrogen bond corresponds to a larger positive charge for the H atom and a larger negative charge for the O atom in the N-H···O=C bond,corresponds to a stronger second-order stabilization energy between the oxygen lone pair and the N-H antibonding orbital,and corresponds to more charge transfer between the hydrogen bonded donor and acceptor molecules.

  9. Thermochemical properties of methyl-substituted cyclic alkyl ethers and radicals for oxiranes, oxetanes, and oxolanes: C-H bond dissociation enthalpy trends with ring size and ether site.

    Science.gov (United States)

    Auzmendi-Murua, Itsaso; Charaya, Sumit; Bozzelli, Joseph W

    2013-01-17

    Cyclic ethers are an important product from the gas-phase reactions of hydrocarbon radicals with molecular oxygen in the atmospheric chemistry of diolefins and in low to moderate temperature combustion and oxidation reaction systems. They are also important in organic synthesis. Structures, and fundamental thermochemical parameters-enthalpy (ΔH°(f,298)), entropy (S°(298)), and heat capacity (C(p)(T))-have been calculated for a series of cyclic alkyl ethers and their carbon centered radicals. Enthalpies of formation (ΔH°(f,298)) are determined at the B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p), and CBS-QB3 levels using several work reactions for each species. Entropy (S) and heat capacity (C(p)(T)) values from vibration, translational, and external rotational contributions are calculated using the rigid-rotor-harmonic-oscillator approximation based on the vibration frequencies and structures obtained from the density functional studies. Contributions from the internal methyl rotors are substituted for torsion frequencies. Calculated enthalpies of formation for a series of 12 cyclic ethers and methyl substituted cyclic ethers are in good agreement with available literature values. C-H bond dissociation enthalpies are reported for 28 carbon sites of 3 to 5 member ring cyclic ethers for use in understanding effects of the ring and the ether oxygen on kinetics and stability. Trends in carbon-hydrogen bond energies for the ring and methyl substituents relative to ring size and to distance from the ether group are described.

  10. Rate coefficients for low-energy electron dissociative attachment to molecular hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Horacek, J.; Houfek, K.; Cizek, M. [Charles University, Faculty of Mathematics and Physics, Prague (Czech Republic); Murakami, I.; Kato, T. [National Inst. for Fusion Science, Toki, Gifu (Japan)

    2003-02-01

    Calculation of rate constants for dissociative electron attachment to molecular hydrogen is reported. The calculation is based on an improved nonlocal resonance model of Cizek, Horacek and Domcke which takes fully into account the nonlocality of the resonance dynamics and uses potentials with correct asymptotic forms. The rate constants are calculated for all quantum numbers v and J of the target molecules and for electron temperature in the range 0-30000 K. (author)

  11. Block-Localized Density Functional Theory (BLDFT), Diabatic Coupling, and Their Use in Valence Bond Theory for Representing Reactive Potential Energy Surfaces.

    Science.gov (United States)

    Cembran, Alessandro; Song, Lingchun; Mo, Yirong; Gao, Jiali

    2009-10-13

    A multistate density functional theory in the framework of the valence bond model is described. The method is based on a block-localized density functional theory (BLDFT) for the construction of valence-bond-like diabatic electronic states and is suitable for the study of electron transfer reactions and for the representation of reactive potential energy surfaces. The method is equivalent to a valence bond theory with the treatment of the localized configurations by using density functional theory (VBDFT). In VBDFT, the electron densities and energies of the valence bond states are determined by BLDFT. A functional estimate of the off-diagonal matrix elements of the VB Hamiltonian is proposed, making use of the overlap integral between Kohn-Sham determinants and the exchange-correlation functional for the ground state substituted with the transition (exchange) density. In addition, we describe an approximate approach, in which the off-diagonal matrix element is computed by wave function theory using block-localized Kohn-Sham orbitals. The key feature is that the electron density of the adiabatic ground state is not directly computed nor used to obtain the ground-state energy; the energy is determined by diagonalization of the multistate valence bond Hamiltonian. This represents a departure from the standard single-determinant Kohn-Sham density functional theory. The multistate VBDFT method is illustrated by the bond dissociation of H2+ and a set of three nucleophilic substitution reactions in the DBH24 database. In the dissociation of H2+, the VBDFT method yields the correct asymptotic behavior as the two protons stretch to infinity, whereas approximate functionals fail badly. For the S(N)2 nucleophilic substitution reactions, the hybrid functional B3LYP severely underestimates the barrier heights, while the approximate two-state VBDFT method overcomes the self-interaction error, and overestimates the barrier heights. Inclusion of the ionic state in a three

  12. Theoretical Electric Dipole Moments and Dissociation Energies for the Ground States of GaH-BrH

    Science.gov (United States)

    Pettersson, Lars G. M.; Langhoff, Stephen R.

    1986-01-01

    Reliable experimental diople moments are available for the ground states of SeH and BrH whereas no values have been reported for GaH and AsH a recently reported experimental dipole moment for GeH of 1.24 + or -0.01 D has been seriously questioned, and a much lower value of, 0.1 + or - 0.05 D, suggested. In this work, we report accurate theoretical dipole moments, dipole derivatives, dissociation energies, and spectroscopic constants (tau(sub e), omega(sub e)) for the ground states of GaH through BrH.

  13. Comparative anti-inflammatory activities of curcumin and tetrahydrocurcumin based on the phenolic O-H bond dissociation enthalpy, ionization potential and quantum chemical descriptor.

    Science.gov (United States)

    Murakami, Yukio; Ishii, Hiroaki; Takada, Naoki; Tanaka, Shoji; Machino, Mamoru; Ito, Shigeru; Fujisawa, Seiichiro

    2008-01-01

    Curcumin and its reduced derivative tetrahydrocurcumin have been shown to exhibit chemopreventive activity. Cyclooxygenase-2 (COX-2) inhibition in lipopolysaccharide (LPS)- or Porphyromonas gingivalis fimbria-stimulated RAW 264.7 cells was investigated using Northern blot analysis. The fimbria-stimulated expression of the COX-2 gene was inhibited by curcumin but not by tetrahydrocurcumin. LPS-stimulated COX-2 gene expression was completely inhibited by curcumin, but an increase in the concentration of tetrahydrocurcumin did not cause complete inhibition of COX-2 expression. The inhibitory effect of curcumin on nuclear factor kappa B (NF-kappaB) activation in the cells was clearly observed, but that of tetrahydrocurcumin was incomplete even at a concentration of 20 microM. To explain the difference in effect between the two compounds, analysis of the frontier orbital was performed using ab initio 6-31G* wave function. The calculated chemical hardness (eta) for curcumin was clearly smaller, whereas its electronegativity (chi) and electrophilicity (omega) were clearly greater than the corresponding values for the curcumin-related compounds tetrahydrocurcumin, isoeugenol and eugenol. This suggested that the anti-inflammatory activities of curcumin may be related to eta-, chi- and/or omega-controlled enzymes. In addition, the bond dissociation enthalpy (BDE) of the phenolic OH was calculated using the density function theory (DFT)/B3LY. The total BDE values of curcumin and tetrahydrocurcumin were almost identical, but the BDE of one-electron oxidation and ionization potential (IP) for curcumin were lower than those for tetrahydrocurcumin, suggesting the highly pro-oxidative activity of curcumin. Curcumin has both oxidant and antioxidant properties. A causal link between the anti-inflammatory activities and molecular properties of phenolic antioxidants is suggested.

  14. Threshold collision-induced dissociation of Sr(2+)(H(2)O)(x) complexes (x=1-6): An experimental and theoretical investigation of the complete inner shell hydration energies of Sr(2+).

    Science.gov (United States)

    Carl, D R; Chatterjee, B K; Armentrout, P B

    2010-01-28

    The sequential bond energies of Sr(2+)(H(2)O)(x) complexes, where x=1-6, are determined by threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer equipped with an electrospray ionization source. The electrospray source produces an initial distribution of Sr(2+)(H(2)O)(x) complexes, where x=6-9. Smaller Sr(2+)(H(2)O)(x) complexes, where x=1-5, are accessed using a recently developed in-source fragmentation technique that takes place in the high pressure region of a rf-only hexapole ion guide. This work constitutes the first experimental study for the complete inner shell of any multiply charged ion. The kinetic energy dependent cross sections are determined over a wide energy range to monitor all possible dissociation products and are modeled to obtain 0 and 298 K binding energies for loss of a single water molecule. These binding energies decrease monotonically for the Sr(2+)(H(2)O) complex to Sr(2+)(H(2)O)(6). Our experimental results agree well with previous literature results obtained by equilibrium and kinetic studies for x=5 and 6. Because there has been limited theory for the hydration of Sr(2+), we also present an in-depth theoretical study on the energetics of the Sr(2+)(H(2)O)(x) systems by employing several levels of theory with multiple effective core potentials for Sr and different basis sets for the water molecules.

  15. How universal are hydrogen bond correlations? A density functional study of intramolecular hydrogen bonding in low-energy conformers of α-amino acids

    Science.gov (United States)

    Ramaniah, Lavanya M.; Kamal, C.; Kshirsagar, Rohidas J.; Chakrabarti, Aparna; Banerjee, Arup

    2013-10-01

    Hydrogen bonding is one of the most important and ubiquitous interactions present in Nature. Several studies have attempted to characterise and understand the nature of this very basic interaction. These include both experimental and theoretical investigations of different types of chemical compounds, as well as systems subjected to high pressure. The O-H..O bond is of course the best studied hydrogen bond, and most studies have concentrated on intermolecular hydrogen bonding in solids and liquids. In this paper, we analyse and characterise normal hydrogen bonding of the general type, D-H...A, in intramolecular hydrogen bonding interactions. Using a first-principles density functional theory approach, we investigate low energy conformers of the twenty α-amino acids. Within these conformers, several different types of intramolecular hydrogen bonds are identified. The hydrogen bond within a given conformer occurs between two molecular groups, either both within the backbone itself, or one in the backbone and one in the side chain. In a few conformers, more than one (type of) hydrogen bond is seen to occur. Interestingly, the strength of the hydrogen bonds in the amino acids spans quite a large range, from weak to strong. The signature of hydrogen bonding in these molecules, as reflected in their theoretical vibrational spectra, is analysed. With the new first-principles data from 51 hydrogen bonds, various parameters relating to the hydrogen bond, such as hydrogen bond length, hydrogen bond angle, bond length and vibrational frequencies are studied. Interestingly, the correlation between these parameters in these bonds is found to be in consonance with those obtained in earlier experimental studies of normal hydrogen bonds on vastly different systems. Our study provides some of the most detailed first-principles support, and the first involving vibrational frequencies, for the universality of hydrogen bond correlations in materials.

  16. Experimental investigation of the complete inner shell hydration energies of Ca2+: threshold collision-induced dissociation of Ca(2+)(H2O)x Complexes (x = 2-8).

    Science.gov (United States)

    Carl, Damon R; Armentrout, P B

    2012-04-19

    The sequential bond energies of Ca(2+)(H(2)O)(x) complexes, where x = 1-8, are measured by threshold collision-induced dissociation (TCID) in a guided ion beam tandem mass spectrometer. From an electrospray ionization source that produces an initial distribution of Ca(2+)(H(2)O)(x) complexes where x = 6-8, complexes down to x = 2 are formed using an in-source fragmentation technique. Ca(2+)(H(2)O) cannot be formed in this source because charge separation into CaOH(+) and H(3)O(+) is a lower energy pathway than simple water loss from Ca(2+)(H(2)O)(2). The kinetic energy dependent cross sections for dissociation of Ca(2+)(H(2)O)(x) complexes, where x = 2-9, are examined over a wide energy range to monitor all dissociation products and are modeled to obtain 0 and 298 K binding energies. Analysis of both primary and secondary water molecule losses from each sized complex provides thermochemistry for the sequential hydration energies of Ca(2+) for x = 1-8 and the first experimental values for x = 1-4. Additionally, the thermodynamic onsets leading to the charge separation products from Ca(2+)(H(2)O)(2) and Ca(2+)(H(2)O)(3) are determined for the first time. Our experimental results for x = 1-6 agree well with previously calculated binding enthalpies as well as quantum chemical calculations performed here. Agreement for x = 1 is improved when the basis set on calcium includes core correlation.

  17. Threshold collision-induced dissociation of hydrated magnesium: experimental and theoretical investigation of the binding energies for Mg(2+)(H2O)x complexes (x=2-10).

    Science.gov (United States)

    Carl, Damon R; Armentrout, Peter B

    2013-03-18

    The sequential bond energies of Mg(2+)(H2O)x complexes, in which x=2-10, are measured by threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer. From an electrospray ionization source that produces an initial distribution of Mg(2+)(H2O)x complexes in which x=7-10, complexes down to x=3 are formed by using an in-source fragmentation technique. Complexes smaller than Mg(2+)(H2O)3 cannot be formed in this source because charge separation into MgOH(+)(H2O) and H3O(+) is a lower-energy pathway than simple water loss from Mg(2+)(H2O)3. The kinetic energy dependent cross sections for dissociation of Mg(2+)(H2O)x complexes, in which x=3-10, are examined over a wide energy range to monitor all dissociation products and are modeled to obtain 0 and 298 K binding energies. Analysis of both primary and secondary water molecule losses from each sized complex provides thermochemistry for the sequential hydration energies of Mg(2+) for x=2-10 and the first experimental values for x=2-4. Additionally, the thermodynamic onsets leading to the charge-separation products from Mg(2+)(H2O)3 and Mg(2+)(H2O)4 are determined for the first time. Our experimental results for x=3-7 agree well with quantum chemical calculations performed here and previously calculated binding enthalpies, as well as previous measurements for x=6. The present values for x=7-10 are slightly lower than previous experimental results and theory, but within experimental uncertainties.

  18. Characterization of the thermosonic wire bonding technique. [Combination of ultrasonic energy and thermocompression

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, D.R.; Chavez, E.L.

    1976-01-01

    This study was designed to evaluate the combination of ultrasonic energy and thermocompression techniques with regard to the bond response of thin film substrate metallization and thick film discrete component terminations. The object was to determine not only the quality of thermosonic gold wire bonds and the performance of these bonds when subjected to thermal environmental tests, but also to determine the process control parameters necessary to produce repeatable, reliable bonds. Comparison was made throughout the study with regard to results previously achieved on the same metallization systems using standard fine wire themocompression bonding techniques. It was concluded that the thermosonic wire bonding technique offered the advantages of lower bonding forces and lower substrate temperatures compared to the thermocompression process. In addition, it was determined that the thermosonic technique eliminates the need for special pre-bond etching and cleaning procedures presently used in production of Sandia hybrid microcircuits. Finally, a wide latitude in bonding parameters was realized with the thermosonic technique, and this was considered advantageous compared to the rigid process controls necessary for thermocompression bonding. (auth)

  19. Dissociative Ionization Mechanism and Appearance Energies in Adipic Acid Revealed by Imaging Photoelectron Photoion Coincidence, Selective Deuteration, and Calculations.

    Science.gov (United States)

    Heringa, Maarten F; Slowik, Jay G; Prévôt, André S H; Baltensperger, Urs; Hemberger, Patrick; Bodi, Andras

    2016-05-26

    Adipic acid, a model compound for oxygenated organic aerosol, has been studied at the VUV beamline of the Swiss Light Source. Internal energy selected cations were prepared by threshold photoionization using vacuum ultraviolet synchrotron radiation and imaging photoelectron photoion coincidence spectroscopy (iPEPICO). The threshold photoelectron spectrum yields a vertical ionization energy (IE) of 10.5 eV, significantly above the calculated adiabatic IE of 8.6 eV. The cationic minimum is accessible after vertical ionization by H-transfer from one of the γ-carbons to a carbonyl oxygen and is sufficiently energetic to decay by water loss at the ionization onset. The slope of the breakdown curves, quantum chemical calculations, and selective deuteration of the carboxylic hydrogens establish the dissociative photoionization mechanism. After ionization, one γ-methylene hydrogen and the two carboxylic hydrogens are randomized prior to H2O loss. On the basis of the deuteration degree in the H2O + CO-loss product at higher energies, a direct water-loss channel without complete randomization also exists. The breakdown diagram and center of gravity of the H2O + CO-loss peak were modeled to obtain 0 K appearance energies of 10.77, 10.32, and 11.53 eV for H2O + CO loss, CH2COOH loss, and H2O + CH2COOH loss from adipic acid. These agree well with the CBS-QB3 calculated values of 10.68, 10.45, and 11.57 eV, respectively, which shows that threshold photoionization can yield energetics data as long as the dissociation is statistical, even when the parent ion cannot be observed. The results can be used as a starting point for a deeper understanding of the ionization and low-energy fragmentation of organic aerosol components.

  20. Calculation of Bond-length, Bond-energy and Force Constant of Hydrogen Molecule by Classical Mechanics

    Institute of Scientific and Technical Information of China (English)

    ChenJing

    2004-01-01

    Until recently the hydrogen molecule structural parameters are calculated with the methods of quantum mechanics. To achieve results close to experimental values, the wave function used is complicated and has no clear physical meaning. Because the distribution of the electron probability density is a statistical rule, the macro-time has actually been used in the concept on a electron cloud graph. Here are obtained three formulas with a classical mechanics method on the bond-length re , bond-energy De and force constant k of the ground state hydrogen molecule, which have a clear physical meaning but no artificial parameters, and compared with experimental values, the relative errors are respectively less than 1% , 2% and 4% .

  1. Bond Graph Modeling and Validation of an Energy Regenerative System for Emulsion Pump Tests

    Directory of Open Access Journals (Sweden)

    Yilei Li

    2014-01-01

    Full Text Available The test system for emulsion pump is facing serious challenges due to its huge energy consumption and waste nowadays. To settle this energy issue, a novel energy regenerative system (ERS for emulsion pump tests is briefly introduced at first. Modeling such an ERS of multienergy domains needs a unified and systematic approach. Bond graph modeling is well suited for this task. The bond graph model of this ERS is developed by first considering the separate components before assembling them together and so is the state-space equation. Both numerical simulation and experiments are carried out to validate the bond graph model of this ERS. Moreover the simulation and experiments results show that this ERS not only satisfies the test requirements, but also could save at least 25% of energy consumption as compared to the original test system, demonstrating that it is a promising method of energy regeneration for emulsion pump tests.

  2. 取代基效应对褐煤模型化合物离解焓影响的理论研究%Theoretical Study of Substituent Effects on Bond Dissociation Enthalpies in Lignite Model Compounds

    Institute of Scientific and Technical Information of China (English)

    王新华; 冯莉; 曹泽星; 刘祥春; 汤海燕; 张曼

    2013-01-01

    为了探究褐煤热解过程中氧桥键C-O均裂这一重要反应,选取a-O-4和-O-4类结构单元作为褐煤模型化合物,运用不同密度泛函计算了部分模型化合物中C-O的离解焓,并以CBS-QB3作为理论基准值进行比较,最后选取M05-2X进行离解焓计算.结果显示,对于选定的a-O-4和-O-4类模型化合物,其平均离解焓分别为51.0 kcal/mol和66.1kcal/mol.周围取代环境能显著影响C-O离解焓,芳环上存在给电子基团(OH,OCH3和CH3)能降低C-O离解焓,而吸电子基团COOH则能增加其离解焓.然后深层次分析了取代基效应对C-O离解焓的影响.此外,分子内氢键的形成对离解焓也有很大的影响.C-O的离解焓与其键长没有特定的相关性,不能简单的通过C-O键长来预测其离解焓.%Lignite is an abundant natural resource that is a potential source of clean fuel and value-added chemicals.The mechanisms by which thermal and catalytic treatments deconstruct lignite remain elusive,which is where quantum mechanical calculations can offer fundamental insights.In order to investigate the cleavage of C-O bridge bond,which is the critical step in the thermal decomposition of lignite,the α-O-4 and β-O-4 types of structural units are selected as lignite model compounds to calculate the C-O bond dissociation enthalpies using several kinds of density functional theory methods (B3PW91,B3P86,PBE1PBE,BMK,M06-2X and M05-2X) at 6-3 l+G(d,p) level.By the comparison between the results and the theoretical benchmark values provided by CBS-QB3 method,M05-2X functional was applied for the calculations on C-O bond dissociation enthalpies.The present results indicate that the C-O average bond dissociation enthalpies are 51.0 kcal/mol and 66.1 kcal/mol for the α-O-4 and β-O-4 types of model compounds,respectively.Local substituents have a great effect on the C-O bond dissociation enthalpies,the C-O bond dissociation enthalpies will decrease when the adjacent arene rings are

  3. A Novel Method to Quantify Soil Aggregate Stability by Measuring Aggregate Bond Energies

    Science.gov (United States)

    Efrat, Rachel; Rawlins, Barry G.; Quinton, John N.; Watts, Chris W.; Whitmore, Andy P.

    2016-04-01

    Soil aggregate stability is a key indicator of soil quality because it controls physical, biological and chemical functions important in cultivated soils. Micro-aggregates are responsible for the long term sequestration of carbon in soil, therefore determine soils role in the carbon cycle. It is thus vital that techniques to measure aggregate stability are accurate, consistent and reliable, in order to appropriately manage and monitor soil quality, and to develop our understanding and estimates of soil as a carbon store to appropriately incorporate in carbon cycle models. Practices used to assess the stability of aggregates vary in sample preparation, operational technique and unit of results. They use proxies and lack quantification. Conflicting results are therefore drawn between projects that do not provide methodological or resultant comparability. Typical modern stability tests suspend aggregates in water and monitor fragmentation upon exposure to an un-quantified amount of ultrasonic energy, utilising a laser granulometer to measure the change in mean weight diameter. In this project a novel approach has been developed based on that of Zhu et al., (2009), to accurately quantify the stability of aggregates by specifically measuring their bond energies. The bond energies are measured operating a combination of calorimetry and a high powered ultrasonic probe, with computable output function. Temperature change during sonication is monitored by an array of probes which enables calculation of the energy spent heating the system (Ph). Our novel technique suspends aggregates in heavy liquid lithium heteropolytungstate, as opposed to water, to avoid exposing aggregates to an immeasurable disruptive energy source, due to cavitation, collisions and clay swelling. Mean weight diameter is measured by a laser granulometer to monitor aggregate breakdown after successive periods of calculated ultrasonic energy input (Pi), until complete dispersion is achieved and bond

  4. Experimental and computational thermochemical study of sulfur-containing amino acids: L-cysteine, L-cystine, and L-cysteine-derived radicals. S-S, S-H, and C-S bond dissociation enthalpies.

    Science.gov (United States)

    Roux, Maria Victoria; Foces-Foces, Concepción; Notario, Rafael; da Silva, Manuel A V Ribeiro; da Silva, Maria das Dores M C Ribeiro; Santos, Ana Filipa L O M; Juaristi, Eusebio

    2010-08-19

    This paper reports an experimental and theoretical study of the standard (p(degrees) = 0.1 MPa) molar enthalpies of formation at T = 298.15 K of the sulfur-containing amino acids l-cysteine [CAS 52-90-4] and l-cystine [CAS 56-89-3]. The standard (p(degrees) = 0.1 MPa) molar enthalpies of formation of crystalline l-cysteine and l-cystine were calculated from the standard molar energies of combustion, in oxygen, to yield CO2(g) and H2SO4.115H2O, measured by rotating-bomb combustion calorimetry at T = 298.15 K. The vapor pressures of l-cysteine were measured as function of temperature by the Knudsen effusion mass-loss technique. The standard molar enthalpy of sublimation, at T = 298.15 K, was derived from the Clausius-Clapeyron equation. The experimental values were used to calculate the standard (p(degrees) = 0.1 MPa) enthalpy of formation of l-cysteine in the gaseous phase, DeltafH(degrees)m(g) = -382.6 +/- 1.8 kJ x mol-1. Due to the low vapor pressures of l-cystine and since this compound decomposes at the temperature range required for a possible sublimation, it was not possible to determine its enthalpy of sublimation. Standard ab initio molecular orbital calculations at the G3(MP2)//B3LYP and/or G3 levels were performed. Enthalpies of formation, using atomization and isodesmic reactions, were calculated and compared with experimental data. A value of -755 +/- 10 kJ x mol-1 was estimated for the enthalpy of formation of cystine. Detailed inspections of the molecular and electronic structures of the compounds studied were carried out. Finally, bond dissociation enthalpies (BDE) of S-H, S-S, and C-S bonds, and enthalpies of formation of l-cysteine-derived radicals, were also computed.

  5. Dynamics of unimolecular dissociation of silylene

    Science.gov (United States)

    NoorBatcha, I.; Raff, Lionel M.; Thompson, Donald L.; Viswanathan, R.

    1986-04-01

    The semiempirical valence-bond surface formulated by Viswanathan et al. [J. Phys. Chem. 89, 1428 (1985)] for the unimolecular dissociation of SiH2 has been fitted to an analytical function of the type suggested by Murrell and co-workers [J. Phys. Chem. 88, 4887 (1984)]. The fitted surface accurately represents most of the experimental and CI results. The dynamics of the unimolecular dissociation of SiH2 to form Si and H2 have been investigated by classical trajectory methods on this fitted surface. The effect of describing the initial state of the molecule using normal and local mode approximations has been studied. In spite of the presence of the heavier atom, no bond or mode specificity is observed. The product energy distribution is found to be statistical. Using the RRK model, the high-pressure limiting rate coefficient is found to be k(T,∞)=3.38×1012 exp[-61.6 kcal mol-1/RT] s-1, which is less than the dissociation rate for SiH4. This has been attributed to the higher activation energy for SiH2 and to a statistical factor.

  6. A Vision of Interdisciplinary Education: Students' Reasoning about "High-Energy Bonds" and ATP

    CERN Document Server

    Dreyfus, Benjamin W; Turpen, Chandra; Gouvea, Julia; Redish, Edward F

    2014-01-01

    As interdisciplinary courses are developed, instructors and researchers have to grapple with questions of how students should make connections across disciplines. We explore the issue of interdisciplinary reconciliation (IDR): how students reconcile seemingly contradictory ideas from different disciplines. While IDR has elements in common with other frameworks for the reconciliation of ideas across contexts, it differs in that each disciplinary idea is considered canonically correct within its own discipline. The setting for the research is an introductory physics course for biology majors that seeks to build greater interdisciplinary coherence and therefore includes biologically relevant topics such as ATP and chemical bond energy. In our case-study data, students grapple with the apparent contradiction between the energy released when the phosphate bond in ATP is broken and the idea that an energy input is required to break a bond. We see students justifying context-dependent modeling choices, showing nuanc...

  7. Experimental study on the initiation and energy release behavior of polymer bonded explosive materials

    Science.gov (United States)

    Zhang, Wei; Cai, Xuanming; Ye, Nan; Gao, Yubo

    2017-01-01

    In this paper, an initially sealed vented test chamber and a test projectile with polymer bonded explosive materials were designed to complete the experiments. As the initiation takes place on the interior, great amounts of thermo-chemical energy gases were vented through a hole formed by the penetration process. The gas pressure inside the chamber was used to evaluate the energy release behavior of polymer bonded explosive materials. The experimental results reveal that the impact velocity is significant to the energy release behavior, and in some extent the gas pressure improves with the velocity of the projectile. And the critical initiation velocity and the velocity as the polymer bonded explosive materials reached the maximum reactive efficiency were obtained.

  8. Atom probe tomography simulations and density functional theory calculations of bonding energies in Cu3Au

    KAUST Repository

    Boll, Torben

    2012-10-01

    In this article the Cu-Au binding energy in Cu3Au is determined by comparing experimental atom probe tomography (APT) results to simulations. The resulting bonding energy is supported by density functional theory calculations. The APT simulations are based on the Müller-Schottky equation, which is modified to include different atomic neighborhoods and their characteristic bonds. The local environment is considered up to the fifth next nearest neighbors. To compare the experimental with simulated APT data, the AtomVicinity algorithm, which provides statistical information about the positions of the neighboring atoms, is applied. The quality of this information is influenced by the field evaporation behavior of the different species, which is connected to the bonding energies. © Microscopy Society of America 2012.

  9. Electronic structure, molecular bonding and potential energy surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ruedenberg, K. [Ames Laboratory, IA (United States)

    1993-12-01

    By virtue of the universal validity of the generalized Born-Oppenheimer separation, potential energy surfaces (PES`) represent the central conceptual as well as quantitative entities of chemical physics and provide the basis for the understanding of most physicochemical phenomena in many diverse fields. The research in this group deals with the elucidation of general properties of PES` as well as with the quantitative determination of PES` for concrete systems, in particular pertaining to reactions involving carbon, oxygen, nitrogen and hydrogen molecules.

  10. Mathematical Simulation of Graphene With Modified c-c Bond Length and Transfer Energy

    OpenAIRE

    P.A. Alvi; S.Z. Hashmi; S. Dalela; Rahman, F.

    2011-01-01

    In nanotechnology research, allotropes of carbon like Graphene, Fullerene (Buckyball) and Carbon nanotubes are widely used due to their remarkable properties. Electrical and mechanical properties of those allotropes vary with their molecular geometry. This paper is specially based on modeling and simulation of graphene in order to calculate energy band structure in k space with varying the C-C bond length and C-C transfer energy. Significant changes have been observed in the energy band struc...

  11. Sufficient minimal model for DNA denaturation: Integration of harmonic scalar elasticity and bond energies.

    Science.gov (United States)

    Singh, Amit Raj; Granek, Rony

    2016-10-14

    We study DNA denaturation by integrating elasticity - as described by the Gaussian network model - with bond binding energies, distinguishing between different base pairs and stacking energies. We use exact calculation, within the model, of the Helmholtz free-energy of any partial denaturation state, which implies that the entropy of all formed "bubbles" ("loops") is accounted for. Considering base pair bond removal single events, the bond designated for opening is chosen by minimizing the free-energy difference for the process, over all remaining base pair bonds. Despite of its great simplicity, for several known DNA sequences our results are in accord with available theoretical and experimental studies. Moreover, we report free-energy profiles along the denaturation pathway, which allow to detect stable or meta-stable partial denaturation states, composed of bubble, as local free-energy minima separated by barriers. Our approach allows to study very long DNA strands with commonly available computational power, as we demonstrate for a few random sequences in the range 200-800 base-pairs. For the latter, we also elucidate the self-averaging property of the system. Implications for the well known breathing dynamics of DNA are elucidated.

  12. Sufficient minimal model for DNA denaturation: Integration of harmonic scalar elasticity and bond energies

    Science.gov (United States)

    Singh, Amit Raj; Granek, Rony

    2016-10-01

    We study DNA denaturation by integrating elasticity — as described by the Gaussian network model — with bond binding energies, distinguishing between different base pairs and stacking energies. We use exact calculation, within the model, of the Helmholtz free-energy of any partial denaturation state, which implies that the entropy of all formed "bubbles" ("loops") is accounted for. Considering base pair bond removal single events, the bond designated for opening is chosen by minimizing the free-energy difference for the process, over all remaining base pair bonds. Despite of its great simplicity, for several known DNA sequences our results are in accord with available theoretical and experimental studies. Moreover, we report free-energy profiles along the denaturation pathway, which allow to detect stable or meta-stable partial denaturation states, composed of bubble, as local free-energy minima separated by barriers. Our approach allows to study very long DNA strands with commonly available computational power, as we demonstrate for a few random sequences in the range 200-800 base-pairs. For the latter, we also elucidate the self-averaging property of the system. Implications for the well known breathing dynamics of DNA are elucidated.

  13. Using Qualified Energy Conservation Bonds for Public Building Upgrades. Reducing Energy Bills in the City of Philadelphia

    Energy Technology Data Exchange (ETDEWEB)

    Zimring, Mark [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2012-07-18

    Qualified Energy Conservation Bonds (QECBs) are federally-subsidized bonds that enable state, tribal, and local government issuers to borrow money to fund a range of energy conservation projects, including public building upgrades that reduce energy use by at least 20 percent, at very attractive borrowing rates and long terms. As part of the American Recovery and Reinvestment Act (ARRA), the City of Philadelphia received a $15 million QECB award from the U.S. Department of the Treasury (Treasury). The city leveraged $6.25 million of its QECB allocation to finance half of a $12.6 million initiative to upgrade the energy efficiency of City buildings. The upgrades to four city facilities are expected to deliver over $10 million of net savings, and are a major step towards achieving the city’s goal of reducing government energy consumption by 30 percent by 2015.

  14. Investigation of Highly Designable Dented Structures in HP Model with Hydrogen Bond Energy

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wei; HUANG Shengyou; YU Tao; ZOU Xianwu

    2007-01-01

    Some highly designable protein structures have dented on the surface of their native structures, and are not full compactly folded. According to hydrophobic-polar (HP) model the most designable structures are full compactly folded. To investigate the designability of the dented structures, we introduce the hydrogen bond energy in the secondary structures by using the secondary-structure-favored HP model proposed by Ou-yang etc. The result shows that the average designability increases with the strength of the hydrogen bond. The designabilities of the structures with same dented shape increase exponentially with the number of secondary structure sites. The dented structures can have the highest designabilities for a certain value of hydrogen bond energy density.

  15. A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

    Energy Technology Data Exchange (ETDEWEB)

    Raupach, Marc; Tonner, Ralf, E-mail: tonner@chemie.uni-marburg.de [Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35032 Marburg (Germany)

    2015-05-21

    The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the bonding energy between two fragments (e.g., the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic, Pauli repulsion, and orbital relaxation energies. This is complemented by consideration of dispersion interactions via a pairwise scheme. One major extension toward a previous implementation [Philipsen and Baerends, J. Phys. Chem. B 110, 12470 (2006)] lies in the separate discussion of electrostatic and Pauli and the addition of a dispersion term. The pEDA presented here for an implementation based on atomic orbitals can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy, and k-space sampling. Four typical bonding scenarios for surface-adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H{sub 2} on M(001), M = Pd, Cu), and semiconducting (CO and C{sub 2}H{sub 2} on Si(001)) substrates. These examples cover diverse substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence that the pEDA will be a powerful tool for the analysis of surface-adsorbate bonding in the future, enabling the transfer of concepts like ionic and covalent bonding, donor-acceptor interaction, steric repulsion, and others to extended systems.

  16. Ionic bond effects on the mean excitation energy for stopping power

    Science.gov (United States)

    Wilson, J. W.; Chang, C. K.; Kamaratos, E.; Xu, Y. J.

    1982-01-01

    Molecular mean excitation energies for ionic bonded molecules calculated according to the local plasma approximation are compared to the Bragg rule. Adjustments of 15% are calculated for LiF in agreement with experiments while 6% adjustments are predicted for HF and 3% for LiH.

  17. Efficient Energy Transfer in Supramolecular, Hydrogen-Bonded Polypyridylruthenium-Osmium Complexes

    NARCIS (Netherlands)

    Rau, Sven; Schäfer, Bernhard; Schebesta, Sebastian; Grüßing, André; Poppitz, Wolfgang; Walther, Dirk; Duati, Marco; Browne, Wesley R.; Vos, Johannes G.

    2003-01-01

    Hydrogen bond association between ruthenium bibenzimidazole and carboxylated polypyridylosmium complexes results in stable supramolecular aggregates. The determined stability constant of logK approximate to 6 +/- 0.3 allows efficient energy transfer from the ruthenium to the osmium moiety. (C) Wiley

  18. Mathematical Simulation of Graphene With Modified c-c Bond Length and Transfer Energy

    Directory of Open Access Journals (Sweden)

    P.A. Alvi

    2011-01-01

    Full Text Available In nanotechnology research, allotropes of carbon like Graphene, Fullerene (Buckyball and Carbon nanotubes are widely used due to their remarkable properties. Electrical and mechanical properties of those allotropes vary with their molecular geometry. This paper is specially based on modeling and simulation of graphene in order to calculate energy band structure in k space with varying the C-C bond length and C-C transfer energy. Significant changes have been observed in the energy band structure of graphene due to variation in C-C bond length and C-C transfer energy. In particular, this paper focuses over the electronic structure of graphene within the frame work of tight binding approximation. It has been reported that conduction and valence states in graphene only meet at two points in k-space and that dispersion around these special points is conical.

  19. I. Dissociation free energies of drug-receptor systems via non-equilibrium alchemical simulations: a theoretical framework.

    Science.gov (United States)

    Procacci, Piero

    2016-06-01

    In this contribution I critically revise the alchemical reversible approach in the context of the statistical mechanics theory of non-covalent bonding in drug-receptor systems. I show that most of the pitfalls and entanglements for the binding free energy evaluation in computer simulations are rooted in the equilibrium assumption that is implicit in the reversible method. These critical issues can be resolved by using a non-equilibrium variant of the alchemical method in molecular dynamics simulations, relying on the production of many independent trajectories with a continuous dynamical evolution of an externally driven alchemical coordinate, completing the decoupling of the ligand in a matter of a few tens of picoseconds rather than nanoseconds. The absolute binding free energy can be recovered from the annihilation work distributions by applying an unbiased unidirectional free energy estimate, on the assumption that any observed work distribution is given by a mixture of normal distributions, whose components are identical in either direction of the non-equilibrium process, with weights regulated by the Crooks theorem. I finally show that the inherent reliability and accuracy of the unidirectional estimate of the decoupling free energies, based on the production of a few hundreds of non-equilibrium independent sub-nanosecond unrestrained alchemical annihilation processes, is a direct consequence of the funnel-like shape of the free energy surface in molecular recognition. An application of the technique to a real drug-receptor system is presented in the companion paper.

  20. Three-body dissociations: The photodissociation of dimethyl sulfoxide at 193 nm

    Energy Technology Data Exchange (ETDEWEB)

    Blank, D.A.; North, S.W.; Stranges, D. [Lawrence Berkeley National Lab., CA (United States)] [and others

    1997-04-01

    When a molecule with two equivalent chemical bonds is excited above the threshold for dissociation of both bonds, how the rupture of the two bonds is temporally coupled becomes a salient question. Following absorption at 193 nm dimethyl sulfoxide (CH{sub 3}SOCH{sub 3}) contains enough energy to rupture both C-S bonds. This can happen in a stepwise (reaction 1) or concerted (reaction 2) fashion where the authors use rotation of the SOCH{sub 3} intermediate prior to dissociation to define a stepwise dissociation: (1) CH{sub 3}SOCH{sub 3} {r_arrow} 2CH{sub 3} + SO; (2a) CH{sub 3}SOCH{sub 3} {r_arrow} CH{sub 3} + SOCH{sub 3}; and (2b) SOCH{sub 3} {r_arrow} SO + CH{sub 3}. Recently, the dissociation of dimethyl sulfoxide following absorption at 193 nm was suggested to involve simultaneous cleavage of both C-S bonds on an excited electronic surface. This conclusion was inferred from laser induced fluorescence (LIF) and resonant multiphoton ionization (2+1 REMPI) measurements of the internal energy content in the CH{sub 3} and SO photoproducts and a near unity quantum yield measured for SO. Since this type of concerted three body dissociation is very interesting and a rather rare event in photodissociation dynamics, the authors chose to investigate this system using the technique of photofragment translational spectroscopy at beamline 9.0.2.1. The soft photoionization provided by the VUV undulator radiation allowed the authors to probe the SOCH{sub 3} intermediate which had not been previously observed and provided good evidence that the dissociation of dimethyl sulfoxide primarily proceeds via a two step dissociation, reaction 2.

  1. Methane dissociation on Ni(111): A fifteen-dimensional potential energy surface using neural network method

    Science.gov (United States)

    Shen, Xiangjian; Chen, Jun; Zhang, Zhaojun; Shao, Kejie; Zhang, Dong H.

    2015-10-01

    In the present work, we develop a highly accurate, fifteen-dimensional potential energy surface (PES) of CH4 interacting on a rigid flat Ni(111) surface with the methodology of neural network (NN) fit to a database consisted of about 194 208 ab initio density functional theory (DFT) energy points. Some careful tests of the accuracy of the fitting PES are given through the descriptions of the fitting quality, vibrational spectrum of CH4 in vacuum, transition state (TS) geometries as well as the activation barriers. Using a 25-60-60-1 NN structure, we obtain one of the best PESs with the least root mean square errors: 10.11 meV for the entrance region and 17.00 meV for the interaction and product regions. Our PES can reproduce the DFT results very well in particular for the important TS structures. Furthermore, we present the sticking probability S0 of ground state CH4 at the experimental surface temperature using some sudden approximations by Jackson's group. An in-depth explanation is given for the underestimated sticking probability.

  2. Average bond energies between boron and elements of the fourth, fifth, sixth, and seventh groups of the periodic table

    Science.gov (United States)

    Altshuller, Aubrey P

    1955-01-01

    The average bond energies D(gm)(B-Z) for boron-containing molecules have been calculated by the Pauling geometric-mean equation. These calculated bond energies are compared with the average bond energies D(exp)(B-Z) obtained from experimental data. The higher values of D(exp)(B-Z) in comparison with D(gm)(B-Z) when Z is an element in the fifth, sixth, or seventh periodic group may be attributed to resonance stabilization or double-bond character.

  3. Rovibrational internal energy transfer and dissociation of N2(1Σg+)-N(4S(u)) system in hypersonic flows.

    Science.gov (United States)

    Panesi, Marco; Jaffe, Richard L; Schwenke, David W; Magin, Thierry E

    2013-01-28

    A rovibrational collisional model is developed to study energy transfer and dissociation of N(2)((1)Σ(g)(+)) molecules interacting with N((4)S(u)) atoms in an ideal isochoric and isothermal chemical reactor. The system examined is a mixture of molecular nitrogen and a small amount of atomic nitrogen. This mixture, initially at room temperature, is heated by several thousands of degrees Kelvin, driving the system toward a strong non-equilibrium condition. The evolution of the population densities of each individual rovibrational level is explicitly determined via the numerical solution of the master equation for temperatures ranging from 5000 to 50,000 K. The reaction rate coefficients are taken from an ab initio database developed at NASA Ames Research Center. The macroscopic relaxation times, energy transfer rates, and dissociation rate coefficients are extracted from the solution of the master equation. The computed rotational-translational (RT) and vibrational-translational (VT) relaxation times are different at low heat bath temperatures (e.g., RT is about two orders of magnitude faster than VT at T = 5000 K), but they converge to a common limiting value at high temperature. This is contrary to the conventional interpretation of thermal relaxation in which translational and rotational relaxation timescales are assumed comparable with vibrational relaxation being considerable slower. Thus, this assumption is questionable under high temperature non-equilibrium conditions. The exchange reaction plays a very significant role in determining the dynamics of the population densities. The macroscopic energy transfer and dissociation rates are found to be slower when exchange processes are neglected. A macroscopic dissociation rate coefficient based on the quasi-stationary distribution, exhibits excellent agreement with experimental data of Appleton et al. [J. Chem. Phys. 48, 599-608 (1968)]. However, at higher temperatures, only about 50% of dissociation is found to

  4. Fabrication and Characterization of a Lead Zirconate Titanate Micro Energy Harvester Based on Eutectic Bonding

    Institute of Scientific and Technical Information of China (English)

    LI Yi-Gui; SUN Jian; YANG Chun-Sheng; LIU Jing-Quan; SUGIYAMA Susumu; TANAKA Katsuhiko

    2011-01-01

    A lead zirconate titanate(PZT)-Si energy harvester cantilever with PZT bulk ceramics is fabricated by eutectic bonding, polishing and dicing processes. The feasibility of this process is studied using a successful operation of the cantilever in both actuation and harvesting modes. The first prototype made from a PZT-Au-Si cantiliever is tested. The testing results show the voltage output of 632mV at the frequency of 815Hz when the excitation acceleration is 0.5 g. The PZT and silicon layers are bonded together to form a sandwiched structure using a gold layer as an intermediate layer.%@@ A lead zirconate titanate(PZT)-Si energy harvester cantilever with PZT bulk ceramics is fabricated by eutectic bonding, polishing and dicing processes.The feasibility of this process is studied using a successful operation of the cantilever in both actuation and harvesting modes.The first prototype made from a PZT-Au-Si cantiliever is tested.The testing results show the voltage output of 632mV at the frequency of 815 Hz when the excitation acceleration is 0.5 g.The PZT and silicon layers are bonded together to form a sandwiched structure using a gold layer as an intermediate layer.

  5. Molecule-surface dissociative scattering of n-C3F7NO from MgO(100) at hyperthermal energies: Nascent NO (X 2Π)

    Science.gov (United States)

    Kolodney, E.; Baugh, D.; Powers, P. S.; Reisler, H.; Wittig, C.

    1989-04-01

    The title reaction was examined for incident kinetic energies in the range 3-7 eV and surface temperatures in the range 500-800 K; dissociation probabilities as high as 3±1% were measured. NO state distributions were obtained near the specular angle using two-photon, two-frequency laser ionization, and spin-orbit ``temperatures''˜170 K were observed, in contrast to higher rotational excitations. Possible mechanisms are mentioned.

  6. Kinetics of CH4 and CO2 hydrate dissociation and gas bubble evolution via MD simulation.

    Science.gov (United States)

    Uddin, M; Coombe, D

    2014-03-20

    Molecular dynamics simulations of gas hydrate dissociation comparing the behavior of CH4 and CO2 hydrates are presented. These simulations were based on a structurally correct theoretical gas hydrate crystal, coexisting with water. The MD system was first initialized and stabilized via a thorough energy minimization, constant volume-temperature ensemble and constant volume-energy ensemble simulations before proceeding to constant pressure-temperature simulations for targeted dissociation pressure and temperature responses. Gas bubble evolution mechanisms are demonstrated as well as key investigative properties such as system volume, density, energy, mean square displacements of the guest molecules, radial distribution functions, H2O order parameter, and statistics of hydrogen bonds. These simulations have established the essential similarities between CH4 and CO2 hydrate dissociation. The limiting behaviors at lower temperature (no dissociation) and higher temperature (complete melting and formation of a gas bubble) have been illustrated for both hydrates. Due to the shift in the known hydrate stability curves between guest molecules caused by the choice of water model as noted by other authors, the intermediate behavior (e.g., 260 K) showed distinct differences however. Also, because of the more hydrogen-bonding capability of CO2 in water, as reflected in its molecular parameters, higher solubility of dissociated CO2 in water was observed with a consequence of a smaller size of gas bubble formation. Additionally, a novel method for analyzing hydrate dissociation based on H-bond breakage has been proposed and used to quantify the dissociation behaviors of both CH4 and CO2 hydrates. Activation energies Ea values from our MD studies were obtained and evaluated against several other published laboratory and MD values. Intrinsic rate constants were estimated and upscaled. A kinetic reaction model consistent with macroscale fitted kinetic models has been proposed to

  7. Description of molecular dynamics in intense laser fields by the time-dependent adiabatic state approach: application to simultaneous two-bond dissociation of CO2 and its control.

    Science.gov (United States)

    Sato, Yukio; Kono, Hirohiko; Koseki, Shiro; Fujimura, Yuichi

    2003-07-02

    We theoretically investigated the dynamics of structural deformations of CO(2) and its cations in near-infrared intense laser fields (approximately 10(15) W cm(-2)) by using the time-dependent adiabatic state approach. To obtain "field-following" adiabatic potentials for nuclear dynamics, the electronic Hamiltonian including the interaction with the instantaneous laser electric field is diagonalized by the multiconfiguration self-consistent-field molecular orbital method. In the CO(2) and CO(2+) stages, ionization occurs before the field intensity becomes high enough to deform the molecule. In the CO(2)(2+) stage, simultaneous symmetric two-bond stretching occurs as well as one-bond stretching. Two-bond stretching is induced by an intense field in the lowest time-dependent adiabatic state |1> of CO(2)(2+), and this two-bond stretching is followed by the occurrence of a large-amplitude bending motion mainly in the second-lowest adiabatic state |2> nonadiabatically created at large internuclear distances by the field from |1>. It is concluded that the experimentally observed stretched and bent structure of CO(2)(3+) just before Coulomb explosions originates from the structural deformation of CO(2)(2+). We also show in this report that the concept of "optical-cycle-averaged potential" is useful for designing schemes to control molecular (reaction) dynamics, such as dissociation dynamics of CO(2), in intense fields. The present approach is simple but has wide applicability for analysis and prediction of electronic and nuclear dynamics of polyatomic molecules in intense laser fields.

  8. Full-dimensional quantum calculations of the dissociation energy, zero-point, and 10 K properties of H7+/D7+ clusters using an ab initio potential energy surface.

    Science.gov (United States)

    Barragán, Patricia; Pérez de Tudela, Ricardo; Qu, Chen; Prosmiti, Rita; Bowman, Joel M

    2013-07-14

    Diffusion Monte Carlo (DMC) and path-integral Monte Carlo computations of the vibrational ground state and 10 K equilibrium state properties of the H7 (+)/D7 (+) cations are presented, using an ab initio full-dimensional potential energy surface. The DMC zero-point energies of dissociated fragments H5 (+)(D5 (+))+H2(D2) are also calculated and from these results and the electronic dissociation energy, dissociation energies, D0, of 752 ± 15 and 980 ± 14 cm(-1) are reported for H7 (+) and D7 (+), respectively. Due to the known error in the electronic dissociation energy of the potential surface, these quantities are underestimated by roughly 65 cm(-1). These values are rigorously determined for first time, and compared with previous theoretical estimates from electronic structure calculations using standard harmonic analysis, and available experimental measurements. Probability density distributions are also computed for the ground vibrational and 10 K state of H7 (+) and D7 (+). These are qualitatively described as a central H3 (+)/D3 (+) core surrounded by "solvent" H2/D2 molecules that nearly freely rotate.

  9. Appropriate choice of collision-induced dissociation energy for qualitative analysis of notoginsenosides based on liquid chromatography hybrid ion trap time-of-flight mass spectrometry.

    Science.gov (United States)

    Wang, Guang-Ji; Fu, Han-Xu; Xiao, Jing-Cheng; Ye, Wei; Rao, Tai; Shao, Yu-Hao; Kang, Dian; Xie, Lin; Liang, Yan

    2016-04-01

    Liquid chromatography hybrid ion trap/time-of-flight mass spectrometry possessesd both the MS(n) ability of ion trap and the excellent resolution of a time-of-flight, and has been widely used to identify drug metabolites and determine trace multi-components for in natural products. Collision energy, one of the most important factors in acquiring MS(n) information, could be set freely in the range of 10%-400%. Herein, notoginsenosides were chosen as model compounds to build a novel methodology for the collision energy optimization. Firstly, the fragmental patterns of the representatives for the authentic standards of protopanaxadiol-type and protopanaxatriol-type notoginsenosides authentic standards were obtained based on accurate MS(2) and MS(3) measurements via liquid chromatography hybrid ion trap/time-of-flight mass spectrometry. Then the extracted ion chromatograms of characteristic product ions of notoginsenosides in Panax Notoginseng Extract, which were produced under a series of collision energies and, were compared to screen out the optimum collision energies values for MS(2) and MS(3). The results demonstrated that the qualitative capability of liquid chromatography hybrid ion trap/time-of-flight mass spectrometry was greatly influenced by collision energies, and 50% of MS(2) collision energy was found to produce the highest collision-induced dissociation efficiency for notoginsenosides. BesidesAddtionally, the highest collision-induced dissociation efficiency appeared when the collision energy was set at 75% in the MS(3) stage.

  10. Calorimetric and computational study of thiacyclohexane 1-oxide and thiacyclohexane 1,1-dioxide (thiane sulfoxide and thiane sulfone). Enthalpies of formation and the energy of the S=O bond.

    Science.gov (United States)

    Roux, María Victoria; Temprado, Manuel; Jiménez, Pilar; Dávalos, Juan Zenón; Notario, Rafael; Guzmán-Mejía, Ramón; Juaristi, Eusebio

    2003-03-01

    A rotating-bomb combustion calorimeter specifically designed for the study of sulfur-containing compounds [J. Chem. Thermodyn. 1999, 31, 635] has been used for the determination of the enthalpy of formation of thiane sulfone, 4, Delta(f)H(o) m(g) = -394.8 +/- 1.5 kJ x mol(-1). This value stands in stark contrast with the enthalpy of formation reported for thiane itself, Delta(f)H(o) m(g) = -63.5 +/- 1.0 kJ x mol(-1), and gives evidence of the increased electronegativity of the sulfur atom in the sulfonyl group, which leads to significantly stronger C-SO2 bonds. Given the known enthalpy of formation of atomic oxygen in the gas phase, Delta(f)H(o) m(O,g) = +249.18 kJ x mol(-1), and the reported bond dissociation energy for the S=O bond in alkyl sulfones, BDE(S=O) = +470.0 kJ x mol(-1), it was possible to estimate the enthalpy of formation of thiane sulfoxide, 5, a hygroscopic compound not easy to use in experimental calorimetric measurements, Delta(f)H(o) m(5) = -174.0 kJ x mol(-1). The experimental enthalpy of formation of both 4 and 5 were closely reproduced by theoretical calculations at the G2(MP2)+ level, Delta(f)H(o) m(4) = -395.0 kJ x mol(-1) and Delta(f)H(o) m(5) = -178.0 kJ x mol(-1). Finally, calculated G2(MP2)+ values for the bond dissociation energy of the S=O bond in cyclic sulfoxide 5 and sulfone 4 are +363.7 and +466.2 kJ x mol(-1), respectively.

  11. Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional

    Science.gov (United States)

    Sun, Jianwei; Remsing, Richard C.; Zhang, Yubo; Sun, Zhaoru; Ruzsinszky, Adrienn; Peng, Haowei; Yang, Zenghui; Paul, Arpita; Waghmare, Umesh; Wu, Xifan; Klein, Michael L.; Perdew, John P.

    2016-09-01

    One atom or molecule binds to another through various types of bond, the strengths of which range from several meV to several eV. Although some computational methods can provide accurate descriptions of all bond types, those methods are not efficient enough for many studies (for example, large systems, ab initio molecular dynamics and high-throughput searches for functional materials). Here, we show that the recently developed non-empirical strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation (meta-GGA) within the density functional theory framework predicts accurate geometries and energies of diversely bonded molecules and materials (including covalent, metallic, ionic, hydrogen and van der Waals bonds). This represents a significant improvement at comparable efficiency over its predecessors, the GGAs that currently dominate materials computation. Often, SCAN matches or improves on the accuracy of a computationally expensive hybrid functional, at almost-GGA cost. SCAN is therefore expected to have a broad impact on chemistry and materials science.

  12. Free energy diagram for the heterogeneous enzymatic hydrolysis of glycosidic bonds in cellulose

    DEFF Research Database (Denmark)

    Westh, Peter; Cruys-Bagger, Nicolaj; Sørensen, Trine Holst

    2015-01-01

    Kinetic and thermodynamic data has been analyzed according to transition state theory and a simplified reaction scheme for the enzymatic hydrolysis of insoluble cellulose. For the cellobiohydrolase Cel7A from Hypocrea jecorina (Tricoderma reesei) we were able to measure or collect relevant values...... for all stable and activated complexes defined by the reaction scheme, and hence propose a free energy diagram for the full heterogeneous process. For other Cel7A enzymes, including variants with and without carbohydrate binding module (CBM), we obtained activation parameters for the association...... was late in the path where most enzyme-substrate contacts were broken. Activation enthalpies revealed that the rate of dissociation was far more temperature sensitive than the rates of both association and the inner catalytic cycle. Comparisons of one- and two-domain variants showed that the CBM had...

  13. Impact of mass and bond energy difference and interface defects on thermal boundary conductance

    Science.gov (United States)

    Choi, ChangJin

    The objective of this study is to use molecular dynamics simulation techniques in order to improve the understanding of phonon transport at the interface of dissimilar materials and the impact of different material properties on thermal boundary conductance (TBC). In order to achieve this goal, we investigated the contributions of mass and bond energy difference and interface defects on TBC at the interface of nanostructured materials using non-equilibrium molecular dynamics (NEMD) simulation and phonon wave-packet (PWP) simulation techniques. NEMD is used to distinguish relative and combined contributions of mass and bond energy difference on TBC. As a result, it is found that the mass has a stronger contribution than the bond energy on lowering the TBC and that the TBC is dependent on the length of interdiffusion region as well as temperature. In addition, evidence of inelastic scattering is observed with interdiffusion regions especially when two materials differ in the bond energy. A detailed description of phonon interactions at the interface is obtained performing PWP simulations. A frequency dependence of the TBC based on phonon dispersion relation is observed. As it is expected, minimum scattering occurs when there exists only vibrational mismatch at the interface and inelastic scattering is to take place at high frequency region when the bond energy of the two materials is different resulting in the strain at the interface. It is also shown that the level of inelastic scattering is dependent on the length of the interdiffusion region. In addition, the TBC calculated with the results of PWP simulations is compared with that of NEMD simulations as well as theoretical predictions from the acoustic mismatch model and the diffuse mismatch model. A simple analytical model, which utilizes knowledge of thermal interface resistance and the interface geometry for the prediction of effective thermal conductivity, is developed. This model is generated based on Si

  14. Theoretical investigation of the competitive mechanism between dissociation and ionization of H₂⁺ in intense field.

    Science.gov (United States)

    Yao, Hongbin; Zhao, Guangjiu

    2014-10-01

    The competitive mechanism between dissociation and ionization of hydrogen molecular ion in intense field has been theoretically investigated by using an accurate non-Born-Oppenheimer method. The relative yield of fragments indicates that the dissociation and ionization channels are competitive with the increasing laser intensity from 5.0 × 10(13) to 2.0 × 10(14) W/cm(2). In the case of intensity lower than 1.0 × 10(14) W/cm(2), the dissociation channel is dominant, with a minor contribution from ionization. The mechanism of dissociation includes the contributions from the bond softening, bond hardening, below-threshold dissociation, and above-threshold dissociation, which are strongly dependent on the laser intensity and initial vibrational state. Furthermore, the ionization dominates over the dissociation channel at the highest intensity of 2.0 × 10(14) W/cm(2). The reasonable origin of ionization is ascribed as the above-threshold Coulomb explosion, which has been demonstrated by the space-time dependent ionization rate. Moreover, the competition mechanism between dissociation and ionization channels are displayed on the total kinetic energy resolved (KER) spectra, which could be tested at current experimental conditions.

  15. Dissociative electron attachment studies on acetone

    Energy Technology Data Exchange (ETDEWEB)

    Prabhudesai, Vaibhav S., E-mail: vaibhav@tifr.res.in; Tadsare, Vishvesh; Ghosh, Sanat; Gope, Krishnendu; Davis, Daly; Krishnakumar, E. [Tata Institute of Fundamental Research, Homi Bhabha Road, Colaba, Mumbai 400005 (India)

    2014-10-28

    Dissociative electron attachment (DEA) to acetone is studied in terms of the absolute cross section for various fragment channels in the electron energy range of 0–20 eV. H{sup −} is found to be the most dominant fragment followed by O{sup −} and OH{sup −} with only one resonance peak between 8 and 9 eV. The DEA dynamics is studied by measuring the angular distribution and kinetic energy distribution of fragment anions using Velocity Slice Imaging technique. The kinetic energy and angular distribution of H{sup −} and O{sup −} fragments suggest a many body break-up for the lone resonance observed. The ab initio calculations show that electron is captured in the multi-centered anti-bonding molecular orbital which would lead to a many body break-up of the resonance.

  16. Low-energy electron-induced dissociation in condensed-phase L-cysteine II: a comparative study on anion desorption from chemisorbed and physisorbed films

    Science.gov (United States)

    Alizadeh, Elahe; Massey, Sylvain; Sanche, Léon; Rowntree, Paul A.

    2016-04-01

    Due to its multifunctional structure, cysteine is becoming an ideal model molecule for investigating the complex interactions of proteins with metallic surfaces such as gold nanoparticles. We report herein the results of low-energy electron induced degradation of L-cysteine films, chemisorbed on a gold substrate via the thiol group or physisorbed into a clean gold surface. The data were recorded under ultra-high vacuum conditions at room temperature. Anion yields desorbed from these films by the impact of 0.5 to 19 eV electrons provide clear evidence of the efficient decomposition of this amino acid via dissociative electron attachment (i.e., from dissociation of intermediate transient anions located between 5 and 14 eV). The peaks in the desorbed-anion yield functions, associated with DEA, are superimposed on a continuously rising signal attributed to dipolar dissociation. Similar to the results previously observed from physisorbed films, light anionic species, with masses lower than 35 amu, have been detected. In addition, we measured for first time fragments at 14 amu (CH2-) and 15 amu (CH3-) desorbing from physisorbed films, as well as heavier fragments of mass 45 and 46 amu desorbing from chemisorbed films. Contribution to the Topical Issue "Low-Energy Interactions related to Atmospheric and Extreme Conditions", edited by S. Ptasinska, M. Smialek-Telega, A. Milosavljevic, B. Sivaraman.

  17. Photofragment translational spectroscopy of three body dissociations and free radicals

    Energy Technology Data Exchange (ETDEWEB)

    North, Simon William [Univ. of California, Berkeley, CA (United States)

    1995-04-01

    This dissertation describes several three-body dissociations and the photodissociation of methyl radicals studied using photofragment translational spectroscopy. The first chapter provides an introduction to three body dissociation, examines current experimental methodology, and includes a discussion on the treatment of photofragment translational spectroscopy data arising from three-body fragmentation. The ultraviolet photodissociation of azomethane into two methyl radicals and nitrogen is discussed in chapter 2. Chapter 3 describes the photodissociation of acetone at 248 nm and 193 nm. At 248 nm the translational energy release from the initial C-C bond cleavage matches the exit barrier height and a comparison with results at 266 nm suggests that T> is invariant to the available energy. A fraction of the nascent CH3CO radicals spontaneously dissociate following rotational averaging. The T> for the second C-C bond cleavage also matches the exit barrier height. At 193 nm the experimental data can be successfully fit assuming that the dynamics are analogous to those at 248 nm. A simplified model of energy partitioning which adequately describes the experimental results is discussed. Experiments on acetyl halides provide additional evidence to support the proposed acetone dissociation mechanism. A value of 17.0±1.0 kcal/mole for the barrier height, CH3CO decomposition has been determined. The photodissociation of methyl radical at 193 nm and 212.8 nm is discussed in the chapter 5. The formation of CH2(1Al) and H (2S) was the only single photon dissociation pathway observed at both wavelengths.

  18. Energy and density analysis of the H2 molecule from the united atom to dissociation: The 3Σg+ and 3Σu+ states

    Science.gov (United States)

    Corongiu, Giorgina; Clementi, Enrico

    2009-11-01

    The first 14 Σ3g+ and the first 15 Σ3u+ states of the H2 molecule are computed with full configuration interaction both from Hartree-Fock molecular orbitals and Heitler-London atomic orbitals within the Born-Oppenheimer approximation, following recent studies for the Σ1g+ and Σ1u+ manifolds [Corongiu and Clementi, J. Chem. Phys. 131, 034301 (2009) and J. Phys. Chem. (in press)]. The basis sets utilized are extended and optimized Slater-type functions and spherical Gaussian functions. The states considered correspond to the configurations (1s1nl1) with n from 1 to 5; the internuclear separations sample the distances from 0.01 to 10 000 bohrs. For the first three Σ3g+ and Σ3u+ states and for the fourth and fifth Σ3g+ states, our computed energies at the equilibrium internuclear separation, when compared to the accurate values by Staszewska and Wolniewicz and by Kołos and Rychlewski, show deviations of about 0.006 kcal/mol, a test on the quality of our computations. Motivation for this work comes not only from obtaining potential energy curves for the high excited states of H2 but also from characterizing the electronic density evolution from the united atom to dissociation to provide a detailed analysis of the energy contributions from selected basis subsets and to quantitatively decompose the state energies into covalent and ionic components. Furthermore, we discuss the origin of the seemingly irregular patterns in potential energy curves in the two manifolds, between 4 and 6-9 bohrs—there are two systems of states: the first, from the united atom to about 4 bohrs, is represented by functions with principal quantum number higher than the one needed at dissociation; this system interacts at around 4 bohrs with the second system, which is represented by functions with principal quantum number corresponding to one of the dissociation products.

  19. Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

    KAUST Repository

    Falivene, Laura

    2013-01-01

    A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

  20. Facile Formation and Dissociation Behaviour of C–C Bond Resulted from the Nucleophilic Attack of Carbanions on a Carbonyl Carbon in [Pt(hfac)2

    OpenAIRE

    2000-01-01

    [Pt(hfac)2] (hfac:hexafluoroacetylacetonate) reacts with MeNH2 in CH2Cl2/MeOH to give an –NHMe adduct complex on one of the carbonyl carbons, (MeNH3)[Pt(hfac)(hfac–NHMe)] 1 which is a tetrahedral intermediate of a Schiff base complex,[Pt(CF3COCHC(NMe)CF3)2] 2. Complex 1 activates H2O,MeOH, MeNO2 or acetone in solution to form the correspondingconjugate base adducts. The C–C bond in–CH2NO2 adduct 6, easily cleaves and generates nitromethane in solution.

  1. Syntheses, photophysical properties, and application of through-bond energy-transfer cassettes for biotechnology.

    Science.gov (United States)

    Jiao, Guan-Sheng; Thoresen, Lars H; Kim, Taeg Gyum; Haaland, Wade C; Gao, Feng; Topp, Michael R; Hochstrasser, Robin M; Metzker, Michael L; Burgess, Kevin

    2006-10-16

    We have designed fluorescent "through-bond energy-transfer cassettes" that can harvest energy of a relatively short wavelength (e.g., 490 nm), and emit it at appreciably longer wavelengths without significant loss of intensity. Probes of this type could be particularly useful in biotechnology for multiplexing experiments in which several different outputs are to be observed from a single excitation source. Cassettes 1-4 were designed, prepared, and studied as model systems to achieve this end. They were synthesized through convergent routes that feature coupling of specially prepared fluorescein- and rhodamine-derived fragments. The four cassettes were shown to emit strongly, with highly efficient energy transfer. Their emission maxima cover a broad range of wavelengths (broader than the four dye cassettes currently used for most high-throughput DNA sequencing), and they exhibit faster energy-transfer rates than a similar through-space energy-transfer cassette. Specifically, energy-transfer rates in these cassettes is around 6-7 ps, in contrast to a similar through-space energy-transfer system shown to have a decay time of around 35 ps. Moreover, the cassettes are considerably more stable to photobleaching than fluorescein, even though they each contain fluorescein-derived donors. This was confirmed by bulk fluorescent measurements, and in single-molecule-detection studies. Modification of a commercial automated DNA-sequencing apparatus to detect the emissions of these four energy-transfer cassettes enabled single-color dye-primer sequencing.

  2. Contribution of π-bonds to effective charges, cohesive energy, and force constants of graphene-like compounds

    Science.gov (United States)

    Davydov, S. Yu.

    2016-02-01

    For 14 two-dimensional hexagonal compounds IV-IV and III-V, analytical expressions have been obtained using the Harrison bond-orbital method for the contribution from the π-interaction to the polarity of interatomic bonds, the effective atomic and transverse dynamical charges and their dependences on the deformation, as well as to the binding energy, the cohesive energy, and the central and non-central force constants.

  3. Complete-active-space second-order perturbation theory (CASPT2//CASSCF) study of the dissociative electron attachment in canonical DNA nucleobases caused by low-energy electrons (0-3 eV)

    Energy Technology Data Exchange (ETDEWEB)

    Francés-Monerris, Antonio; Segarra-Martí, Javier; Merchán, Manuela; Roca-Sanjuán, Daniel, E-mail: Daniel.Roca@uv.es [Instituto de Ciencia Molecular, Universitat de València, P.O. Box 22085, 46071 València (Spain)

    2015-12-07

    Low-energy (0-3 eV) ballistic electrons originated during the irradiation of biological material can interact with DNA/RNA nucleobases yielding transient-anion species which undergo decompositions. Since the discovery that these reactions can eventually lead to strand breaking of the DNA chains, great efforts have been dedicated to their study. The main fragmentation at the 0-3 eV energy range is the ejection of a hydrogen atom from the specific nitrogen positions. In the present study, the methodological approach introduced in a previous work on uracil [I. González-Ramírez et al., J. Chem. Theory Comput. 8, 2769-2776 (2012)] is employed to study the DNA canonical nucleobases fragmentations of N–H bonds induced by low-energy electrons. The approach is based on minimum energy path and linear interpolation of internal coordinates computations along the N–H dissociation channels carried out at the complete-active-space self-consistent field//complete-active-space second-order perturbation theory level. On the basis of the calculated theoretical quantities, new assignations for the adenine and cytosine anion yield curves are provided. In addition, the π{sub 1}{sup −} and π{sub 2}{sup −} states of the pyrimidine nucleobases are expected to produce the temporary anions at electron energies close to 1 and 2 eV, respectively. Finally, the present theoretical results do not allow to discard neither the dipole-bound nor the valence-bound mechanisms in the range of energies explored, suggesting that both possibilities may coexist in the experiments carried out with the isolated nucleobases.

  4. Complete-active-space second-order perturbation theory (CASPT2//CASSCF) study of the dissociative electron attachment in canonical DNA nucleobases caused by low-energy electrons (0-3 eV)

    Science.gov (United States)

    Francés-Monerris, Antonio; Segarra-Martí, Javier; Merchán, Manuela; Roca-Sanjuán, Daniel

    2015-12-01

    Low-energy (0-3 eV) ballistic electrons originated during the irradiation of biological material can interact with DNA/RNA nucleobases yielding transient-anion species which undergo decompositions. Since the discovery that these reactions can eventually lead to strand breaking of the DNA chains, great efforts have been dedicated to their study. The main fragmentation at the 0-3 eV energy range is the ejection of a hydrogen atom from the specific nitrogen positions. In the present study, the methodological approach introduced in a previous work on uracil [I. González-Ramírez et al., J. Chem. Theory Comput. 8, 2769-2776 (2012)] is employed to study the DNA canonical nucleobases fragmentations of N-H bonds induced by low-energy electrons. The approach is based on minimum energy path and linear interpolation of internal coordinates computations along the N-H dissociation channels carried out at the complete-active-space self-consistent field//complete-active-space second-order perturbation theory level. On the basis of the calculated theoretical quantities, new assignations for the adenine and cytosine anion yield curves are provided. In addition, the π1- and π2- states of the pyrimidine nucleobases are expected to produce the temporary anions at electron energies close to 1 and 2 eV, respectively. Finally, the present theoretical results do not allow to discard neither the dipole-bound nor the valence-bound mechanisms in the range of energies explored, suggesting that both possibilities may coexist in the experiments carried out with the isolated nucleobases.

  5. Synthesis of Novel High Energy Polyaniline Derivative Containing S-S Bond in Six-membered Cycle

    Institute of Scientific and Technical Information of China (English)

    ZHOU Lei; DENG Shi-Ren; LI Zao-Ying

    2003-01-01

    @@ A novel conducting polymer as new class of high energy storage material, [1,2] which has one six-membered cycle containing S-S bond in the moiety of aniline was synthesized. The polymer had enhanced redox progress due to an intramolecular electrocatalytic effect of polyaniline on S-S bond. The polymer has some advantages because of its high theoretical specific energy and fast kinetics when used in lithium batteries. The most promised advantage of it is that the intramolecular cleavage and recombination of the S-S bond improve the cyclicability greatly.

  6. Comparison of DFT with Traditional Methods for the Calculation of Vibrational Frequencies and Bond Energies

    Science.gov (United States)

    Bauschlicher, Charles W.; Arnold, James O. (Technical Monitor)

    1997-01-01

    The vibrational frequencies of MO2 are computed at many levels of theory, including HF, B3LYP, BP86, CASSCF, MP2, and CCSD(T). The computed results are compared with the available experimental results. Most of the methods fail for at least one state of the systems considered. The accuracy of the results and the origin of the observed failures are discussed. The B3LYP bond energies are compared with traditional methods for a variety of systems, ranging from FeCOn+ to SiCln and its positive ions. The cases where B3LYP differs from the traditional methods are discussed.

  7. VUV photophysics and dissociative photoionization of pyrimidine, purine, imidazole and benzimidazole in the 7-18 eV photon energy range

    Energy Technology Data Exchange (ETDEWEB)

    Schwell, Martin [Laboratoire Interuniversitaire des Systemes Atmospheriques (LISA), CNRS-UMR 7583, Universite Paris 7 and 12, 61 Avenue du General de Gaulle, 94010 Creteil (France)], E-mail: schwell@lisa.univ-paris12.fr; Jochims, Hans-Werner; Baumgaertel, Helmut [Institut fuer Physikalische und Theoretische Chemie der Freien Universitaet Berlin, Takustr. 3, Berlin 14195 (Germany); Leach, Sydney [Laboratoire d' Etude du Rayonnement et de la Matiere en Astrophysique (LERMA), CNRS-UMR 8112, Observatoire de Paris-Meudon, 5 Place Jules-Janssen, 92195 Meudon (France)], E-mail: Sydney.Leach@obspm.fr

    2008-11-03

    Photoionization mass spectrometry is used to study ionization processes and fragmentation pathways of four prebiotic species, pyrimidine, purine, imidazole and benzimidazole, in the 7-18 eV photon energy region, with synchrotron radiation as excitation source. These molecules are possible precursors of the nucleic acid bases that occur in DNA and RNA. Ionization energies and ion appearance energies are reported. They are compared with electron impact and other studies and are discussed in terms of the electronic and nuclear structures of these species and their cations. The ion appearance energies, in conjunction with thermochemical data, were used to propose dissociative photoionization pathways, principally involving loss of HCN molecules in each of the four species. Astrophysical implications of the results concern the prospects for observation and survival of these molecules in the interstellar medium, in comets and in meteorites. Suggestions are made concerning suitable sites for radioastronomical searches for these purines and pyrimidines.

  8. AIScore chemically diverse empirical scoring function employing quantum chemical binding energies of hydrogen-bonded complexes.

    Science.gov (United States)

    Raub, Stephan; Steffen, Andreas; Kämper, Andreas; Marian, Christel M

    2008-07-01

    In this work we report on a novel scoring function that is based on the LUDI model and focuses on the prediction of binding affinities. AIScore extends the original FlexX scoring function using a chemically diverse set of hydrogen-bonded interactions derived from extensive quantum chemical ab initio calculations. Furthermore, we introduce an algorithmic extension for the treatment of multifurcated hydrogen bonds (XFurcate). Charged and resonance-assisted hydrogen bond energies and hydrophobic interactions as well as a scaling factor for implicit solvation were fitted to experimental data. To this end, we assembled a set of 101 protein-ligand complexes with known experimental binding affinities. Tightly bound water molecules in the active site were considered to be an integral part of the binding pocket. Compared to the original FlexX scoring function, AIScore significantly improves the prediction of the binding free energies of the complexes in their native crystal structures. In combination with XFurcate, AIScore yields a Pearson correlation coefficient of R P = 0.87 on the training set. In a validation run on the PDBbind test set we achieved an R P value of 0.46 for 799 attractively scored complexes, compared to a value of R P = 0.17 and 739 bound complexes obtained with the FlexX original scoring function. The redocking capability of AIScore, on the other hand, does not fully reach the good performance of the original FlexX scoring function. This finding suggests that AIScore should rather be used for postscoring in combination with the standard FlexX incremental ligand construction scheme.

  9. Energy and Density Analyses of the 1Σu+ States in the H2 Molecule from the United Atom to Dissociation

    Science.gov (United States)

    Corongiu, Giorgina; Clementi, Enrico

    2009-07-01

    The 1Σu+ excited states of the H2 molecule are computed following a recent study by Corongiu and Clementi (J. Chem. Phys. 2009, 131, 034301) on the 1Σg+ states. Full configuration interaction computations both from Hartree-Fock molecular orbitals and Heitler-London atomic orbitals are presented and correlated with a comprehensive analysis. The basis sets utilized are either extended and optimized Slater type functions, STO, or spherical Gaussian functions, GTO. Computations and analyses are presented for states 1 to 14, covering the internuclear distances from 0.01 to 10000 bohr. The accurate data by L. Wolniewicz and collaborators, available for the first six excited states, verify the good quality of our computations. We focus on the characterization of the orbitals in the excited state wave functions, on the electronic density evolution from the united atom to dissociation, on quantitative decomposition of the total energy into covalent and ionic components and on detailed analyses of energy contributions to the total state energy from selected STO subsets. Each manifold has one state, specifically the states 1, 3 and 6, where the second minimum has strong ionic character. State 10 dissociates into the ion pair H+H-.

  10. Energy and density analyses of the 1Sigma(u)+ states in the H2 molecule from the united atom to dissociation.

    Science.gov (United States)

    Corongiu, Giorgina; Clementi, Enrico

    2009-12-31

    The 1Sigma(u)+ excited states of the H2 molecule are computed following a recent study by Corongiu and Clementi (J. Chem. Phys. 2009, 131, 034301) on the 1Sigma(g)+ states. Full configuration interaction computations both from Hartree-Fock molecular orbitals and Heitler-London atomic orbitals are presented and correlated with a comprehensive analysis. The basis sets utilized are either extended and optimized Slater type functions, STO, or spherical Gaussian functions, GTO. Computations and analyses are presented for states 1 to 14, covering the internuclear distances from 0.01 to 10000 bohr. The accurate data by L. Wolniewicz and collaborators, available for the first six excited states, verify the good quality of our computations. We focus on the characterization of the orbitals in the excited state wave functions, on the electronic density evolution from the united atom to dissociation, on quantitative decomposition of the total energy into covalent and ionic components and on detailed analyses of energy contributions to the total state energy from selected STO subsets. Each manifold has one state, specifically the states 1, 3 and 6, where the second minimum has strong ionic character. State 10 dissociates into the ion pair H+H-.

  11. Empirical valence bond models for reactive potential energy surfaces: a parallel multilevel genetic program approach.

    Science.gov (United States)

    Bellucci, Michael A; Coker, David F

    2011-07-28

    We describe a new method for constructing empirical valence bond potential energy surfaces using a parallel multilevel genetic program (PMLGP). Genetic programs can be used to perform an efficient search through function space and parameter space to find the best functions and sets of parameters that fit energies obtained by ab initio electronic structure calculations. Building on the traditional genetic program approach, the PMLGP utilizes a hierarchy of genetic programming on two different levels. The lower level genetic programs are used to optimize coevolving populations in parallel while the higher level genetic program (HLGP) is used to optimize the genetic operator probabilities of the lower level genetic programs. The HLGP allows the algorithm to dynamically learn the mutation or combination of mutations that most effectively increase the fitness of the populations, causing a significant increase in the algorithm's accuracy and efficiency. The algorithm's accuracy and efficiency is tested against a standard parallel genetic program with a variety of one-dimensional test cases. Subsequently, the PMLGP is utilized to obtain an accurate empirical valence bond model for proton transfer in 3-hydroxy-gamma-pyrone in gas phase and protic solvent.

  12. Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice-Ramsperger-Kassel theory.

    Science.gov (United States)

    Bao, Junwei Lucas; Zhang, Xin; Truhlar, Donald G

    2016-11-29

    Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice-Ramsperger-Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements.

  13. Energy decomposition analysis of cation-π, metal ion-lone pair, hydrogen bonded, charge-assisted hydrogen bonded, and π-π interactions.

    Science.gov (United States)

    Sharma, Bhaskar; Srivastava, Hemant Kumar; Gayatri, Gaddamanugu; Sastry, Garikapati Narahari

    2015-03-30

    This study probes the nature of noncovalent interactions, such as cation-π, metal ion-lone pair (M-LP), hydrogen bonding (HB), charge-assisted hydrogen bonding (CAHB), and π-π interactions, using energy decomposition schemes-density functional theory (DFT)-symmetry-adapted perturbation theory and reduced variational space. Among cation-π complexes, the polarization and electrostatic components are the major contributors to the interaction energy (IE) for metal ion-π complexes, while for onium ion-π complexes (NH4+, PH4+, OH3+, and SH3+) the dispersion component is prominent. For M-LP complexes, the electrostatic component contributes more to the IE except the dicationic metal ion complexes with H2 S and PH3 where the polarization component dominates. Although electrostatic component dominates for the HB and CAHB complexes, dispersion is predominant in π-π complexes.

  14. Unified description of hydrogen bonding by a two-state effective Hamiltonian

    CERN Document Server

    McKenzie, Ross H

    2011-01-01

    An effective Hamiltonian is considered for hydrogen bonding between two molecules due to the quantum mechanical interaction between the orbitals of the H-atom and the donor and acceptor atoms in the molecules. The Hamiltonian acts on two diabatic states and has a simple chemically motivated form for its matrix elements. The model gives insight into the "H-bond puzzle", describes different classes of bonds, and empirical correlations between the donor-acceptor distance $R$ and binding energies, bond lengths, and the softening of vibrational frequencies. A key prediction is the UV photo-dissociation of H-bonded complexes via an excited electronic state with an exalted vibrational frequency.

  15. Quantum chemical study of chlorine-dissociation of oxalyl chloride (ClCO)2→2Cl + 2CO

    Institute of Scientific and Technical Information of China (English)

    DAI; Nianzhen; (戴年珍); LI; Zonghe; (李宗和)

    2003-01-01

    The multi-bond dissociation dynamics of oxalyl chloride ((ClCO)2) is investigated by ab initio calculation. Dissociation of C-Cl bond of oxalyl chloride in the ground state is of barrierless. After the absorption of a photon, (ClCO)2 is excited to the first excited state and one of its C-Cl bonds is broken toyield Cl and ClCOCO* free radicals. In addition, ClCOCO* with high energy is prone to release energy (Q), and to turn into ClCOCO in the ground state. The energy (Q) is adequate for ClCOCO to break down into ClCO and CO, and even for ClCO into Cl and CO. The result is consistent with the experimental data that Kong reported.

  16. Energy dependent sticking coefficients of trimethylamine on Si(001)-Influence of the datively bonded intermediate state on the adsorption dynamics

    Science.gov (United States)

    Lipponer, M. A.; Reutzel, M.; Dürr, M.; Höfer, U.

    2016-11-01

    The adsorption dynamics of the datively bonded trimethylamine (TMA) on Si(001) was investigated by means of molecular beam techniques. The initial sticking probability s0 of TMA on Si(001) was measured as a function of kinetic energy at two different surface temperatures (230 and 550 K). At given surface temperature, s0 was found to decrease with increasing kinetic energy (0.1 to 0.6 eV) indicating a non-activated reaction channel. At increased surface temperature, s0 is reduced due to the onset of desorption into the gas phase. The energy dependence of s0 is compared to the results for the adsorption of tetrahydrofuran (THF) on Si(001), which reacts via a datively bonded intermediate into a covalently bound final state. As s0 follows the same energy dependence both for TMA and THF, the datively bonded intermediate state is concluded to dominate the reaction dynamics in the latter case as well.

  17. Vibrational analysis on the revised potential energy curve of the low-barrier hydrogen bond in photoactive yellow protein

    Directory of Open Access Journals (Sweden)

    Yusuke Kanematsu

    2016-01-01

    Full Text Available Photoactive yellow protein (PYP has a characteristic hydrogen bond (H bond between p-coumaric acid chromophore and Glu46, whose OH bond length has been observed to be 1.21 Å by the neutron diffraction technique [Proc. Natl. Acad. Sci. 106, 440–4]. Although it has been expected that such a drastic elongation of the OH bond could be caused by the quantum effect of the hydrogen nucleus, previous theoretical computations including the nuclear quantum effect have so far underestimated the bond length by more than 0.07 Å. To elucidate the origin of the difference, we performed a vibrational analysis of the H bond on potential energy curve with O…O distance of 2.47 Å on the equilibrium structure, and that with O…O distance of 2.56 Å on the experimental crystal structure. While the vibrationally averaged OH bond length for equilibrium structure was underestimated, the corresponding value for crystal structure was in reasonable agreement with the corresponding experimental values. The elongation of the O…O distance by the quantum mechanical or thermal fluctuation would be indispensable for the formation of a low-barrier hydrogen bond in PYP.

  18. The influence of large-amplitude librational motion on the hydrogen bond energy for alcohol–water complexes

    DEFF Research Database (Denmark)

    Andersen, Jonas; Heimdal, J.; Larsen, René Wugt

    2015-01-01

    unambiguous assignments of the intermolecular high-frequency out-of-plane and low-frequency in-plane donor OH librational modes for mixed alcohol–water complexes. The vibrational assignments confirm directly that water acts as the hydrogen bond donor in the most stable mixed complexes and the tertiary alcohol...... is a superior hydrogen bond acceptor. The class of large-amplitude donor OH librational motion is shown to account for up to 5.1 kJ mol-1 of the destabilizing change of vibrational zero-point energy upon intermolecular OH...O hydrogen bond formation. The experimental findings are supported by complementary...

  19. Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 2. Preparation, dissociations, and energetics of 3-hydroxyoxolan-3-yl radical and cation.

    Science.gov (United States)

    Vivekananda, Shetty; Sadílek, Martin; Chen, Xiaohong; Adams, Luke E; Turecek, Frantisek

    2004-07-01

    The title radical (1) is generated in the gas-phase by collisional neutralization of carbonyl-protonated oxolan-3-one. A 1.5% fraction of 1 does not dissociate and is detected following reionization as survivor ions. The major dissociation of 1 (approximately 56%) occurs as loss of the hydroxyl H atom forming oxolan-3-one (2). The competing ring cleavages by O[bond]C-2 and C-4[bond]C-5 bond dissociations combined account for approximately 42% of dissociation and result in the formation of formaldehyde and 2-hydroxyallyl radical. Additional ring-cleavage dissociations of 1 resulting in the formation of C(2)H(3)O and C(2)H(4)O cannot be explained as occurring competitively on the doublet ground (X) electronic state of 1, but are energetically accessible from the A and higher electronic states accessed by vertical electron transfer. Exothermic protonation of 2 also produces 3-oxo-(1H)-oxolanium cation (3(+)) which upon collisional neutralization gives hypervalent 3-oxo-(1H)-oxolanium radical (3). The latter dissociates spontaneously by ring opening and expulsion of hydroxy radical. Experiment and calculations suggest that carbohydrate radicals incorporating the 3-hydroxyoxolan-3-yl motif will prefer ring-cleavage dissociations at low internal energies or upon photoexcitation by absorbing light at approximately 590 and approximately 400 nm.

  20. On the mean kinetic energy of the proton in strong hydrogen bonded systems

    Energy Technology Data Exchange (ETDEWEB)

    Finkelstein, Y. [Nuclear Research Center–Negev, Beer-Sheva 84190 (Israel); Moreh, R. [Physics Department, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel); Shang, S. L.; Wang, Y.; Liu, Z. K. [Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States); Shchur, Ya. [Institute for Condensed Matter Physics, 1 Svientsitskii str., L’viv 79011 (Ukraine)

    2016-02-07

    The mean atomic kinetic energies of the proton, Ke(H), and of the deuteron, Ke(D), were calculated in moderate and strongly hydrogen bonded (HB) systems, such as the ferro-electric crystals of the KDP type (XH{sub 2}PO{sub 4}, X = K, Cs, Rb, Tl), the DKDP (XD{sub 2}PO{sub 4}, X = K, Cs, Rb) type, and the X{sub 3}H(SO{sub 4}){sub 2} superprotonic conductors (X = K, Rb). All calculations utilized the simulated partial phonon density of states, deduced from density functional theory based first-principle calculations and from empirical lattice dynamics simulations in which the Coulomb, short range, covalent, and van der Waals interactions were accounted for. The presently calculated Ke(H) values for the two systems were found to be in excellent agreement with published values obtained by deep inelastic neutron scattering measurements carried out using the VESUVIO instrument of the Rutherford Laboratory, UK. The Ke(H) values of the M{sub 3}H(SO{sub 4}){sub 2} compounds, in which the hydrogen bonds are centro-symmetric, are much lower than those of the KDP type crystals, in direct consistency with the oxygen-oxygen distance R{sub OO}, being a measure of the HB strength.

  1. Energy and density analysis of the H2 molecule from the united atom to dissociation: the 3Sigma(g)+ and 3Sigma(u)+ states.

    Science.gov (United States)

    Corongiu, Giorgina; Clementi, Enrico

    2009-11-14

    The first 14 (3)Sigma(g)(+) and the first 15 (3)Sigma(u)(+) states of the H(2) molecule are computed with full configuration interaction both from Hartree-Fock molecular orbitals and Heitler-London atomic orbitals within the Born-Oppenheimer approximation, following recent studies for the (1)Sigma(g)(+) and (1)Sigma(u)(+) manifolds [Corongiu and Clementi, J. Chem. Phys. 131, 034301 (2009) and J. Phys. Chem. (in press)]. The basis sets utilized are extended and optimized Slater-type functions and spherical Gaussian functions. The states considered correspond to the configurations (1s(1)nl(1)) with n from 1 to 5; the internuclear separations sample the distances from 0.01 to 10,000 bohrs. For the first three (3)Sigma(g)(+) and (3)Sigma(u)(+) states and for the fourth and fifth (3)Sigma(g)(+) states, our computed energies at the equilibrium internuclear separation, when compared to the accurate values by Staszewska and Wolniewicz and by Kołos and Rychlewski, show deviations of about 0.006 kcal/mol, a test on the quality of our computations. Motivation for this work comes not only from obtaining potential energy curves for the high excited states of H(2) but also from characterizing the electronic density evolution from the united atom to dissociation to provide a detailed analysis of the energy contributions from selected basis subsets and to quantitatively decompose the state energies into covalent and ionic components. Furthermore, we discuss the origin of the seemingly irregular patterns in potential energy curves in the two manifolds, between 4 and 6-9 bohrs--there are two systems of states: the first, from the united atom to about 4 bohrs, is represented by functions with principal quantum number higher than the one needed at dissociation; this system interacts at around 4 bohrs with the second system, which is represented by functions with principal quantum number corresponding to one of the dissociation products.

  2. Electronic bond tuning with heterocyclic carbenes

    KAUST Repository

    Falivene, Laura

    2013-01-01

    We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

  3. Probing the bonding and structures of metal-organic radicals with zero energy electrons

    Institute of Scientific and Technical Information of China (English)

    YANG DongSheng

    2012-01-01

    Metal-organic radicals are reactive and transient because of the existence of unpaired valence electrons,and thus the characterization of these open-shell systems is challenging.In our work,the radicals are synthesized by the reaction of bare metal atoms and organic ligands in a laser-vaporization supersonic molecular beam source and characterized with pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy.The molecular beam ZEKE technique routinely yields sub-meV spectral resolution and is a powerful means to study the molecular bonding and structures.This account presents several examples of single-photon ZEKE spectroscopic applications in determining metal binding modes and molecular conformations.

  4. Carbon Bonds and the saving of energy; Bonos de carbono y el ahorro de energia

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez Ramirez, Alejandro [NovaEnergia (Mexico)

    2005-07-01

    This document deals with the development of the carbon bond project, the energy saving and the entry into force of the Kyoto Protocol at a world-wide level. In this project Mexico opts for a development model in which the economic growth brakes ties with the discharge of greenhouse effect gases and in which the progress does not mean more damages to our planet. [Spanish] Este documento trata sobre el desarrollo del proyecto de bonos de carbono, ahorro de energia y la entrada en vigor del Protocolo de Kyoto a nivel mundial, en el cual Mexico opta por un modelo de desarrollo en el que el crecimiento economico esta desvinculado de la emision de gases de efecto invernadero y en donde el progreso no signifique mas danos a nuestro planeta.

  5. Water adsorption and dissociation on BeO (001) and (100) surfaces

    CERN Document Server

    Gómez, M A; Kress, J D; Pratt, L R; Gomez, Maria A.; Kress, Joel D.; Pratt, Lawrence R.

    2007-01-01

    Plateaus in water adsorption isotherms on hydroxylated BeO surfaces suggest significant differences between the hydroxylated (100) and (001) surface structures and reactivities. Density functional theory structures and energies clarify these differences. Using relaxed surface energies, a Wulff construction yields a prism crystal shape exposing long (100) sides and much smaller (001) faces. This is consistent with the BeO prisms observed when beryllium metal is oxidized. A water oxygen atom binds to a single surface beryllium ion in the preferred adsorption geometry on either surface. The water oxygen/beryllium bonding is stronger on the surface with greater beryllium atom exposure, namely the less-stable (001) surface. Water/beryllium coordination facilitates water dissociation. On the (001) surface, the dissociation products are a hydroxide bridging two beryllium ions and a metal coordinated hydride with some surface charge depletion. On the (100) surface, water dissociates into a hydroxide ligating a Be ato...

  6. The Nature of Bonding in WC and WN

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The nature of bonding in the title compounds has been studied by using CASSCF and FOCl techniques. The ground states of WC and WN are found to be 3Δ and 4∑- state arising primarily from:...1σ2σ21π41δ13σ1 and ...1σ2σ21π41δ23σ1 configuration respectively. WC shows a strong character of covalent bond while WN have obvious character of ionic bond and the dissociation energy of WN is larger than that of WC (6.15 and 5.41 eV respective).

  7. An application of the novel quantum mechanical/molecular mechanical method combined with the theory of energy representation: An ionic dissociation of a water molecule in the supercritical water.

    Science.gov (United States)

    Takahashi, Hideaki; Satou, Wataru; Hori, Takumi; Nitta, Tomoshige

    2005-01-22

    A novel quantum chemical approach recently developed has been applied to an ionic dissociation of a water molecule (2H(2)O-->H(3)O(+)+OH(-)) in ambient and supercritical water. The method is based on the quantum mechanical/molecular mechanical (QM/MM) simulations combined with the theory of energy representation (QM/MM-ER), where the energy distribution function of MM solvent molecules around a QM solute serves as a fundamental variable to determine the hydration free energy of the solute according to the rigorous framework of the theory of energy representation. The density dependence of the dissociation free energy in the supercritical water has been investigated for the density range from 0.1 to 0.6 g/cm(3) with the temperature fixed at a constant. It has been found that the product ionic species significantly stabilizes in the high density region as compared with the low density. Consequently, the dissociation free energy decreases monotonically as the density increases. The decomposition of the hydration free energy has revealed that the entropic term (-TDeltaS) strongly depends on the density of the solution and dominates the behavior of the dissociation free energy with respect to the variation of the density. The increase in the entropic term in the low density region can be attributed to the decrease in the translational degrees of freedom brought about by the aggregation of solvent water molecules around the ionic solute.

  8. Threshold collision induced dissociation experiment for azobenzene and its derivatives

    Science.gov (United States)

    Rezaee, Mohammadreza; Compton, Robert

    In this study we investigated protonated azobenzene cation and properties of trans 2,2',6,6'-tetrafluoroazobenzene anion using the collision induced dissociation method and the results are compared with the results from ab initio electronic structure calculations. We measured the bond dissociation energies experimentally and found which theoretical quantum chemistry methods yield best results. Several high accuracy multi-level calculations such as CBS-QB3, G3 and G4 had been carried out to obtain reliable thermochemical information for azobenzene and several of its derivatives and their anion or cation. We also performed other experiments such as Raman spectroscopy to study these light sensitive molecules with promising applications such as photo-switching.

  9. Bond breaking in a Morse chain under tension: Fragmentation patterns, higher index saddles, and bond healing

    Science.gov (United States)

    Mauguière, F. A. L.; Collins, P.; Ezra, G. S.; Wiggins, S.

    2013-04-01

    We investigate the fragmentation dynamics of an atomic chain under tensile stress. We have classified the location, stability type (indices), and energy of all equilibria for the general n-particle chain, and have highlighted the importance of saddle points with index >1. We show that for an n = 2-particle chain under tensile stress the index 2 saddle plays a central role in organizing the dynamics. We apply normal form theory to analyze phase space structure and dynamics in a neighborhood of the index 2 saddle. We define a phase dividing surface (DS) that enables us to classify trajectories passing through a neighborhood of the saddle point using the values of the integrals associated with the normal form. We also generalize our definition of the dividing surface and define an extended dividing surface (EDS), which is used to sample and classify all trajectories that pass through a phase space neighborhood of the index 2 saddle at total energies less than that of the saddle. Classical trajectory simulations are used to study fragmentation patterns for the n = 2 chain under tension. That is, we investigate the relative probability for breaking one bond versus concerted fission of several (two, in this case) bonds. Initial conditions for trajectories are obtained by sampling the EDS at constant energy. We sample trajectories at fixed energies both above and below the energy of the saddle. The fate of trajectories (single versus multiple bond breakage) is explored as a function of the location of the initial condition on the EDS, and a connection made to the work of Chesnavich on collision-induced dissociation. A significant finding is that we can readily identify trajectories that exhibit bond healing. Such trajectories pass outside the nominal (index 1) transition state for single bond dissociation, but return to the potential well region, possibly several times, before ultimately dissociating.

  10. Influence of warm air-drying on enamel bond strength and surface free-energy of self-etch adhesives.

    Science.gov (United States)

    Shiratsuchi, Koji; Tsujimoto, Akimasa; Takamizawa, Toshiki; Furuichi, Tetsuya; Tsubota, Keishi; Kurokawa, Hiroyasu; Miyazaki, Masashi

    2013-08-01

    We examined the effect of warm air-drying on the enamel bond strengths and the surface free-energy of three single-step self-etch adhesives. Bovine mandibular incisors were mounted in self-curing resin and then wet ground with #600 silicon carbide (SiC) paper. The adhesives were applied according to the instructions of the respective manufacturers and then dried in a stream of normal (23°C) or warm (37°C) air for 5, 10, and 20 s. After visible-light irradiation of the adhesives, resin composites were condensed into a mold and polymerized. Ten samples per test group were stored in distilled water at 37°C for 24 h and then the bond strengths were measured. The surface free-energies were determined by measuring the contact angles of three test liquids placed on the cured adhesives. The enamel bond strengths varied according to the air-drying time and ranged from 15.8 to 19.1 MPa. The trends for the bond strengths were different among the materials. The value of the γS⁺ component increased slightly when drying was performed with a stream of warm air, whereas that of the γS⁻ component decreased significantly. These data suggest that warm air-drying is essential to obtain adequate enamel bond strengths, although increasing the drying time did not significantly influence the bond strength.

  11. Nanoscale metals and semiconductors for the storage of solar energy in chemical bonds

    Science.gov (United States)

    Manthiram, Karthish

    The transduction of electrical energy into chemical bonds represents one potential strategy for storing energy derived from intermittent sources such as solar and wind. Driving the electrochemical reduction of carbon dioxide using light requires (1) developing light absorbers which convert photons into electron-hole pairs and (2) catalysts which utilize these electrons and holes to reduce carbon dioxide and oxidize water, respectively. For both the light absorbers and catalysts, the use of nanoscale particles is advantageous, as charge transport length scales are minimized in the case of nanoscale light absorbers and catalytic surface-area-to-volume ratio is maximized for nanoscale catalysts. In many cases, although semiconductors and metals in the form of thin films and foils are increasingly well-characterized as photoabsorbers and electrocatalysts for carbon dioxide reduction, respectively, the properties of their nanoscale counterparts remain poorly understood. This dissertation explores the nature of the light absorption mode of non-stoichiometric semiconductors which are utilized as light absorbers and the development of catalysts with enhanced stability, activity, and selectivity for carbon dioxide reduction. Chapter 1 provides an overview of the state of development of methods of transducing the energy of photons into chemical bonds. Chapters 2 and 3 investigate the development of stable, active, and selective catalysts for the electrochemical reduction of carbon dioxide. Chapter 2 examines how copper nanoparticles have enhanced activities and selectivities for methanation compared to copper foils. Chapter 3 focuses on the development of strategies to stabilize high-surface-area catalysts to prevent surface area loss during electrochemical carbon dioxide reduction. Chapters 4 and 5 entail a fundamental understanding of the light absorption mode of nanoscale photoabsorbers used in both photoelectrochemical cells and in photovoltaics. Chapter 4 focuses on the

  12. Microsolvation of methylmercury: structures, energies, bonding and NMR constants ((199)Hg, (13)C and (17)O).

    Science.gov (United States)

    Flórez, Edison; Maldonado, Alejandro F; Aucar, Gustavo A; David, Jorge; Restrepo, Albeiro

    2016-01-21

    Hartree-Fock (HF) and second order perturbation theory (MP2) calculations within the scalar and full relativistic frames were carried out in order to determine the equilibrium geometries and interaction energies between cationic methylmercury (CH3Hg(+)) and up to three water molecules. A total of nine structures were obtained. Bonding properties were analyzed using the Quantum Theory of Atoms In Molecules (QTAIM). The analyses of the topology of electron densities reveal that all structures exhibit a partially covalent HgO interaction between methylmercury and one water molecule. Consideration of additional water molecules suggests that they solvate the (CH3HgOH2)(+) unit. Nuclear magnetic shielding constants σ((199)Hg), σ((13)C) and σ((17)O), as well as indirect spin-spin coupling constants J((199)Hg-(13)C), J((199)Hg-(17)O) and J((13)C-(17)O), were calculated for each one of the geometries. Thermodynamic stability and the values of NMR constants correlate with the ability of the system to directly coordinate oxygen atoms of water molecules to the mercury atom in methylmercury and with the formation of hydrogen bonds among solvating water molecules. Relativistic effects account for 11% on σ((13)C) and 14% on σ((17)O), which is due to the presence of Hg (heavy atom on light atom, HALA effect), while the relativistic effects on σ((199)Hg) are close to 50% (heavy atom on heavy atom itself, HAHA effect). J-coupling constants are highly influenced by relativity when mercury is involved as in J((199)Hg-(13)C) and J((199)Hg-(17)O). On the other hand, our results show that the values of NMR constants for carbon and oxygen, atoms which are connected through mercury (C-HgO), are highly correlated and are greatly influenced by the presence of water molecules. Water molecules introduce additional electronic effects to the relativistic effects due to the mercury atom.

  13. Electric and magnetic properties computed for valence bond structures: is there a link between pauling resonance energy and ring current?

    Science.gov (United States)

    Havenith, Remco W A

    2006-04-28

    To establish the link between the aromaticity descriptors based on the Pauling resonance energy and the molecular properties, the electric (polarizability) and magnetic (magnetizability) field response properties have been calculated using the valence bond approach for various molecules and their individual Kekulé resonance structures. The results show that there is no direct relationship between the Pauling resonance energy and the properties; the response properties are weighted averages of the properties of the individual structures. According to the aromaticity criteria based on molecular properties, one-structure benzene would be aromatic; thus, concerning molecular properties, spin-coupled bonds do not behave like localized bonds in Lewis structures, with which they are usually associated.

  14. Identification of c-Type Heme-Containing Peptides Using Non-Activated Immobilized Metal Affinity Cchromatography Resin Enrichment and Higher-Energy Collisional Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Haizhen; Yang, Feng; Qian, Weijun; Brown, Roslyn N.; Wang, Yuexi; Merkley, Eric D.; Park, Jea H.; Monroe, Matthew E.; Purvine, Samuel O.; Moore, Ronald J.; Shi, Liang; Fredrickson, Jim K.; Pasa-Tolic, Ljiljana; Smith, Richard D.; Lipton, Mary S.

    2011-10-01

    c-type cytochromes play essential roles in many biological activities of both prokaryotic and eukaryotic cells, including electron transfer, enzyme catalysis and induction of apoptosis. We report a novel enrichment strategy for identifying c-type heme-containing peptides that uses non-activated IMAC resin. The strategy demonstrated at least seven-fold enrichment for heme-containing peptides digested from a cytochrome c protein standard, and quantitative linear performance was also assessed for heme-containing peptide enrichment. Heme-containing peptides extracted from the periplasmic fraction of Shewanella oneidensis MR-1 were further identified using higher-energy collisional dissociation tandem mass spectrometry. The results demonstrated the applicability of this enrichment strategy to identify c-type heme-containing peptides from a highly complex biological sample, and at the same time, confirmed the periplasmic localization of heme-containing proteins during suboxic respiration activities of S. oneidensis MR-1.

  15. Molecular resonant dissociation of surface-adsorbed molecules by plasmonic nanoscissors

    Science.gov (United States)

    Zhang, Zhenglong; Sheng, Shaoxiang; Zheng, Hairong; Xu, Hongxing; Sun, Mengtao

    2014-04-01

    The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis, photosynthesis and the degradation of plastic, it is hard to break individual molecular bonds for those molecules adsorbed on the surface because of the weak light-absorption in molecules and the redistribution of the resulting vibrational energy both inside the molecule and to its surrounding environment. Here we show how to overcome these obstacles with a plasmonic hot-electron mediated process and demonstrate a new method that allows the sensitive control of resonant dissociation of surface-adsorbed molecules by `plasmonic' scissors. To that end, we used a high-vacuum tip-enhanced Raman spectroscopy (HV-TERS) setup to dissociate resonantly excited NC2H6 fragments from Malachite green. The surface plasmons (SPs) excited at the sharp metal tip not only enhance the local electric field to harvest the light incident from the laser, but crucially supply `hot electrons' whose energy can be transferred to individual bonds. These processes are resonant Raman, which result in some active chemical bonds and then weaken these bonds, followed by dumping in lots of indiscriminant energy and breaking the weakest bond. The method allows for sensitive control of both the rate and probability of dissociation through their dependence on the density of hot electrons, which can be manipulated by tuning the laser intensity or tunneling current/bias voltage in the HV-TERS setup, respectively. The concepts of plasmonic scissors open up new versatile avenues for the deep understanding of in situ surface-catalyzed chemistry.The ability to break individual bonds or specific modes in chemical reactions is an ardently sought goal by chemists and physicists. While photochemistry based methodologies are very successful in controlling e.g. photocatalysis

  16. Electric and Magnetic properties Computed for Valence Bond Structures: Is There a Link between Pauling Resonance Energy and Ring Current?

    NARCIS (Netherlands)

    Havenith, R.W.A.

    2006-01-01

    To establish the link between the aromaticity descriptors based on the Pauling resonance energy and the molecular properties, the electric (polarizability) and magnetic (magnetizability) field response properties haven been calculated using the valence bond approach for various molecules and their i

  17. Co-C Dissociation of Adenosylcobalamin (Coenzyme B-12): Role of Dispersion, Induction Effects, Solvent Polarity, and Relativistic and Thermal Corrections

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2014-01-01

    of its unique organometallic Co-C bond has inspired multiple studies of this cofactor. This paper reports the fully relaxed potential energy surface of Co-C cleavage of Ado Cbl, including for the first time all side-chain interactions with the dissociating Ado group. Various methods and corrections...

  18. Measurements of internal stresses in bond coating using high energy x-rays from synchrotron radiation source

    CERN Document Server

    Suzuki, K; Akiniwa, Y; Nishio, K; Kawamura, M; Okado, H

    2002-01-01

    Thermal barrier coating (TBC) techniques enable high temperature combustion of turbines made of Ni-base alloy. TBC is made of zirconia top coating on NiCoCrAlY bond coating. The internal stresses in the bond coating play essential role in the delamination or fracture of TBC in service. With the X-rays from laboratory equipments, it is impossible to measure nondestructively the internal stress in the bond coating under the top coating. synchrotron radiations with a high energy and high brightness have a large penetration depth as compared with laboratory X-rays. Using the high energy X-rays from the synchrotron radiation, it is possible to measure the internal stress in the bond coating through the top coating. In this study, the furnace, which can heat a specimen to 1473 K, was developed for the stress measurement of the thermal barrier coatings. The internal stresses in the bond coating were measured at the room temperature, 773 K, 1073 K and 1373 K by using the 311 diffraction from Ni sub 3 Al with about 73...

  19. Multiphoton dissociative ionization of CS+

    Science.gov (United States)

    Rajput, Jyoti; Jochim, Bethany; Zohrabi, M.; Betsch, K. J.; Ablikim, U.; Berry, Ben; Severt, T.; Summers, A. M.; Armstrong, G. S. J.; Esry, B. D.; Carnes, K. D.; Ben-Itzhak, I.

    2015-05-01

    We have studied the dissociative photoionization of a CS+ molecular ion beam in the strong-field regime using <50 fs IR laser pulses (λ ~ 790 nm) from a 10 kHz, ~2 mJ (per pulse) Ti:Sapphire laser system. A coincidence three-dimensional momentum imaging method was used to measure all ions and neutrals formed during this multiphoton process. Two prominent channels were observed: charge-symmetric dissociation, yielding C+ + S+, and charge-asymmetric dissociation, yielding C + S2+. The differences between these two channels with reference to their relative production probability, energetics, and angular distributions is the focus of this work. This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy. BJ is also supported by DOE-SCGF (DE-AC05-06OR23100).

  20. Mediatorless solar energy conversion by covalently bonded thylakoid monolayer on the glassy carbon electrode.

    Science.gov (United States)

    Lee, Jinhwan; Im, Jaekyun; Kim, Sunghyun

    2016-04-01

    Light reactions of photosynthesis that take place in thylakoid membranes found in plants or cyanobacteria are among the most effective ways of utilizing light. Unlike most researches that use photosystem I or photosystem II as conversion units for converting light to electricity, we have developed a simple method in which the thylakoid monolayer was covalently immobilized on the glassy carbon electrode surface. The activity of isolated thylakoid membrane was confirmed by measuring evolving oxygen under illumination. Glassy carbon surfaces were first modified with partial or full monolayers of carboxyphenyl groups by reductive C-C coupling using 4-aminobenzoic acid and aniline and then thylakoid membrane was bioconjugated through the peptide bond between amine residues of thylakoid and carboxyl groups on the surface. Surface properties of modified surfaces were characterized by cyclic voltammetry, contact angle measurements, and electrochemical impedance spectroscopy. Photocurrent of 230 nA cm(-2) was observed when the thylakoid monolayer was formed on the mixed monolayer of 4-carboxylpheny and benzene at applied potential of 0.4V vs. Ag/AgCl. A small photocurrent resulted when the 4-carboxyphenyl full monolayer was used. This work shows the possibility of solar energy conversion by directly employing the whole thylakoid membrane through simple surface modification.

  1. First-Principles Modeling of Direct versus Oxygen-Assisted Water Dissociation on Fe(100 Surfaces

    Directory of Open Access Journals (Sweden)

    Wenju Wang

    2016-02-01

    Full Text Available The O–H bond breaking in H2O molecules on metal surfaces covered with pre-adsorbed oxygen atoms is an important topic in heterogeneous catalysis. The adsorption configurations of H2O and relevant dissociation species on clean and O-pre-adsorbed Fe(100 surfaces were investigated by density functional theory (DFT. The preferential sites for H2O, HO, O, and H were investigated on both surfaces. Both the first H abstraction from adsorbed H2O and the subsequent OH dissociation are exothermic on the O-pre-adsorbed Fe(100 surface. However, the pre-adsorbed O significantly reduces the kinetics energy barriers for both reactions. Our results confirmed that the presence of pre-adsorbed oxygen species could significantly promote H2O dissociation.

  2. Dynamics of the dissociative electron attachment in H2O and D2O: The A1 resonance and axial recoil approximation

    Indian Academy of Sciences (India)

    N Bhargava Ram; Vaibhav S Prabhudesai; E Krishnakumar

    2012-01-01

    The dynamics of the formation and decay of negative ion resonance of A1 symmetry at 8.5 eV electron energy in the dissociative electron attachment (DEA) process in H2O and D2O are investigated using the velocity slice imaging technique. While the highest energy hydride ions formed by DEA show angular distributions characteristic to the A1 symmetry, those formed with low-kinetic energy show considerably different angular distributions indicating changes in the orientation of the dissociating bond due to bending mode vibrations. Our observations are quite different from the recently reported measurements, but consistent with the fully quantum calculations.

  3. Thermochemical benchmarking of hydrocarbon bond separation reaction energies: Jacob's ladder is not reversed!

    Science.gov (United States)

    Krieg, Helge; Grimme, Stefan

    2010-10-01

    We reinvestigate the performance of Kohn-Sham density functional (DF) methods for a thermochemical test set of bond separation reactions of alkanes (BSR36) published recently by Steinmann et al. [J. Chem. Theory Comput. 5, 2950 (2009)]. According to our results, the tested approximations perform for this rather special benchmark as usual. We show that the choice of reference enthalpies plays a crucial role in the assessment. Due to the large stoichiometric factors involved, errors of various origin are strongly amplified. Inconsistent reference data are avoided by computing reference energies at the CCSD(T)/CBS level. These are compared to results for a variety of standard DFs. Two different versions of London dispersion corrections (DFT-D2 and DFT-D3) are applied and found to be very significant. The most accurate results are obtained with B2GPPLYP-D2 (MAD = 0.4 kcal mol-1) B2PLYP-D2 (MAD = 0.5 kcal mol-1) and B97-D2 (MAD = 0.9 kcal mol-1 methods. Dispersion corrections not only improve the computed BSR energies but also diminish the accuracy differences between the DFs. The previous DFT-D2 version performs better due to error compensation of medium-range correlation effects between the semi-classical and the density-based description. We strongly recommend not to overinterpret results regarding DF accuracy when based on a single set of chemical reactions and to use high-level theoretical data for benchmarking purposes.

  4. Bond energies and structures of ammonia-sulfuric acid positive cluster ions.

    Science.gov (United States)

    Froyd, Karl D; Lovejoy, Edward R

    2012-06-21

    New particle formation in the atmosphere is initiated by nucleation of gas-phase species. The small molecular clusters that act as seeds for new particles are stabilized by the incorporation of an ion. Ion-induced nucleation of molecular cluster ions containing sulfuric acid generates new particles in the background troposphere. The addition of a proton-accepting species to sulfuric acid cluster ions can further stabilize them and may promote nucleation under a wider range of conditions. To understand and accurately predict atmospheric nucleation, the stabilities of each molecular cluster within a chemical family must be known. We present the first comprehensive measurements of the ammonia-sulfuric acid positive ion cluster system NH(4)(+)(NH(3))(n)(H(2)SO(4))(s). Enthalpies and entropies of individual growth steps within this system were measured using either an ion flow reactor-mass spectrometer system under equilibrium conditions or by thermal decomposition of clusters in an ion trap mass spectrometer. Low level ab initio structural calculations provided inputs to a master equation model to determine bond energies from thermal decomposition measurements. Optimized ab initio structures for clusters up through n = 3, s = 3 are reported. Upon addition of ammonia and sulfuric acid pairs, internal proton transfer generates multiple NH(4)(+) and HSO(4)(-) ions within the clusters. These multiple-ion structures are up to 50 kcal mol(-1) more stable than corresponding isomers that retain neutral NH(3) and H(2)SO(4) species. The lowest energy n = s clusters are composed entirely of ions. The addition of acid-base pairs to the core NH(4)(+) ion generates nanocrystals that begin to resemble the ammonium bisulfate bulk crystal starting with the smallest n = s cluster, NH(4)(+)(NH(3))(1)(H(2)SO(4))(1). In the absence of water, this cluster ion system nucleates spontaneously for conditions that encompass most of the free troposphere.

  5. Adhesive-Bonded Composite Joint Analysis with Delaminated Surface Ply Using Strain-Energy Release Rate

    Science.gov (United States)

    Chadegani, Alireza; Yang, Chihdar; Smeltzer, Stanley S. III

    2012-01-01

    This paper presents an analytical model to determine the strain energy release rate due to an interlaminar crack of the surface ply in adhesively bonded composite joints subjected to axial tension. Single-lap shear-joint standard test specimen geometry with thick bondline is followed for model development. The field equations are formulated by using the first-order shear-deformation theory in laminated plates together with kinematics relations and force equilibrium conditions. The stress distributions for the adherends and adhesive are determined after the appropriate boundary and loading conditions are applied and the equations for the field displacements are solved. The system of second-order differential equations is solved to using the symbolic computation tool Maple 9.52 to provide displacements fields. The equivalent forces at the tip of the prescribed interlaminar crack are obtained based on interlaminar stress distributions. The strain energy release rate of the crack is then determined by using the crack closure method. Finite element analyses using the J integral as well as the crack closure method are performed to verify the developed analytical model. It has been shown that the results using the analytical method correlate well with the results from the finite element analyses. An attempt is made to predict the failure loads of the joints based on limited test data from the literature. The effectiveness of the inclusion of bondline thickness is justified when compared with the results obtained from the previous model in which a thin bondline and uniform adhesive stresses through the bondline thickness are assumed.

  6. Discovering Chemistry With Natural Bond Orbitals

    CERN Document Server

    Weinhold, Frank

    2012-01-01

    This book explores chemical bonds, their intrinsic energies, and the corresponding dissociation energies which are relevant in reactivity problems. It offers the first book on conceptual quantum chemistry, a key area for understanding chemical principles and predicting chemical properties. It presents NBO mathematical algorithms embedded in a well-tested and widely used computer program (currently, NBO 5.9). While encouraging a "look under the hood" (Appendix A), this book mainly enables students to gain proficiency in using the NBO program to re-express complex wavefunctions in terms of intui

  7. Dissociation and dissociative ionization of H2+ using the time-dependent surface flux method

    CERN Document Server

    Yue, Lun

    2014-01-01

    The time-dependent surface flux method developed for the description of electronic spectra [L. Tao and A. Scrinzi, New J. Phys. 14, 013021 (2012); A. Scrinzi, New J. Phys. 14, 085008 (2012)] is extended to treat dissociation and dissociative ionization processes of H2+ interacting with strong laser pulses. By dividing the simulation volume into proper spatial regions associated with the individual reaction channels and monitoring the probability flux, the joint energy spectrum for the dissociative ionization process and the energy spectrum for dissociation is obtained. The methodology is illustrated by solving the time-dependent Schr\\"{o}dinger equation (TDSE) for a collinear one-dimensional model of H2+ with electronic and nuclear motions treated exactly and validated by comparison with published results for dissociative ionization. The results for dissociation are qualitatively explained by analysis based on dressed diabatic Floquet potential energy curves, and the method is used to investigate the breakdow...

  8. Dissociative Electron Attachment

    Science.gov (United States)

    Arreola, Esmeralda; Esmeralda Arreola Collaboration; Leigh Hargreaves Collaboration

    Since the pioneering work of Boudiaffa et al., it has been understood that electrons, even with energies near or below the ionization threshold, are capable of initiating strand-breaks in human DNA. This discovery raised important questions for cancer treatments, since sub-ionizing electrons are known to be the most copiously produced secondary product of radiation therapy. But even to date these factors are largely excluded from dosimetry calculations. This lack of inclusion is, at least in part, certainly due to the dearth of fundamental data describing low-energy electron interactions with nucleotide molecules that form the basis of DNA. Understanding of how such slow electrons are able to damage DNA remains incomplete, but the strongly peaked nature of Boudiaffa et al.'s data gives strong hints at resonantly driven collision processes. DNA damage is therefore most likely driven by ``dissociative electron attachment'' (DEA). DEA is a rather complicated process to model due to the coupling of electronic and nuclear degrees of freedom in the molecule. At the California State University Fullerton, we are currently commissioning a new spectrometer to study dissociation channels, reaction rates and orientation effects in DEA collisions between slow electrons and nucleotide molecules. At the meeting we will present design parameters and commissioning data for this new apparatus.

  9. Dissociative electron attachments to ethanol and acetaldehyde: A combined experimental and simulation study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xu-Dong; Xuan, Chuan-Jin; Feng, Wen-Ling; Tian, Shan Xi, E-mail: sxtian@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at the Microscale, Center of Advanced Chemical Physics, and Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2015-02-14

    Dissociation dynamics of the temporary negative ions of ethanol and acetaldehyde formed by the low-energy electron attachments is investigated by using the anion velocity map imaging technique and ab initio molecular dynamics simulations. The momentum images of the dominant fragments O{sup −}/OH{sup −} and CH{sub 3}{sup −} are recorded, indicating the low kinetic energies of O{sup −}/OH{sup −} for ethanol while the low and high kinetic energy distributions of O{sup −} ions for acetaldehyde. The CH{sub 3}{sup −} image for acetaldehyde also shows the low kinetic energy. With help of the dynamics simulations, the fragmentation processes are qualitatively clarified. A new cascade dissociation pathway to produce the slow O{sup −} ion via the dehydrogenated intermediate, CH{sub 3}CHO{sup −} (acetaldehyde anion), is proposed for the dissociative electron attachment to ethanol. After the electron attachment to acetaldehyde molecule, the slow CH{sub 3}{sup −} is produced quickly in the two-body dissociation with the internal energy redistributions in different aspects before bond cleavages.

  10. Dissociation of CO induced by He2+ ions : II. Dissociation pathways and states

    NARCIS (Netherlands)

    Schlatholter, T; Hoekstra, R; Morgenstern, R

    1997-01-01

    The dissociation of COq+ ions (q less than or equal to 3) produced in collisions of 2-10 keV amu(-1) He2+ ions with CO has been studied by time-of-flight methods. From the time-of-flight spectra the energy released in the dissociation process is determined. Our results for the kinetic energy release

  11. On optimal designing of low frequency polychromatic fields for facile photo-dissociation of model diatomic molecules

    Indian Academy of Sciences (India)

    S Ghosh; K Maji; R Sharma; S P Bhattacharyya

    2009-09-01

    The dissociation of a diatomic molecule in low frequency polychromatic fields of moderate intensities is studied. Genetic Algorithm is invoked to search out a set of four optimal non-resonant frequencies (1 - 4), intensities (1 - 4) the and phase angles (1 - 4), for achieving a facile photo dissociation. Time-dependent Hellmann-Feynman theorem is used to gain insight into the frequency resolved energy absorption pattern. The ‘quantum phase space’ structures indicate occurrence of bond breaking dynamics akin to the classical one.

  12. Dissociation dynamics of methylal

    Energy Technology Data Exchange (ETDEWEB)

    Beaud, P.; Frey, H.-M.; Gerber, T.; Mischler, B.; Radi, P.P.; Tzannis, A.-P. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The dissociation of methylal is investigated using mass spectrometry, combined with a pyrolytic radical source and femtosecond pump probe experiments. Based on preliminary results two reaction paths of methylal dissociation are proposed and discussed. (author) 4 fig., 3 refs.

  13. Perturbation calculations on the variation of hydrogen---bond energies with intermolecular distance

    NARCIS (Netherlands)

    Duijneveldt-van de Rijdt, J.G.C.M. van; Duijneveldt, F.B. van

    1968-01-01

    In previous perturbation calculations on the hydrogen bond [6] the short-range repulsion was seriously underestimated. It is shown that this can be remedied by choosing a more realistic model system and using exact 3-centre integrals.

  14. Is the decrease of the total electron energy density a covalence indicator in hydrogen and halogen bonds?

    Science.gov (United States)

    Angelina, Emilio L; Duarte, Darío J R; Peruchena, Nélida M

    2013-05-01

    In this work, halogen bonding (XB) and hydrogen bonding (HB) complexes were studied with the aim of analyzing the variation of the total electronic energy density H(r b ) with the interaction strengthening. The calculations were performed at the MP2/6-311++G(2d,2p) level of approximation. To explain the nature of such interactions, the atoms in molecules theory (AIM) in conjunction with reduced variational space self-consistent field (RVS) energy decomposition analysis were carried out. Based on the local virial theorem, an equation to decompose the total electronic energy density H(r b ) in two energy densities, (-G(r b )) and 1/4∇(2)ρ(r b ), was derived. These energy densities were linked with the RVS interaction energy components. Through the connection between both decomposition schemes, it was possible to conclude that the decrease in H(r b ) with the interaction strengthening observed in the HB as well as the XB complexes, is mainly due to the increase in the attractive electrostatic part of the interaction energy and in lesser extent to the increase in its covalent character, as is commonly considered.

  15. Non-dissociative and dissociative ionization of a CO+ beam in intense ultrashort laser pulses

    Science.gov (United States)

    Gaire, B.; Ablikim, U.; Zohrabi, M.; Roland, S.; Carnes, K. D.; Ben-Itzhak, I.

    2011-05-01

    We have investigated the ionization of CO+ beams in intense ultrashort laser pulses. With the recent upgrades to our coincidence three-dimensional momentum imaging method we are able to measure both non-dissociative and dissociative ionization of the molecular-ion beam targets. Using CO+ as an example, we have found that non-dissociative ionization (leading to the metastable dication CO2+) involves a direct transition, i.e. the molecule is ionized with little or no internuclear distance stretch. Dissociative ionization (C+ + O+) occurs both directly and indirectly, stretching first and then ionizing. Our results show that the yield of dissociative ionization is higher than that of non-dissociative ionization and can be manipulated with the laser pulse duration by suppressing the indirect ionization path using ultrashort pulses (Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy.

  16. High-energy, stable and recycled molecular solar thermal storage materials using AZO/graphene hybrids by optimizing hydrogen bonds

    Science.gov (United States)

    Luo, Wen; Feng, Yiyu; Qin, Chengqun; Li, Man; Li, Shipei; Cao, Chen; Long, Peng; Liu, Enzuo; Hu, Wenping; Yoshino, Katsumi; Feng, Wei

    2015-10-01

    An important method for establishing a high-energy, stable and recycled molecular solar heat system is by designing and preparing novel photo-isomerizable molecules with a high enthalpy and a long thermal life by controlling molecular interactions. A meta- and ortho-bis-substituted azobenzene chromophore (AZO) is covalently grafted onto reduced graphene oxide (RGO) for solar thermal storage materials. High grafting degree and close-packed molecules enable intermolecular hydrogen bonds (H-bonds) for both trans-(E) and cis-(Z) isomers of AZO on the surface of nanosheets, resulting in a dramatic increase in enthalpy and lifetime. The metastable Z-form of AZO on RGO is thermally stabilized with a half-life of 52 days by steric hindrance and intermolecular H-bonds calculated using density functional theory (DFT). The AZO-RGO fuel shows a high storage capacity of 138 Wh kg-1 by optimizing intermolecular H-bonds with a good cycling stability for 50 cycles induced by visible light at 520 nm. Our work opens up a new method for making advanced molecular solar thermal storage materials by tuning molecular interactions on a nano-template.An important method for establishing a high-energy, stable and recycled molecular solar heat system is by designing and preparing novel photo-isomerizable molecules with a high enthalpy and a long thermal life by controlling molecular interactions. A meta- and ortho-bis-substituted azobenzene chromophore (AZO) is covalently grafted onto reduced graphene oxide (RGO) for solar thermal storage materials. High grafting degree and close-packed molecules enable intermolecular hydrogen bonds (H-bonds) for both trans-(E) and cis-(Z) isomers of AZO on the surface of nanosheets, resulting in a dramatic increase in enthalpy and lifetime. The metastable Z-form of AZO on RGO is thermally stabilized with a half-life of 52 days by steric hindrance and intermolecular H-bonds calculated using density functional theory (DFT). The AZO-RGO fuel shows a high

  17. Critical surface energy of composite cement containing MDP (10-methacryloyloxydecyl dihydrogen phosphate) and chemical bonding to hydroxyapatite.

    Science.gov (United States)

    Dabsie, Firas; Grégoire, Geneviève; Sharrock, Patrick

    2012-01-01

    Self-adhesive composite cements are increasingly used for cementing inlays/onlays, intraradicular posts, crowns and laminate veneers. Wider clinical acceptance is driven by simpler and faster handling procedures, much like observed for self-etching adhesives. 10-Methacryloyloxydecyl dihydrogen phosphate (MDP) is a bi-functional monomer incorporated as the reactive ingredient in a contemporary self-adhesive cement. We have examined the surface free energy parameters of this cement and studied the mode of action of the cement on dentine substrate by contact angle measurements to determine the critical surface energy of the cement. Retention of the infrared absorption bands characteristic of the acrylate moieties on the surface of hydroxyapatite particles suggests that MDP contributes to the overall bonding to dentine by forming ionic chemical bonds with surface calcium ions in dentine crystalites.

  18. Quantum entanglement and the dissociation process of diatomic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Esquivel, Rodolfo O; Molina-Espiritu, Moyocoyani [Departamento de Quimica, Universidad Autonoma Metropolitana, 09340-Mexico DF (Mexico); Flores-Gallegos, Nelson [Unidad Profesional Interdisciplinaria de IngenierIa, Campus Guanajuato del Instituto Politecnico Nacional, 36275-Guanajuato (Mexico); Plastino, A R; Angulo, Juan Carlos; Dehesa, Jesus S [Instituto Carlos I de Fisica Teorica y Computacional, and Departamento de Fisica Atomica, Molecular y Nuclear, Universidad de Granada, 18071-Granada (Spain); Antolin, Juan, E-mail: esquivel@xanum.uam.mx, E-mail: arplastino@ugr.es [Departamento de Fisica Aplicada, EUITIZ, Universidad de Zaragoza, 50018-Zaragoza (Spain)

    2011-09-14

    In this work, we investigate quantum entanglement-related aspects of the dissociation process of some selected, representative homo- and heteronuclear diatomic molecules. This study is based upon high-quality ab initio calculations of the (correlated) molecular wavefunctions involved in the dissociation processes. The values of the electronic entanglement characterizing the system in the limit cases corresponding to (i) the united-atom representation and (ii) the asymptotic region when atoms dissociate are discussed in detail. It is also shown that the behaviour of the electronic entanglement as a function of the reaction coordinate R exhibits remarkable correspondences with the phenomenological description of the physically meaningful regimes comprising the processes under study. In particular, the extrema of the total energies and the electronic entanglement are shown to be associated with the main physical changes experienced by the molecular spatial electronic density, such as charge depletion and accumulation or bond cleavage regions. These structural changes are characterized by several selected descriptors of the density, such as the Laplacian of the electronic molecular distributions (LAP), the molecular electrostatic potential (MEP) and the atomic electric potentials fitted to the MEP.

  19. Using beryllium bonds to change halogen bonds from traditional to chlorine-shared to ion-pair bonds.

    Science.gov (United States)

    Alkorta, Ibon; Elguero, José; Mó, Otilia; Yáñez, Manuel; Del Bene, Janet E

    2015-01-21

    Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the structures, binding energies, and bonding characteristics of binary complexes HFBe:FCl, R2Be:FCl, and FCl:N-base, and of ternary complexes HFBe:FCl:N-base and R2Be:FCl:N-base for R = H, F, Cl; N-base = NH3, NHCH2, NCH. Dramatic synergistic cooperative effects have been found between the Be···F beryllium bonds and the Cl···N halogen bonds in ternary complexes. The Cl···N traditional halogen bonds and the Be···F beryllium bonds in binary complexes become significantly stronger in ternary complexes, while the F-Cl bond weakens. Charge-transfer from F to the empty p(σ) orbital of Be leads to a bending of the XYBe molecule and a change in the hybridization of Be, which in the limit becomes sp(2). As a function of the intrinsic basicity of the nitrogen base and the intrinsic acidity of the Be derivative, the halogen-bond type evolves from traditional to chlorine-shared to ion-pair bonds. The mechanism by which an ion-pair complex is formed is similar to that involved in the dissociative proton attachment process. EOM-CCSD spin-spin coupling constants (1X)J(Cl-N) across the halogen bond in these complexes also provide evidence of the same evolution of the halogen-bond type.

  20. Gadolinium (Gd) Oxide, Carbide, and Carbonyl Cation Bond Energies and Evaluation of the Gd + O → GdO(+) + e(-) Chemi-Ionization Reaction Enthalpy.

    Science.gov (United States)

    Demireva, Maria; Kim, JungSoo; Armentrout, P B

    2016-11-03

    Guided ion beam mass spectrometry (GIBMS) is used to measure the kinetic energy dependent product ion cross sections for reactions of the lanthanide metal gadolinium cation (Gd(+)) with O2, CO2, and CO and for reactions of GdO(+) with CO, O2, and Xe. GdO(+) is formed through barrierless and exothermic processes in the reactions of Gd(+) with O2 and CO2. All other reactions observed are endothermic, and analyses of their kinetic energy dependent cross sections yield 0 K bond dissociation energies (BDEs) for GdO(+), GdC(+), and GdCO(+). The 0 K BDE for GdO(+) is determined from five different reactions to be 7.69 ± 0.10 eV, and this value is combined with literature data to derive the ionization energy (IE) of GdO as 5.82 ± 0.16 eV. Additionally, GdC(+) and GdCO(+) BDEs of 3.18 ± 0.18 eV and 0.65 ± 0.06 eV are obtained from analysis of the Gd(+) reactions with CO and CO2, respectively. Theoretical GdO(+), GdC(+), and GdCO(+) BDEs are calculated for comparison with experiment using various Gd basis sets with an effective core potential and several levels of theory. For calculations that correctly predict a (10)D ground state for Gd(+), good agreement between theoretical and measured GdC(+) and GdCO(+) BDEs is obtained, whereas the GdO(+) BDE is underestimated in these calculations by about 0.8 eV. Additional BDEs for GdO(+) and GdC(+) are calculated using triple- and quadruple-ζ correlation consistent all-electron basis sets for Gd. Calculations with these basis sets provide better agreement with experiment for GdO(+) but not for GdC(+). The measured Gd(+) oxide, carbide, and carbonyl BDEs are similar to those for the group 3 metal ions, Sc(+) and Y(+). This is attributed to similarities in the ground state electronic configurations of these metal ions leading to similar interaction strengths. The experimental GdO(+) BDE measured here combined with the known IE of Gd is used to determine an exothermicity of 1.54 ± 0.10 eV for the Gd chemi-ionization reaction

  1. High-energy, stable and recycled molecular solar thermal storage materials using AZO/graphene hybrids by optimizing hydrogen bonds.

    Science.gov (United States)

    Luo, Wen; Feng, Yiyu; Qin, Chengqun; Li, Man; Li, Shipei; Cao, Chen; Long, Peng; Liu, Enzuo; Hu, Wenping; Yoshino, Katsumi; Feng, Wei

    2015-10-21

    An important method for establishing a high-energy, stable and recycled molecular solar heat system is by designing and preparing novel photo-isomerizable molecules with a high enthalpy and a long thermal life by controlling molecular interactions. A meta- and ortho-bis-substituted azobenzene chromophore (AZO) is covalently grafted onto reduced graphene oxide (RGO) for solar thermal storage materials. High grafting degree and close-packed molecules enable intermolecular hydrogen bonds (H-bonds) for both trans-(E) and cis-(Z) isomers of AZO on the surface of nanosheets, resulting in a dramatic increase in enthalpy and lifetime. The metastable Z-form of AZO on RGO is thermally stabilized with a half-life of 52 days by steric hindrance and intermolecular H-bonds calculated using density functional theory (DFT). The AZO-RGO fuel shows a high storage capacity of 138 Wh kg(-1) by optimizing intermolecular H-bonds with a good cycling stability for 50 cycles induced by visible light at 520 nm. Our work opens up a new method for making advanced molecular solar thermal storage materials by tuning molecular interactions on a nano-template.

  2. Tubulin bond energies and microtubule biomechanics determined from nanoindentation in silico

    CERN Document Server

    Kononova, Olga; Theisen, Kelly E; Marx, Kenneth A; Dima, Ruxandra I; Ataullakhanov, Fazly I; Grishchuk, Ekaterina L; Barsegov, Valeri

    2015-01-01

    Microtubules, the primary components of the chromosome segregation machinery, are stabilized by longitudinal and lateral non-covalent bonds between the tubulin subunits. However, the thermodynamics of these bonds and the microtubule physico-chemical properties are poorly understood. Here, we explore the biomechanics of microtubule polymers using multiscale computational modeling and nanoindentations in silico of a contiguous microtubule fragment. A close match between the simulated and experimental force-deformation spectra enabled us to correlate the microtubule biomechanics with dynamic structural transitions at the nanoscale. Our mechanical testing revealed that the compressed MT behaves as a system of rigid elements interconnected through a network of lateral and longitudinal elastic bonds. The initial regime of continuous elastic deformation of the microtubule is followed by the transition regime, during which the microtubule lattice undergoes discrete structural changes, which include first the reversib...

  3. Bond Orientational Order, Molecular Motion and Free Energy of High Density DNA Mesophases

    CERN Document Server

    Podgornik, R; Gawrisch, K; Rau, D C; Rupprecht, A; Parsegian, V A

    1995-01-01

    By equilibrating condensed DNA arrays against reservoirs of known osmotic stress and examining them with several structural probes, it has been possible to achieve a detailed thermodynamic and structural characterization of the change between two distinct regions on the liquid crystalline phase digram: a higher-density hexagonally packed region with long-range bond orientational order in the plane perpendicular to the average molecular direction; and a lower-density cholesteric region with fluid-like positional order. X-rays scattering on highly ordered DNA arrays at high density and with the helical axis oriented parallel to the incoming beam showed a six-fold azimuthal modulation of the first order diffraction peak that reflects the macroscopic bond-orientational order. Transition to the less-dense cholesteric phase through osmotically controlled swelling shows the loss of this bond orientational order that had been expected from the change in optical birefringence patterns and that is consistent with a rap...

  4. The relationship between bond ionicity, lattice energy, coefficient of thermal expansion and microwave dielectric properties of Nd(Nb(1-x)Sb(x))O4 ceramics.

    Science.gov (United States)

    Zhang, Ping; Zhao, Yonggui; Wang, Xiuyu

    2015-06-28

    The crystalline structure refinement, chemical bond ionicity, lattice energy and coefficient of thermal expansion were carried out for Nd(Nb(1-x)Sb(x))O4 ceramics with a monoclinic fergusonite structure to investigate the correlations between the crystalline structure, phase stability, bond ionicity, lattice energy, coefficient of thermal expansion, and microwave dielectric properties. The bond ionicity, lattice energy, and coefficient of thermal expansion of Nd(Nb(1-x)Sb(x))O4 ceramics were calculated using a semiempirical method based on the complex bond theory. The phase structure stability varied with the lattice energy which was resulted by the substitution constant of Sb(5+). With the increasing of the Sb(5+) contents, the decrease of Nb/Sb-O bond ionicity was observed, which could be contributed to the electric polarization. The ε(r) had a close relationship with the Nb/Sb-O bond ionicity. The increase of the Q×f and |τ(f)| values could be attributed to the lattice energy and the coefficient of thermal expansion. The microwave dielectric properties of Nd(Nb(1-x)Sb(x))O4 ceramics with the monoclinic fergusonite structure were strongly dependent on the chemical bond ionicity, lattice energy and coefficient of thermal expansion.

  5. Bonding in Mercury Molecules Described by the Normalized Elimination of the Small Component and Coupled Cluster Theory

    NARCIS (Netherlands)

    Cremer, Dieter; Kraka, Elfi; Filatov, Michael

    2008-01-01

    Bond dissociation energies (BDEs) of neutral HgX and cationic HgX(+) molecules range from less than a kcal mol(-1) to as much as 60 kcal mol(-1). Using NESCICCCSD(T) [normalized elimination of the small component and coupled-cluster theory with all single and double excitations and a perturbative tr

  6. Density functional for van der Waals forces accounts for hydrogen bond in benchmark set of water hexamers

    DEFF Research Database (Denmark)

    Kelkkanen, Kari André; Lundqvist, Bengt; Nørskov, Jens Kehlet

    2009-01-01

    A recent extensive study has investigated how various exchange-correlation (XC) functionals treat hydrogen bonds in water hexamers and has shown traditional generalized gradient approximation and hybrid functionals used in density-functional (DF) theory to give the wrong dissociation-energy trend...

  7. \\title{Low-Cost Bump-Bonding Processes for High Energy Physics Pixel Detectors}

    CERN Document Server

    Caselle, Michele; Colombo, Fabio; Dierlamm, Alexander Hermann; Husemann, Ulrich; Kudella, Simon; Weber, M

    2015-01-01

    In the next generation of collider experiments detectors will be challenged by unprecedented particle fluxes. Thus large detector arrays of highly pixelated detectors with minimal dead area at reasonable costs are required. Bump-bonding of pixel detectors has been shown to be a major cost-driver. KIT is one of the production centers of the CMS barrel pixel detector for the Phase I Upgrade. In this contribution the SnPb bump-bonding process and the production yield is reported. In parallel to the production of the new CMS pixel detector, several alternatives to the expensive photolithography electroplating/electroless metal deposition technologies are developing. Recent progress and challenges faced in the development of bump-bonding technology based on gold-stud bonding by thin ($15\\,\\rm{\\mu m}$) gold wire is presented. This technique allows producing metal bumps with diameters down to $30\\,\\rm{\\mu m}$ without using photolithography processes, which are typically required to provide suitable under bu...

  8. A Model of Thermal Energy Storage According to the Convention of Bond Graphs (Bg and State Equations (Se

    Directory of Open Access Journals (Sweden)

    Cichy Marian

    2015-12-01

    Full Text Available The main advantage of the use of the Bond Graphs method and State Equations for modeling energy systems with a complex structure (marine power plants, hybrid vehicles, etc. is the ability to model the system components of different physical nature using identical theoretical basis. The paper presents a method of modeling thermal energy storage, which is in line with basic BG theory. Critical comments have been put forward concerning multiport energy storage introduced by other authors or the so-called C-field. In suggested approach, the decision not to use pseudo Bond Graphs has been justified as not being in line with basic BG theory. On the basis of molecular physics it was considered that the state variable, in physical and mathematical sense, should be temperature rather than entropy. Examples of the application of the proposed approach to thermodynamic processes and heat exchange have been presented. The application of a single graph as a model for thermal energy storage has been illustrated by a way of numerical simulation examples.

  9. Accounting for the differences in the structures and relative energies of the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I4 2+, the Se-I pi-bonded Se2I4 2+, and their higher-energy isomers by AIM, MO, NBO, and VB methodologies.

    Science.gov (United States)

    Brownridge, Scott; Crawford, Margaret-Jane; Du, Hongbin; Harcourt, Richard D; Knapp, Carsten; Laitinen, Risto S; Passmore, Jack; Rautiainen, J Mikko; Suontamo, Reijo J; Valkonen, Jussi

    2007-02-05

    The bonding in the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I42+ (three sigma + two pi bonds), the Se-I pi-bonded Se2I42+ (four sigma + one pi bonds), and their higher-energy isomers have been studied using modern DFT and ab initio calculations and theoretical analysis methods: atoms in molecules (AIM), molecular orbital (MO), natural bond orbital (NBO), and valence bond (VB) analyses, giving their relative energies, theoretical bond orders, and atomic charges. The aim of this work was to seek theory-based answers to four main questions: (1) Are the previously proposed simple pi*-pi* bonding models valid for S2I42+ and Se2I42+? (2) What accounts for the difference in the structures of S2I42+ and Se2I42+? (3) Why are the classically bonded isolobal P2I4 and As2I4 structures not adopted? (4) Is the high experimentally observed S-S bond order supported by theoretical bond orders, and how does it relate to high bond orders between other heavier main group elements? The AIM analysis confirmed the high bond orders and established that the weak bonds observed in S2I42+ and Se2I42+ are real and the bonding in these cations is covalent in nature. The full MO analysis confirmed that S2I42+ contains three sigma and two pi bonds, that the positive charge is essentially equally distributed over all atoms, that the bonding between S2 and two I2+ units in S2I42+ is best described by two mutually perpendicular 4c2e pi*-pi* bonds, and that in Se2I42+, two SeI2+ moieties are joined by a 6c2e pi*-pi* bond, both in agreement with previously suggested models. The VB treatment provided a complementary approach to MO analysis and provided insight how the formation of the weak bonds affects the other bonds. The NBO analysis and the calculated AIM charges showed that the minimization of the electrostatic repulsion between EI2+ units (E = S, Se) and the delocalization of the positive charge are the main factors that explain why the nonclassical structures are favored for S2I42

  10. Phenol dissociation on pristine and defective graphene

    Science.gov (United States)

    Widjaja, Hantarto; Oluwoye, Ibukun; Altarawneh, Mohammednoor; Hamra, A. A. B.; Lim, H. N.; Huang, N. M.; Yin, Chun-Yang; Jiang, Zhong-Tao

    2017-03-01

    Phenol (C6H5O‒H) dissociation on both pristine and defective graphene sheets in terms of associated enthalpic requirements of the reaction channels was investigated. Here, we considered three common types of defective graphene, namely, Stone-Wales, monovacancy and divacancy configurations. Theoretical results demonstrate that, graphene with monovacancy creates C atoms with dangling bond (unpaired valence electron), which remains particularly useful for spontaneous dissociation of phenol into phenoxy (C6H5O) and hydrogen (H) atom. The reactions studied herein appear barrierless with reaction exothermicity as high as 2.2 eV. Our study offers fundamental insights into another potential application of defective graphene sheets.

  11. Density function theory study of the adsorption and dissociation of carbon monoxide on tungsten nanoparticles.

    Science.gov (United States)

    Weng, Meng-Hsiung; Ju, Shin-Pon; Chen, Hsin-Tsung; Chen, Hui-Lung; Lu, Jian-Ming; Lin, Ken-Huang; Lin, Jenn-Sen; Hsieh, Jin-Yuan; Yang, Hsi-Wen

    2013-02-01

    The adsorption and dissociation properties of carbon monoxide (CO) molecule on tungsten W(n) (n = 10-15) nanoparticles have been investigated by density-functional theory (DFT) calculations. The lowest-energy structures for W(n) (n = 10-15) nanoparticles are found by the basin-hopping method and big-bang method with the modified tight-binding many-body potential. We calculated the corresponding adsorption energies, C-O bond lengths and dissociation barriers for adsorption of CO on nanoparticles. The electronic properties of CO on nanoparticles are studied by the analysis of density of state and charge density. The characteristic of CO on W(n) nanoparticles are also compared with that of W bulk.

  12. Nature of the chemical bond and origin of the inverted dipole moment in boron fluoride: a generalized valence bond approach.

    Science.gov (United States)

    Fantuzzi, Felipe; Cardozo, Thiago Messias; Nascimento, Marco Antonio Chaer

    2015-05-28

    The generalized product function energy partitioning (GPF-EP) method has been applied to investigate the nature of the chemical bond and the origin of the inverted dipole moment of the BF molecule. The calculations were carried out with GPF wave functions treating all of the core electrons as a single Hartree-Fock group and the valence electrons at the generalized valence bond perfect-pairing (GVB-PP) or full GVB levels, with the cc-pVTZ basis set. The results show that the chemical structure of both X (1)Σ(+) and a (3)Π states is composed of a single bond. The lower dissociation energy of the excited state is attributed to a stabilizing intraatomic singlet coupling involving the B 2sp-like lobe orbitals after bond dissociation. An increase of electron density on the B atom caused by the reorientation of the boron 2sp-like lobe orbitals is identified as the main responsible effect for the electric dipole inversion in the ground state of BF. Finally, it is shown that π back-bonding from fluorine to boron plays a minor role in the electron density displacement to the bonding region in both states. Moreover, this effect is associated with changes in the quasi-classical component of the electron density only and does not contribute to covalency in either of the states. Therefore, at least for the case of the BF molecule, the term back-bonding is misleading, since it does not contribute to the bond formation.

  13. High-energy and low-energy collision-induced dissociation of protonated flavonoids generated by MALDI and by electrospray ionization

    Science.gov (United States)

    March, Raymond E.; Li, Hongxia; Belgacem, Omar; Papanastasiou, Dimitris

    2007-04-01

    Product ion mass spectra of a series of nine protonated flavonoids have been observed by electrospray ionization combined with quadrupole/time-of-flight (ESI QTOF), and matrix-assisted laser desorption ionization combined either with quadrupole ion trap (MALDI QIT) tandem mass spectrometry or time-of-flight tandem mass spectrometry (MALDI TOF ReTOF). The compounds examined are 3,6-, 3,2'-, and 3,3'-dihydoxyflavone, apigenin (5,7,4'-trihydroxyflavone), luteolin (5,7,3',4'-tetrahydroxyflavone), apigenin-7-O-glucoside, hesperidin (5,7,3'-trihydroxy-4'-methoxyflavanone), daidzen (7,4'-dihydroxyisoflavone), and rutin (quercitin-3-O-rutinoside) where quercitin is 3,5,7,3',4'-pentahydroxyflavone; sodiated rutin was examined also. The center-of-mass energies in ESI QTOF and MALDI QIT are similar (1-4 eV) and their product ion mass spectra are virtually identical. In the MALDI TOF ReTOF instrument, center-of-mass energies range from 126-309 eV for sodiated rutin to protonated dihydroxyflavones, respectively. Due to the high center-of-mass energies available with the MALDI TOF ReTOF instrument, some useful structural information may be obtained; however, with increasing precursor mass/charge ratio, product ion mass spectra become simplified so as to be of limited structural value. Electronic excitation of the protonated (and sodiated) species examined here offers an explanation for the very simple product ion mass spectra observed particularly for glycosylated flavonoids.

  14. Thermodynamic properties (enthalpy, bond energy, entropy, and heat capacity) and internal rotor potentials of vinyl alcohol, methyl vinyl ether, and their corresponding radicals.

    Science.gov (United States)

    da Silva, Gabriel; Kim, Chol-Han; Bozzelli, Joseph W

    2006-06-29

    Vinyl alcohols (enols) have been discovered as important intermediates and products in the oxidation and combustion of hydrocarbons, while methyl vinyl ethers are also thought to occur as important combustion intermediates. Vinyl alcohol has been detected in interstellar media, while poly(vinyl alcohol) and poly(methyl vinyl ether) are common polymers. The thermochemical property data on these vinyl alcohols and methyl vinyl ethers is important for understanding their stability, reaction paths, and kinetics in atmospheric and thermal hydrocarbon-oxygen systems. Enthalpies , entropies , and heat capacities (C(p)()(T)) are determined for CH(2)=CHOH, C(*)H=CHOH, CH(2)=C(*)OH, CH(2)=CHOCH(3), C(*)H=CHOCH(3), CH(2)=C(*)OCH(3), and CH(2)=CHOC(*)H(2). Molecular structures, vibrational frequencies, , and C(p)(T) are calculated at the B3LYP/6-31G(d,p) density functional calculation level. Enthalpies are also determined using the composite CBS-Q, CBS-APNO, and G3 methods using isodesmic work reactions to minimize calculation errors. Potential barriers for internal rotors are calculated at the B3LYP/6-31G(d,p) level and used to determine the hindered internal rotational contributions to entropy and heat capacity. The recommended ideal gas phase values calculated in this study are the following (in kcal mol(-1)): -30.0, -28.9 (syn, anti) for CH(2)=CHOH; -25.6, -23.9 for CH(2)=CHOCH(3); 31.3, 33.5 for C(*)H=CHOH; 27.1 for anti-CH(2)=C(*)OH; 35.6, 39.3 for C(*)H=CHOCH(3); 33.5, 32.2 for CH(2)=C(*)OCH(3); 21.3, 22.0 for CH(2)=CHOC(*)H(2). Bond dissociation energies (BDEs) and group additivity contributions are also determined. The BDEs reveal that the O-H, O-CH(3), C-OH, and C-OCH(3) bonds in vinyl alcohol and methyl vinyl ether are similar in energy to those in the aromatic molecules phenol and methyl phenyl ether, being on average around 3 kcal mol(-1) weaker in the vinyl systems. The keto-enol tautomerization enthalpy for the interconversion of vinyl alcohol to acetaldehyde is

  15. Effect of ZnO on the interfacial bonding between Na 2O-B 2O 3-SiO 2 vitrified bond and diamond

    Science.gov (United States)

    Wang, P. F.; Li, Zh. H.; Li, J.; Zhu, Y. M.

    2009-08-01

    Diamond composites were prepared by sintering diamond grains with low melting Na 2O-B 2O 3-SiO 2 vitrified bonds in air. The influence of ZnO on the wettability and flowing ability of Na 2O-B 2O 3-SiO 2 vitrified bonds was characterized by wetting angle, the interfacial bonding states between diamond grains and the vitrified bonds were observed by scanning electron microscope (SEM), and the micro-scale bonding mechanism in the interfaces was investigated by means of energy-dispersive spectrometer (EDS), Fourier transform infrared (FTIR) spectrometer and X-ray photoelectron spectroscopy (XPS). The experimental results showed that ZnO facilitated the dissociation of boron/silicon-oxygen polyhedra and the formation of larger amount of non-bridging oxygen in the glass network, which resulted in the increase of the vitrified bonds' wettability and the formation of -C dbnd O, -O-H and -C-H bonds on the surface of diamond grains. B and Si diffused from the vitrified bonds to the interface, and C-C, C-O, C dbnd O and C-B bond formed on the surface of sintered diamond grains during sintering process, by which the interfacial bonding between diamond grains and the vitrified bonds was strengthened.

  16. Molecular and dissociative adsorption of water at a defective Cu(110) surface

    Science.gov (United States)

    Lousada, Cláudio M.; Johansson, Adam Johannes; Korzhavyi, Pavel A.

    2017-04-01

    We performed a density functional theory (DFT) investigation of the molecular and dissociative adsorption of water at the perfect Cu(110) and at a defective Cu surface that provides a broad spectrum of adsorption sites in terms of coordination of Cu atoms, with the aim of understanding the role of surface defects in the dissociation of water molecules. The molecular adsorption of water is spontaneous at both surfaces but at the defective surface we found two stable molecular adsorption structures that differ slightly in the disposition of the O-atoms of H2O on the surface plane but differ considerably on the orientation of their H-atoms. Additionally we studied the dissociative adsorption of water accompanied with formation of H2(g). At the defective surface, starting from 1 ML of molecularly adsorbed H2O, the dissociation of 0.22 ML of H2O leading to 0.22 ML of HO, 0.78 ML H2O and H2(g) is exergonic but the dissociation of 0.44 ML or more H2O molecules is endergonic. These findings are discussed in terms of the two main factors that affect the adsorption energies: the existence of exposed adatoms provides an environment that facilitates the interaction with small adsorbates leading to stronger bonds between the surface and such adsorbates; and at the same time, the limited polarizability of the defect sites causes high coverages of adsorbates that drag electron density from the surface to be unfavorable. The overall effect is that at the defective Cu(110) formation of low coverages of HO groups is more favorable than at the perfect Cu(110) while forming coverages higher than 0.44 ML of HO is less favorable than at the perfect Cu(110). These effects have their origin in the extent of the polarization of the Cu-O bonds.

  17. Effects of Cluster Size on Platinum-Oxygen Bonds Formation in Small Platinum Clusters

    Science.gov (United States)

    Oemry, Ferensa; Padama, Allan Abraham B.; Kishi, Hirofumi; Kunikata, Shinichi; Nakanishi, Hiroshi; Kasai, Hideaki; Maekawa, Hiroyoshi; Osumi, Kazuo; Sato, Kaoru

    2012-03-01

    We present the results of density functional theory calculation in oxygen dissociative adsorption process on two types of isolated platinum (Pt) clusters: Pt4 and Pt10, by taking into account the effect of cluster reconstruction. The strength of Pt-Pt bonds in the clusters is mainly defined by d-d hybridization and interstitial bonding orbitals (IBO). Oxygen that adsorbed on the clusters is weakening the IBO and thus inducing geometry reconstruction as occurred in Pt10 cluster. However, cluster that could undergo structural deformation is found to promote oxygen dissociation with no energy barrier. The details show that maintaining well-balanced of attractive and repulsive (Hellmann-Feynman) forces between atoms is considered to be the main key to avoid any considerable rise of energy barrier. Furthermore, a modest energy barrier that gained in Pt4 cluster is presumed to be originate from inequality of intramolecular forces between atoms.

  18. Dissociation: Cognitive capacity or dysfunction?

    NARCIS (Netherlands)

    de Ruiter, M.B.; Bernet, M.; Phaf, R.H.

    2006-01-01

    Dissociative experiences are mostly studied as a risk factor for dissociative pathology. Nonpathological dissociation is quite common in the general population, however, and may reflect a constitutionally determined cognitive style rather than a pathological trait acquired through the experience of

  19. Comment on ``Electron-induced bond breaking at low energies in HCOOH and glycine: The role of very short-lived σ∗ anion states''

    Science.gov (United States)

    Rescigno, T. N.; Trevisan, C. S.; Orel, A. E.

    2009-10-01

    Recent model calculations by Gallup [Phys. Rev. A79, 042710 (2009)] suggest that low-energy dissociative electron attachment to formic acid can be explained solely in terms of a very short-lived σ∗ anion state and that no σ∗/π∗ coupling is required. We argue that this interpretation of the experimental data, which is at odds with our earlier study, is flawed.

  20. General formulation of rovibrational kinetic energy operators and matrix elements in internal bond-angle coordinates using factorized Jacobians

    Science.gov (United States)

    Kopp, Wassja A.; Leonhard, Kai

    2016-12-01

    We show how inverse metric tensors and rovibrational kinetic energy operators in terms of internal bond-angle coordinates can be obtained analytically following a factorization of the Jacobian worked out by Frederick and Woywod. The structure of these Jacobians is exploited in two ways: On one hand, the elements of the metric tensor as well as its determinant all have the form ∑rmsin (αn) cos (βo) . This form can be preserved by working with the adjugate metric tensor that can be obtained without divisions. On the other hand, the adjugate can be obtained with less effort by exploiting the lower triangular structure of the Jacobians. Together with a suitable choice of the wavefunction, we avoid singularities and show how to obtain analytical expressions for the rovibrational kinetic energy matrix elements.

  1. Determination of Hydrogen Bond Structure in Water versus Aprotic Environments To Test the Relationship Between Length and Stability

    Energy Technology Data Exchange (ETDEWEB)

    Sigala, Paul A.; Ruben, Eliza A.; Liu, Corey W.; Piccoli, Paula M. B.; Hohenstein, Edward G.; Martinez, Todd J.; Schultz, Arthur J.; Herschiag, Daniel

    2015-05-06

    Hydrogen bonds profoundly influence the architecture and activity of biological macromolecules. Deep appreciation of hydrogen bond contributions to biomolecular function thus requires a detailed understanding of hydrogen bond structure and energetics and the relationship between these properties. Hydrogen bond formation energies (Delta G(f)) are enormously more favorable in aprotic solvents than in water, and two classes of contributing factors have been proposed to explain this energetic difference, focusing respectively on the isolated and hydrogen-bonded species: (I) water stabilizes the dissociated donor and acceptor groups much better than aprotic solvents, thereby reducing the driving force for hydrogen bond formation; and (II) water lengthens hydrogen bonds compared to aprotic environments, thereby decreasing the potential energy within the hydrogen bond. Each model has been proposed to provide a dominant contribution to Delta G(f), but incisive tests that distinguish the importance of these contributions are lacking. Here we directly test the structural basis of model II. Neutron crystallography, NMR spectroscopy, and quantum mechanical calculations demonstrate that O-H center dot center dot center dot O hydrogen bonds in crystals, chloroform, acetone, and water have nearly identical lengths and very similar potential energy surfaces despite Delta G(f) differences >8 kcal/mol across these solvents. These results rule out a substantial contribution from solvent-dependent differences in hydrogen bond structure and potential energy after association (model II) and thus support the conclusion that differences in hydrogen bond Delta G(f) are predominantly determined by solvent interactions with the dissociated groups (model I). These findings advance our understanding of universal hydrogen-bonding interactions and have important implications for biology and engineering.

  2. Intense two-cycle laser pulses induce time-dependent bond hardening in a polyatomic molecule.

    Science.gov (United States)

    Dota, K; Garg, M; Tiwari, A K; Dharmadhikari, J A; Dharmadhikari, A K; Mathur, D

    2012-02-17

    A time-dependent bond-hardening process is discovered in a polyatomic molecule (tetramethyl silane, TMS) using few-cycle pulses of intense 800 nm light. In conventional mass spectrometry, symmetrical molecules such as TMS do not exhibit a prominent molecular ion (TMS(+)) as unimolecular dissociation into [Si(CH(3))(3)](+) proceeds very fast. Under a strong field and few-cycle conditions, this dissociation channel is defeated by time-dependent bond hardening: a field-induced potential well is created in the TMS(+) potential energy curve that effectively traps a wave packet. The time dependence of this bond-hardening process is verified using longer-duration (≥100 fs) pulses; the relatively slower falloff of optical field in such pulses allows the initially trapped wave packet to leak out, thereby rendering TMS(+) unstable once again.

  3. Effect of metal cationization on the low-energy collision-induced dissociation of loganin, epi-loganin and ketologanin studied by electrospray ionization tandem mass spectrometry

    Science.gov (United States)

    Madhusudanan; Raj; Bhaduri

    2000-07-01

    The effect of alkali metal and silver cationization on the collision-induced dissociation (CID) of loganin (1), epi-loganin (2) and ketologanin (3) is discussed. Their protonated molecular ions fragment mainly by glycosidic cleavages. The epimeric pairs (1 and 2) show differences in the abundances of the resulting fragment ions. Lithium cationization induces new dissociation pathways such as the retro-Diels-Alder (RDA) fragmentation followed by rearrangement. Unlike the dissociation of protonated molecular ions, the dissociation of lithiated molecules also provides lithiated sugar fragments. The CID of dilithiated molecules is substantially different from that of the monolithiated precursors. RDA reaction appears to be favoured by the presence of the additional lithium atom in the molecule. In addition, other ring cleavages are also induced. The abundances of the various fragment ions are different in the CID spectra of the epimeric pairs. Extensive D labelling and (6)Li labelling experiments confirmed many of the ion structures proposed. The CID spectra of the sodiated ions are generally weaker, although similar to those of the corresponding lithiated species. Higher alkali metal ion (K(+), Rb(+) and Cs(+)) adducts generated only the corresponding metal ions as products of CID. Similar fragmentations were also observed in the CID of the [M + Ag](+) ions of these compounds, the epimeric pairs showing characteristic differences in their CID behaviour. Copyright 2000 John Wiley & Sons, Ltd.

  4. Quarkonium suppression: Gluonic dissociation vs. colour screening

    Indian Academy of Sciences (India)

    Binoy Krishna Patra; Dinesh Kumar Srivastava

    2003-05-01

    We evaluate the suppression of / production in an equilibrating quark gluon plasma for two competing mechanisms: Debye screening of colour interaction and dissociation due to energetic gluons. Results are obtained for S + S and Au + Au collisions at RHIC and LHC energies. At RHIC energies the gluonic dissociation of the charmonium is found to be equally important for both the systems while the screening of the interaction plays a significant role only for the larger systems. At LHC energies the Debye mechanism is found to dominate both the systems. While considering the suppression of directly produced $\\Upsilon$ at LHC energies, we find that only the gluonic dissociation mechanism comes into play for the initial conditions taken from the self screened parton cascade model in these studies.

  5. Dissociative recombination in aeronomy

    Science.gov (United States)

    Fox, J. L.

    1989-01-01

    The importance of dissociative recombination in planetary aeronomy is summarized, and two examples are discussed. The first is the role of dissociative recombination of N2(+) in the escape of nitrogen from Mars. A previous model is updated to reflect new experimental data on the electronic states of N produced in this process. Second, the intensity of the atomic oxygen green line on the nightside of Venus is modeled. Use is made of theoretical rate coefficients for production of O (1S) in dissociative recombination from different vibrational levels of O2(+).

  6. The dissociation constant of water at extreme conditions

    Science.gov (United States)

    Gonzalez-Vazquez, Otto; Giacomazzi, Luigi; Pinilla, C.; Scandolo, Sandro

    2013-06-01

    Only one out of 107 water molecules is dissociated in liquid water at ambient conditions, but the concentration of dissociated molecules increases with pressure ad temperature, and water eventually reaches a fully dissociated state when pressure exceeds 50-100 GPa and temperature reaches a few thousand Kelvin. The behavior of the dissociation constant of water (pKa) at conditions intermediate between ambient and the fully dissociated state is poorly known. Yet, the water pKa is a parameter of primary importance in the aqueous geochemistry as it controls the solubility of ions in geological fluids. We present results of molecular dynamics calculations of the pKa water at extreme conditions. Free-energy differences between the undissociated and the dissociated state are calculated by thermodynamic integration along the dissociation path. The calculations are based on a recently developed all-atom polarizable force-field for water, parametrized on density-functional theory calculations.

  7. CO product distribution in the unimolecular dissociation of HCO

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The unimolecular dissociation of HCO ground state was investigated with the time-dependent full-quantum symplectic propagation based on the newest potential energy surface of the system. Calculated energy and widths of HCO resonance states agree well with those in the literature. CO product distribution was systematically investigated. A simple model was presented to interpret the rovibrational distributions in HCO dissociation.

  8. Explicitly correlated intermolecular distances and interaction energies of hydrogen bonded complexes

    DEFF Research Database (Denmark)

    Lane, Joseph R; Kjærgaard, Henrik G

    2009-01-01

    We have optimized the lowest energy structures and calculated interaction energies for the H(2)O-H(2)O, H(2)O-H(2)S, H(2)O-NH(3), and H(2)O-PH(3) dimers with the recently developed explicitly correlated CCSD(T)-F12 methods and the associated VXZ-F12 (where X = D,T,Q) basis sets. For a given...

  9. Adsorption and dissociation of O2 on Ni-doped (5, 5) SWCNT: A DFT study

    Science.gov (United States)

    Li, Xiaodong; Liu, Liangliang; Wang, Mingguang; Wang, Zhu

    2016-05-01

    The effect of nickel doping on the adsorption and dissociation of the O2 molecule on a (5, 5) single-walled carbon nanotube (SWCNT) is investigated using first-principles density functional theory calculations in company with the nudged elastic band (NEB). Our calculated results show that nickel doping can make it much easier for oxygen adsorbed on the SWCNT, and the chemisorption energy is high enough to alter the O-O bond. What's more, the activation barrier for oxygen dissociation is lowered to 0.399 eV through nickel doping, which is much lower than Pt doped CNT. Our work have done here would be of help to develop platinum-free oxygen reduction reaction catalysts based on SWCNTs.

  10. Spectroscopic evidence for the partial dissociation of H2O on ZnO(1010).

    Science.gov (United States)

    Wang, Y; Muhler, M; Wöll, Ch

    2006-04-01

    The interaction of water with the non-polar ZnO(1010) surface has been studied by high resolution electron energy loss spectroscopy (HREELS) and thermal desorption spectroscopy (TDS). Adsorption of water at room temperature leads to the partial dissociation of water molecules giving rise to a well defined (2x1) superstructure. This observation was confirmed by the HREELS data which show the water-induced O-H stretching modes at 396 and 460 meV (3193 and 3709 cm-1) as well as the peak at 456 meV (3677 cm-1) arising from the OH species. The large red shift of the loss at 396 meV indicates unusually strong hydrogen bonding interactions of water to both neighbouring adsorbate molecules and the surface O atoms which are responsible for the partial dissociation of water molecules on the perfect ZnO(1010) surface.

  11. The effect of carbon monoxide Co-adsorption on Ni-catalysed water dissociation.

    Science.gov (United States)

    Mohsenzadeh, Abas; Borjesson, Anders; Wang, Jeng-Han; Richards, Tobias; Bolton, Kim

    2013-01-01

    The effect of carbon monoxide (CO) co-adsorption on the dissociation of water on the Ni(111) surface has been studied using density functional theory. The structures of the adsorbed water molecule and of the transition state are changed by the presence of the CO molecule. The water O-H bond that is closest to the CO is lengthened compared to the structure in the absence of the CO, and the breaking O-H bond in the transition state structure has a larger imaginary frequency in the presence of CO. In addition, the distances between the Ni surface and H2O reactant and OH and H products decrease in the presence of the CO. The changes in structures and vibrational frequencies lead to a reaction energy that is 0.17 eV less exothermic in the presence of the CO, and an activation barrier that is 0.12 eV larger in the presence of the CO. At 463 K the water dissociation rate constant is an order of magnitude smaller in the presence of the CO. This reveals that far fewer water molecules will dissociate in the presence of CO under reaction conditions that are typical for the water-gas-shift reaction.

  12. The Effect of Carbon Monoxide Co-Adsorption on Ni-Catalysed Water Dissociation

    Directory of Open Access Journals (Sweden)

    Abas Mohsenzadeh

    2013-11-01

    Full Text Available The effect of carbon monoxide (CO co-adsorption on the dissociation of water on the Ni(111 surface has been studied using density functional theory. The structures of the adsorbed water molecule and of the transition state are changed by the presence of the CO molecule. The water O–H bond that is closest to the CO is lengthened compared to the structure in the absence of the CO, and the breaking O–H bond in the transition state structure has a larger imaginary frequency in the presence of CO. In addition, the distances between the Ni surface and H2O reactant and OH and H products decrease in the presence of the CO. The changes in structures and vibrational frequencies lead to a reaction energy that is 0.17 eV less exothermic in the presence of the CO, and an activation barrier that is 0.12 eV larger in the presence of the CO. At 463 K the water dissociation rate constant is an order of magnitude smaller in the presence of the CO. This reveals that far fewer water molecules will dissociate in the presence of CO under reaction conditions that are typical for the water-gas-shift reaction.

  13. A periodic Energy Decomposition Analysis (pEDA) method for the Investigation of Chemical Bonding in Extended Systems

    CERN Document Server

    Raupach, Marc

    2015-01-01

    The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the binding energy between two fragments (e.g. the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic and dispersion interaction, Pauli repulsion and orbital relaxation energies. The pEDA presented here for an AO-based implementation can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy and k-space sampling. Four typical bonding scenarios for surface adsorbate complexes were chosen to highlight th...

  14. Accurate Reference Data for the Non-Additive Non-Interacting Kinetic Energy in Covalent Bonds

    CERN Document Server

    Nafziger, Jonathan; Wasserman, Adam

    2016-01-01

    The non-additive non-interacting kinetic energy is calculated exactly for fragments of H$_2$, Li$_2$, Be$_2$, C$_2$, N$_2$, F$_2$, and Na$_2$ within partition density-functional theory. The resulting fragments are uniquely determined and their sum reproduces the Kohn-Sham molecular density of the corresponding XC functional. We compare the use of fractional orbital occupation to the usual PDFT ensemble method for treating the fragment energies and densities. We also compare Thomas-Fermi and von Weiz{\\"a}cker approximate kinetic energy functionals to the numerically exact solution and find significant regions where the von Weiz{\\"a}cker solution is nearly exact.

  15. Dissecting Individual Ligand-Receptor Bonds with a Laminar Flow Chamber

    CERN Document Server

    Pierres, Anne; Benoliel, Anne-Marie; Bongrand, Pierre

    2008-01-01

    The most important function of proteins may well be to bind to other biomolecules. It has long been felt that kinetic rates of bond formation and dissociation between soluble receptors and ligands might account for most features of the binding process. Only theoretical considerations allowed to predict the behaviour of surface-attached receptors from the properties of soluble forms. During the last decade, experimental progress essentially based on flow chambers, atomic force microscopes or biomembrane force probes allowed direct analysis of biomolecule interaction at the single bond level and gave new insight into previously ignored features such as bond mechanical properties or energy landscapes. The aim of this review is (i) to describe the main advances brought by laminar flow chambers, including information on bond response to forces, multiplicity of binding states, kinetics of bond formation between attached structures, effect of molecular environment on receptor efficiency and behaviour of multivalent ...

  16. A bottom-up valence bond derivation of excitation energies in 1D-like delocalized systems.

    Science.gov (United States)

    Kepenekian, Mikaël; Robert, Vincent; Boilleau, Corentin; Malrieu, Jean-Paul

    2012-01-28

    Using the chemically relevant parameters hopping integral t(0) and on-site repulsion energy U, the charge gap (lowest dipolarly allowed transition energy) in 1D systems is examined through a bottom-up strategy. The method is based on the locally ionized states, the energies of which are corrected using short-range delocalization effects. In a valence bond framework, these states interact to produce an excitonic matrix which accounts for the delocalized character of excited states. The treatment, which gives access to the correlated spectrum of ionization potentials, is entirely analytical and valid whatever the U/|t(0)| ratio for such systems ruled by Peierls-Hubbard Hamiltonians. This second-order analytical derivation is finally confronted to numerical results of a renormalized excitonic treatment using larger blocks as functions of the U/|t(0)| ratio. The method is applied to dimerized chains and to fused polybenzenic 1D lattices. Such approaches complement the traditional Bloch-function based picture and deliver a conceptual understanding of the charge gap opening process based on a chemical intuitive picture.

  17. Carbon monoxide dissociative attachment and resonant dissociation by electron-impact

    Science.gov (United States)

    Laporta, V.; Tennyson, J.; Celiberto, R.

    2016-02-01

    Low-energy dissociative electron attachment and resonant electron impact dissociation of CO molecule are considered. Ro-vibrationally resolved cross sections and rate coefficients for both the processes are calculated using an ab-initio model based on the low-lying \\text{X}{{}2}\\Pi resonance of CO-. Final results show that the cross sections increases very rapidly as a function of the ro-vibrational level; these cross sections should be useful for understanding kinetic dissociation of CO in strongly non-equilibrium plasmas.

  18. Above-Threshold Dissociation of HD+ in Femtosecond Laser Field

    Institute of Scientific and Technical Information of China (English)

    BA Song-Yue; YUAN Kai-Jun; HAN Yong-Chang; CONG Shu-Lin

    2008-01-01

    @@ The above-threshold dissociation (ATD) of the HD+ molecular ion in femtosecond laser field is investigated theoretically. The energy-dependent distribution of the dissociated fragments is calculated using an asymptotic-flow expression in the momentum space. The calculations show that the ATD of HD+ is sensitive to the initial vibrational level of ground electronic state. Multiphoton ATDs can be observed in the dissociation processes. The dynamics phenomena are interpreted by using the concept of light-dressed potential.

  19. Crystallographic studies evidencing the high energy tolerance to disrupting the interface disulfide bond of thioredoxin 1 from white leg shrimp Litopenaeus vannamei.

    Science.gov (United States)

    Campos-Acevedo, Adam A; Rudiño-Piñera, Enrique

    2014-12-15

    Thioredoxin (Trx) is a small 12-kDa redox protein that catalyzes the reduction of disulfide bonds in proteins from different biological systems. A recent study of the crystal structure of white leg shrimp thioredoxin 1 from Litopenaeus vannamei (LvTrx) revealed a dimeric form of the protein mediated by a covalent link through a disulfide bond between Cys73 from each monomer. In the present study, X-ray-induced damage in the catalytic and the interface disulfide bond of LvTrx was studied at atomic resolution at different transmission energies of 8% and 27%, 12.8 keV at 100 K in the beamline I-24 at Diamond Light Source. We found that at an absorbed dose of 32 MGy, the X-ray induces the cleavage of the disulfide bond of each catalytic site; however, the interface disulfide bond was cleaved at an X-ray adsorbed dose of 85 MGy; despite being the most solvent-exposed disulfide bond in LvTrx (~50 Å2). This result clearly established that the interface disulfide bond is very stable and, therefore, less susceptible to being reduced by X-rays. In fact, these studies open the possibility of the existence in solution of a dimeric LvTrx.

  20. Crystallographic Studies Evidencing the High Energy Tolerance to Disrupting the Interface Disulfide Bond of Thioredoxin 1 from White Leg Shrimp Litopenaeus vannamei

    Directory of Open Access Journals (Sweden)

    Adam A. Campos-Acevedo

    2014-12-01

    Full Text Available Thioredoxin (Trx is a small 12-kDa redox protein that catalyzes the reduction of disulfide bonds in proteins from different biological systems. A recent study of the crystal structure of white leg shrimp thioredoxin 1 from Litopenaeus vannamei (LvTrx revealed a dimeric form of the protein mediated by a covalent link through a disulfide bond between Cys73 from each monomer. In the present study, X-ray-induced damage in the catalytic and the interface disulfide bond of LvTrx was studied at atomic resolution at different transmission energies of 8% and 27%, 12.8 keV at 100 K in the beamline I-24 at Diamond Light Source. We found that at an absorbed dose of 32 MGy, the X-ray induces the cleavage of the disulfide bond of each catalytic site; however, the interface disulfide bond was cleaved at an X-ray adsorbed dose of 85 MGy; despite being the most solvent-exposed disulfide bond in LvTrx (~50 Å2. This result clearly established that the interface disulfide bond is very stable and, therefore, less susceptible to being reduced by X-rays. In fact, these studies open the possibility of the existence in solution of a dimeric LvTrx.

  1. Density Functional Studies of the C-F Bond Activation of CF3 Radical by Bare Co +

    Institute of Scientific and Technical Information of China (English)

    张冬菊; 刘成卜; 胡海泉; 刘永军

    2001-01-01

    The C—F bond activation mechanism of CF3 radical by bare Co + has been studied by density functional theory. Three local minima and two first-order saddle points were located for the potential energy surface (PES) of [Co, C, F3] + . The activation barrier involving C-F bond activation was calculated to be only 14.73 kJ/mol, while the largest barrier of 149.29 kJ/mol on the PES involves Co-C bond rupture.The bonding mechanism between Co + , C and F atoms were discussed based on Mulliken population. The relevant bond dissociation energy and thermochmistry data were calculated with the limited experimental values, and the results are in good agreement with the experimental findings.

  2. VUV Photoionization and Dissociation of Tyramine and Dopamine: the Joint Experimental and Theoretical Studies

    Institute of Scientific and Technical Information of China (English)

    Hui-jun Guo; Li-li Ye; Liang-yuan Jia; Li-dong Zhang; Fei Qi

    2012-01-01

    Photon induced dissociation investigations of neutral tyramine and dopamine are carried out with synchrotron vacuum ultraviolet photoionization mass spectrometry and theoretical calculations.At low photon energy,only molecular ions are measured by virtue of nearthreshold photoionization.While increasing photon energy to 11.7 eV or more,four distinct fragment ions are obtained for tyramine and dopamine,respectively.Besides,the ionization energies of tyramine and dopamine are determined to be 7.98±0.05 and 7.67±0.05 eV by measuring the photoionization efficiency curves of corresponding molecular ions.With help of density function theory calculations,the detailed fragmentation pathways are established as well.These two molecular cations have similar aminoethyl group elimination pathways,C7H8O2+ (m/z=124) and C7H8O+ (m/z=108) are supposed to be generated by the McLafferty rearrangement via γ-hydrogen (γ-H) shift inducing β-fission.And CH2NH2+is proposed to derive from the direct fission of C7-C8 bond.Besides,the McLafferty rearrangement and the C7-C8 bond fission are validated to be dominant dissociation pathways for tyramine and dopamine cations.

  3. Analytical Potential Energy Function for the Ground State X1∑+ of Lanthanum Monofluoride

    Institute of Scientific and Technical Information of China (English)

    CHEN Lin-Hong; SHANG Ren-Cheng

    2003-01-01

    The equilibrium geometry, harmonic frequency and bond dissociation energy of lanthanum monofluoride have been calculated using Density-Functional Theory (DFT), post-HF methods MP2 and CCSD(T) with the energyconsistent relativistic effective core potentials. The possible electronic state and reasonable dissociation limit of the ground state of LaF are determined based on atomic and molecular reaction statics. Potential energy curve scans for the ground state X 1∑+ have been performed at B3LYP and CCSD(T) levels, due to their better results of harmonic frequency and bond dissociation energy. We find that the potential energy calculated with CCSD(T) is about 0.6 eV larger than the bond dissociation energy, when the internuclear distance is as large as 0.8 nm. The problem that single-reference ab initio methods do not meet dissociation limit during calculations of lanthanide heavy-metal elements is analyzed. We propose the calculation scheme to derive the analytical Murrell-Sorbie potential energy function. Vibrotational spectroscopic constants Be, ωe, ωeχe, αe, βe, De and He obtained by the standard Dunham treatment coincide well with the results of rotational analyses on spectroscopic experiments.

  4. Benchmarking ab initio binding energies of hydrogen-bonded molecular clusters based on FTIR spectroscopy

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Du, Lin; Reiman, Heidi;

    2014-01-01

    Models of formation and growth of atmospheric aerosols are highly dependent on accurate cluster binding energies. These are most often calculated by ab initio electronic structure methods but remain associated with significant uncertainties. We present a computational benchmarking study......) and compare this range to predictions from several widely used electronic structure methods, including five density functionals, Møller-Plesset perturbation theory, and five coupled cluster methods up to CCSDT quality, considering also the D3 dispersion correctional scheme. With some exceptions, we find...... that most electronic structure methods overestimate ΔG°295 K. The effects of vibrational anharmonicity is approximated using scaling factors, reducing ΔG°295 K by ca. 1.8 kJ mol(-1), whereby ΔG°295 K predictions well within the experimental range can be obtained....

  5. High-Resolution and Time-Resolved Electron Energy Loss Spectroscopy Studies of Adsorbate Bonding and Reactivity.

    Science.gov (United States)

    Richter, Lee James

    1988-12-01

    Electron energy loss spectroscopy (EELS) of the quantized vibrations of atoms and molecules adsorbed on single crystal surfaces has emerged as one of the most powerful probes of the structure, adsorption sites and reaction paths of adsorbates. This thesis explores EELS as a probe of the structure of adsorbed hydrogen on Pt(111) and Rh(100), and the structure of both CO and H coadsorbed on Rh(100). It also describes aspects of the development of a custom time-resolved EEL (TREEL) spectrometer and the application of the spectrometer to the study of the kinetics of the decomposition of methanol (CH_3 OH) and formaldehyde (H_2CO) on Ni(110) and Rh(100). In studies of H/Pt(111) and H/Rh(100) it was determined that the extended nature of the single crystal surface complicates quantitative analysis of the vibrational spectra. The nearest-neighbor central force constant model, commonly used to estimate bonding geometries, is qualitatively incorrect for both surfaces. The study of H/Rh(100) also established that local models of the potential anharmonicity are of limited utility due to the different dispersion of the fundamental and overtone losses. Adsorbate-adsorbate interactions can significantly affect adsorbate structure and reactivity. For the system of CO adsorbed on H precovered Rh(100), a strong CO-H repulsion results in a series of ordered H and CO lattices, each associated with a distinct H desorption behavior. One of the structures consists of bridge bound H and CO, each species binding to a site different from that preferred when adsorbed alone. Time-resolved EELS studies of the decomposition of methanol on Ni(110) and Rh(100) found the reaction follows the same pathway: a metastable methoxy species is formed, by cleavage of the OH bond, which subsequently decomposes to CO and H. The removal of the first methoxy hydrogen is the rate limiting step in the decomposition. The high reactivity of the 'CH_2O' product of the methoxy CH bond scission is supported by the

  6. Exploring the Nature of Silicon-Noble Gas Bonds in H3SiNgNSi and HSiNgNSi Compounds (Ng = Xe, Rn

    Directory of Open Access Journals (Sweden)

    Sudip Pan

    2015-03-01

    Full Text Available Ab initio and density functional theory-based computations are performed to investigate the structure and stability of H3SiNgNSi and HSiNgNSi compounds (Ng = Xe, Rn. They are thermochemically unstable with respect to the dissociation channel producing Ng and H3SiNSi or HSiNSi. However, they are kinetically stable with respect to this dissociation channel having activation free energy barriers of 19.3 and 23.3 kcal/mol for H3SiXeNSi and H3SiRnNSi, respectively, and 9.2 and 12.8 kcal/mol for HSiXeNSi and HSiRnNSi, respectively. The rest of the possible dissociation channels are endergonic in nature at room temperature for Rn analogues. However, one three-body dissociation channel for H3SiXeNSi and one two-body and one three-body dissociation channels for HSiXeNSi are slightly exergonic in nature at room temperature. They become endergonic at slightly lower temperature. The nature of bonding between Ng and Si/N is analyzed by natural bond order, electron density and energy decomposition analyses. Natural population analysis indicates that they could be best represented as (H3SiNg+(NSi− and (HSiNg+(NSi−. Energy decomposition analysis further reveals that the contribution from the orbital term (ΔEorb is dominant (ca. 67%–75% towards the total attraction energy associated with the Si-Ng bond, whereas the electrostatic term (ΔEelstat contributes the maximum (ca. 66%–68% for the same in the Ng–N bond, implying the covalent nature of the former bond and the ionic nature of the latter.

  7. Time-dependent coupling of electron energy distribution function, vibrational kinetics of the asymmetric mode of CO2 and dissociation, ionization and electronic excitation kinetics under discharge and post-discharge conditions

    Science.gov (United States)

    Pietanza, L. D.; Colonna, G.; D'Ammando, G.; Capitelli, M.

    2017-01-01

    A time-dependent self-consistent model based on the coupling of the Boltzmann equation for the electron energy distribution function (EEDF) with the non-equilibrium vibrational kinetics of the asymmetric mode, as well as a simplified global model, have been implemented for a pure CO2 plasma. The simplified time-dependent global model takes into account dissociation and ionization as well as the reverse of these processes. It also takes into account the excitation/de-excitation of an electronic excited state at 10.5 eV. The model has been applied to describe the discharge and post-discharge conditions typically met in an atmospheric-pressure dielectric barrier discharge (DBD) and in a moderate-pressure microwave discharge. The reported results show the strong coupling between the excited state and the electron energy distribution kinetics due to superelastic (vibrational and electronic) collisions. Moreover, the dissociation rate from a pure vibrational mechanism can become competitive with the corresponding rate from the direct electron impact mechanism at high values of vibrational temperature.

  8. Comprehensive thermochemistry of W-H bonding in the metal hydrides CpW(CO)2(IMes)H, [CpW(CO)2(IMes)H](•+), and [CpW(CO)2(IMes)(H)2]+. Influence of an N-heterocyclic carbene ligand on metal hydride bond energies.

    Science.gov (United States)

    Roberts, John A S; Appel, Aaron M; DuBois, Daniel L; Bullock, R Morris

    2011-09-21

    The free energies interconnecting nine tungsten complexes have been determined from chemical equilibria and electrochemical data in MeCN solution (T = 22 °C). Homolytic W-H bond dissociation free energies are 59.3(3) kcal mol(-1) for CpW(CO)(2)(IMes)H and 59(1) kcal mol(-1) for the dihydride [CpW(CO)(2)(IMes)(H)(2)](+) (where IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), indicating that the bonds are the same within experimental uncertainty for the neutral hydride and the cationic dihydride. For the radical cation, [CpW(CO)(2)(IMes)H](•+), W-H bond homolysis to generate the 16-electron cation [CpW(CO)(2)(IMes)](+) is followed by MeCN uptake, with free energies for these steps being 51(1) and -16.9(5) kcal mol(-1), respectively. Based on these two steps, the free energy change for the net conversion of [CpW(CO)(2)(IMes)H](•+) to [CpW(CO)(2)(IMes)(MeCN)](+) in MeCN is 34(1) kcal mol(-1), indicating a much lower bond strength for the 17-electron radical cation of the metal hydride compared to the 18-electron hydride or dihydride. The pK(a) of CpW(CO)(2)(IMes)H in MeCN was determined to be 31.9(1), significantly higher than the 26.6 reported for the related phosphine complex, CpW(CO)(2)(PMe(3))H. This difference is attributed to the electron donor strength of IMes greatly exceeding that of PMe(3). The pK(a) values for [CpW(CO)(2)(IMes)H](•+) and [CpW(CO)(2)(IMes)(H)(2)](+) were determined to be 6.3(5) and 6.3(8), much closer to the pK(a) values reported for the PMe(3) analogues. The free energy of hydride abstraction from CpW(CO)(2)(IMes)H is 74(1) kcal mol(-1), and the resultant [CpW(CO)(2)(IMes)](+) cation is significantly stabilized by binding MeCN to form [CpW(CO)(2)(IMes)(MeCN)](+), giving an effective hydride donor ability of 57(1) kcal mol(-1) in MeCN. Electrochemical oxidation of [CpW(CO)(2)(IMes)](-) is fully reversible at all observed scan rates in cyclic voltammetry experiments (E° = -1.65 V vs Cp(2)Fe(+/0) in MeCN), whereas CpW(CO)(2

  9. Strain-Induced Water Dissociation on Supported Ultrathin Oxide Films

    CERN Document Server

    Song, Zhenjun; Xu, Hu

    2015-01-01

    Controlling the dissociation of single water molecule on an insulating surface plays a crucial role in many catalytic reactions. In this Letter, we have identified the enhanced chemical reactivity of ultrathin MgO(100) films deposited on Mo(100) substrate that causes water dissociation. We reveal that the ability to split water on insulating surface closely depends on the lattice mismatch between ultrathin films and the underlying substrate, and substrate-induced in-plane tensile strain dramatically results in water dissociation on MgO(100). Three dissociative adsorption configurations of water with lower energy are predicted, and the structural transition going from molecular form to dissociative form is almost barrierless. Our results provide an effective avenue to achieve water dissociation at the single-molecule level and shed light on how to tune the chemical reactions of insulating surfaces by choosing the suitable substrates.

  10. The effect of tensile stress on the conformational free energy landscape of disulfide bonds.

    Directory of Open Access Journals (Sweden)

    Padmesh Anjukandi

    Full Text Available Disulfide bridges are no longer considered to merely stabilize protein structure, but are increasingly recognized to play a functional role in many regulatory biomolecular processes. Recent studies have uncovered that the redox activity of native disulfides depends on their C-C-S-S dihedrals, χ2 and χ'2. Moreover, the interplay of chemical reactivity and mechanical stress of disulfide switches has been recently elucidated using force-clamp spectroscopy and computer simulation. The χ2 and χ'2 angles have been found to change from conformations that are open to nucleophilic attack to sterically hindered, so-called closed states upon exerting tensile stress. In view of the growing evidence of the importance of C-C-S-S dihedrals in tuning the reactivity of disulfides, here we present a systematic study of the conformational diversity of disulfides as a function of tensile stress. With the help of force-clamp metadynamics simulations, we show that tensile stress brings about a large stabilization of the closed conformers, thereby giving rise to drastic changes in the conformational free energy landscape of disulfides. Statistical analysis shows that native TDi, DO and interchain Ig protein disulfides prefer open conformations, whereas the intrachain disulfide bridges in Ig proteins favor closed conformations. Correlating mechanical stress with the distance between the two a-carbons of the disulfide moiety reveals that the strain of intrachain Ig protein disulfides corresponds to a mechanical activation of about 100 pN. Such mechanical activation leads to a severalfold increase of the rate of the elementary redox S(N2 reaction step. All these findings constitute a step forward towards achieving a full understanding of functional disulfides.

  11. Energy-efficient green catalysis: supported gold nanoparticle-catalyzed aminolysis of esters with inert tertiary amines by C-O and C-N bond activations.

    Science.gov (United States)

    Bao, Yong-Sheng; Baiyin, Menghe; Agula, Bao; Jia, Meilin; Zhaorigetu, Bao

    2014-07-18

    Catalyzed by supported gold nanoparticles, an aminolysis reaction between various aryl esters and inert tertiary amines by C-O and C-N bond activations has been developed for the selective synthesis of tertiary amides. Comparison studies indicated that the gold nanoparticles could perform energy-efficient green catalysis at room temperature, whereas Pd(OAc)2 could not.

  12. Nucleon-XcJ Dissociation Cross Sections

    Institute of Scientific and Technical Information of China (English)

    冯又层; 许晓明; 周代翠

    2002-01-01

    Nucleon-XcJ dissociation cross sections are calculated in a constituent interexchange model in which quark-quark potential is derived from the Buchmüller-Tye quark-anti-quark potential. These new cross sections for dominant reaction channels depend on the centre-of-mass energy of the nucleon and the charmonium.

  13. Non-dissociative and dissociative ionisation of H sub 2 by 50-2000 keV antiprotons

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, L.H.; Hvelplund, P.; Knudsen, H.; Moeller, S.P.; Pedersen, J.O.P.; Tang-Petersen, S.; Uggerhoej, E. (Aarhus Univ. (Denmark). Inst. of Physics); Elsener, K. (European Organization for Nuclear Research, Geneva (Switzerland)); Morenzoni, E. (Paul Scherrer Inst. (PSI), Villigen (Switzerland))

    1990-08-14

    A beam of antiprotons with energies between 50 keV and 2 MeV has been used for measurements of non-dissociative ionisation and dissociative ionisation cross sections of H{sub 2}. The results are compared with cross sections for equivelocity protons and electrons, and the role of interference effects in two-electron processes is discussed. (author).

  14. Sexuality of dissocial persons

    Directory of Open Access Journals (Sweden)

    Marta Janus

    2016-02-01

    Full Text Available Introduction. The development of personality disorders as well as sexual disorders is defined by the common time spectrum as well as deficits and changes in such areas as biological, environmental and mental area. Dissocial (antisocial personality disorder is characterised by a pervasive pattern of disregard for, or violation of, the rights of others. The indices of the discussed disorder can be found in specific patterns of social inadequacy occurring during childhood and puberty. At the same time, characteristic indices of social functioning at a young age often indicate subsequent dysfunctions in the area of sexuality. Aim. The aim of this paper is to explain sexual functioning of persons with dissocial personality disorder (including the relation with sexual dysfunctions, and to ascertain issues that need further empirical studies. Method. As a result of analysis of available literature (matched with EBSCO database search fulfilling criteria of sample size, accuracy of examination procedure, conclusions and discussion 5 articles fulfilling criteria cited above has been found. Conclusions: Based on literature overview, it appeared to be impossible to determine one coherent way of sexual functioning of dissocial persons, and to establish causal relationship of sexual dysfunctions and dissocial personality disorder. However, it is possible to indicate group of most characteristic dysfunctional sexual behaviours. Noteworthy, available publication analyse only selected aspects of sexual behaviours in small, homogenous groups. There is a lack of review studies as well as multi-faceted studies.

  15. Dissociative Identity Disorder

    Science.gov (United States)

    Schmidt, Tom

    2007-01-01

    Few psychological disorders in the Diagnostic Statistical Manual have generated as much controversy as Dissociative Identity Disorder (DID). For the past 35 years diagnoses of DID, previously referred to as Multiple Personality Disorder (MPD), have increased exponentially, causing various psychological researchers and clinicians to question the…

  16. Polarization induced water molecule dissociation below the first-order electronic-phase transition temperature.

    Science.gov (United States)

    Das Arulsamy, Andrew; Kregar, Zlatko; Eleršič, Kristina; Modic, Martina; Subramani, Uma Shankar

    2011-09-01

    Hydrogen produced from the photocatalytic splitting of water is one of the reliable alternatives to replace the polluting fossil and the radioactive nuclear fuels. Here, we provide unequivocal evidence for the existence of blue- and red-shifting O-H covalent bonds within a single water molecule adsorbed on the MgO surface as a result of asymmetric displacement polarizabilities. The adsorbed H-O-H on MgO gives rise to one weaker H-O bond, while the other O-H covalent bond from the same adsorbed water molecule compensates this effect with a stronger bond. The weaker bond (nearest to the surface), the interlayer tunneling electrons and the silver substrate are shown to be the causes for the smallest dissociative activation energy on the MgO monolayer. The origin that is responsible to initiate the splitting mechanism is proven to be due to the changes in the polarizability of an adsorbed water molecule, which are further supported by the temperature-dependent static dielectric constant measurements for water below the first-order electronic-phase transition temperature.

  17. Polarization induced water molecule dissociation below the first-order electronic-phase transition temperature

    CERN Document Server

    Arulsamy, Andrew Das; Elersic, Kristina; Modic, Martina; Subramani, Uma Shankar

    2011-01-01

    Hydrogen produced from the photocatalytic splitting of water is one of the reliable alternatives to replace the polluting fossil and the radioactive nuclear fuels. Here, we provide unequivocal evidence for the existence of blue- and red-shifting O$-$H covalent bonds within a single water molecule adsorbed on MgO surface as a result of asymmetric displacement polarizabilities. The adsorbed H-O-H on MgO gives rise to one weaker H-O bond, while the other O-H covalent bond from the same adsorbed water molecule compensates this effect with a stronger bond. The weaker bond (nearest to the surface), the interlayer tunneling electrons and the silver substrate are shown to be the causes for the smallest dissociative activation energy on MgO monolayer. The origin that is responsible to initiate the splitting mechanism is proven to be due to the changes in the polarizability of an adsorbed water molecule, which are further supported by the temperature-dependent static dielectric constant measurements for water below the...

  18. Dissociation of equimolar mixtures of aqueous carboxylic acids in ionic liquids: role of specific interactions.

    Science.gov (United States)

    Shukla, Shashi Kant; Kumar, Anil

    2015-04-30

    Hammett acidity function observes the effect of protonation/deprotonation on the optical density/absorbance of spectrophotometric indicator. In this work, the Hammett acidity, H0, of equimolar mixtures of aqueous HCOOH, CH3COOH, and CH3CH2COOH was measured in 1-methylimidazolium-, 1-methylpyrrolidinium-, and 1-methylpiperidinium-based protic ionic liquids (PILs) and 1-butyl-3-methylimidazolium-based aprotic ionic liquid (AIL) with formate (HCOO(-)) anion. Higher H0 values were observed for the equimolar mixtures of aqueous carboxylic acids in protic ionic liquids compared with those of the aprotic ionic liquid because of the involvement of the stronger specific interactions between the conjugate acid of ionic liquid and conjugate base of carboxylic acids as suggested by the hard-soft acid base (HSAB) theory. The different H0 values for the equimolar mixtures of aqueous carboxylic acids in protic and aprotic ionic liquids were noted to depend on the activation energy of proton transfer (Ea,H(+)). The higher activation energy of proton transfer was obtained in AIL, indicating lower ability to form specific interactions with solute than that of PILs. Thermodynamic parameters determined by the "indicator overlapping method" further confirmed the involvement of the secondary interactions in the dissociation of carboxylic acids. On the basis of the thermodynamic parameter values, the potential of different ionic liquids in the dissociation of carboxylic acids was observed to depend on the hydrogen bond donor acidity (α) and hydrogen bond acceptor basicity (β), characteristics of specific interactions.

  19. Ionisation and dissociation of water induced by swift multicharged ions; Etude de l'ionisation et de la dissociation d'H{sub 2}O induites par collision avec des ions multicharges rapides

    Energy Technology Data Exchange (ETDEWEB)

    Legendre, S

    2006-02-15

    Ionization and dissociation of water molecules and water clusters induced by 11.7 MeV/A Ni{sup 25+} ions were carried out by imaging techniques. Branching ratios, ionisation cross sections and Kinetic Energy Released distributions have been measured together with fragmentation dynamics studies. Multiple ionization represents approximately 30% of the ionizing events. Double ionization produces in significant way atomic oxygen, considered as a possible precursor of the large production of HO{sub 2} radical in liquid water radiolysis by ions of high Linear Energy Transfer. We evidence a strong selectivity of bond breakage in the case of ion-induced HOD fragmentation. Once the molecule doubly ionized, the breakage of the O-H bond is found 6.5 times more probable than that of the O-D bond. A semi-classical calculation simulating the fragmentation dynamics on the potential energy surface of the ground-state of di-cation H{sub 2}O{sup 2+} makes possible to as well reproduce the preferential nature of the breakage of the O-H bond as the position and the shift of the kinetic energy distributions. First results concerning interaction with water clusters are also reported. Measurements in coincidence are carried out giving access to correlation, with the distributions in energy and angle of the emitted fragments. Mass spectrum points fast intra-cluster proton transfer, leading to the emission of protonated clusters. (author)

  20. Quantum dynamics of dissociative chemisorption of CH(4) on Ni(111): Influence of the bending vibration.

    Science.gov (United States)

    Krishnamohan, G P; Olsen, R A; Kroes, G-J; Gatti, F; Woittequand, S

    2010-10-14

    Two-dimensional, three-dimensional, and four-dimensional quantum dynamic calculations are performed on the dissociative chemisorption of CH(4) on Ni(111) using the multiconfiguration time-dependent Hartree (MCTDH) method. The potential energy surface used for these calculations is 15-dimensional (15D) and was obtained with density functional theory for points which are concentrated in the region that is dynamically relevant to reaction. Many reduced dimensionality calculations were already performed on this system, but the molecule was generally treated as pseudodiatomic. The main improvement of our model is that we try to describe CH(4) as a polyatomic molecule by including a degree of freedom describing a bending vibration in our three-dimensional and four-dimensional models. Using a polyspherical coordinate system, a general expression for the 15D kinetic energy operator is derived, which discards all the singularities in the operator and includes rotational and Coriolis coupling. We use seven rigid constraints to fix the CH(3) umbrella of the molecule to its gas phase equilibrium geometry and to derive two-dimensional, three-dimensional, and four-dimensional Hamiltonians, which were used in the MCTDH method. Only four degrees of freedom evolve strongly along the 15D minimum energy path: the distance of the center of mass of the molecule to the surface, the dissociative C[Single Bond]H bond distance, the polar orientation of the molecule, and the bending angle between the dissociative C[Single Bond]H bond and the umbrella. A selection of these coordinates is included in each of our models. The polar rotation is found to be important in determining the mode selective behavior of the reaction. Furthermore, our calculations are in good agreement with the finding of Xiang et al. [J. Chem. Phys. 117, 7698 (2002)] in their reduced dimensional calculation that the helicopter motion of the umbrella symmetry axis is less efficient than its cartwheel motion for promoting

  1. Uniform Free-Energy Profiles of the P-O Bond Formation and Cleavage Reactions Catalyzed by DNA Polymerases β and λ.

    Science.gov (United States)

    Klvaňa, Martin; Bren, Urban; Florián, Jan

    2016-12-29

    Human X-family DNA polymerases β (Polβ) and λ (Polλ) catalyze the nucleotidyl-transfer reaction in the base excision repair pathway of the cellular DNA damage response. Using empirical valence bond and free-energy perturbation simulations, we explore the feasibility of various mechanisms for the deprotonation of the 3'-OH group of the primer DNA strand, and the subsequent formation and cleavage of P-O bonds in four Polβ, two truncated Polλ (tPolλ), and two tPolλ Loop1 mutant (tPolλΔL1) systems differing in the initial X-ray crystal structure and nascent base pair. The average calculated activation free energies of 14, 18, and 22 kcal mol(-1) for Polβ, tPolλ, and tPolλΔL1, respectively, reproduce the trend in the observed catalytic rate constants. The most feasible reaction pathway consists of two successive steps: specific base (SB) proton transfer followed by rate-limiting concerted formation and cleavage of the P-O bonds. We identify linear free-energy relationships (LFERs) which show that the differences in the overall activation and reaction free energies among the eight studied systems are determined by the reaction free energy of the SB proton transfer. We discuss the implications of the LFERs and suggest pKa of the 3'-OH group as a predictor of the catalytic rate of X-family DNA polymerases.

  2. Performance of a Nonempirical Density Functional on Molecules and Hydrogen-Bonded Complexes

    CERN Document Server

    Mo, Yuxiang; Car, Roberto; Staroverov, Viktor N; Scuseria, Gustavo E; Tao, Jianmin

    2016-01-01

    Recently, Tao and Mo (TM) derived a new meta-generalized gradient approximation based on a model exchange hole. In this work, the performance of this functional is assessed on standard test sets, using the 6-311++G(3df,3pd) basis set. These test sets include 223 G3/99 enthalpies of formation, 58 electron affinities, 8 proton affinities, 96 bond lengths, 82 harmonic vibrational frequencies, and 10 hydrogen-bonded molecular complexes. Our calculations show that the TM functional can achieve remarkable accuracy for most molecular properties, improving upon non-empirical density functionals considered here. In particular, it delivers the best accuracy for proton affinities, harmonic vibrational frequencies, and hydrogen-bonded dissociation energies and bond lengths, compared to other semilocal density-functional approximations considered in this work.

  3. Charge Transfer Dissociation (CTD) Mass Spectrometry of Peptide Cations: Study of Charge State Effects and Side-Chain Losses

    Science.gov (United States)

    Li, Pengfei; Jackson, Glen P.

    2017-01-01

    1+, 2+, and 3+ precursors of substance P and bradykinin were subjected to helium cation irradiation in a 3D ion trap mass spectrometer. Charge exchange with the helium cations produces a variety of fragment ions, the number and type of which are dependent on the charge state of the precursor ions. For 1+ peptide precursors, fragmentation is generally restricted to C-CO backbone bonds (a and x ions), whereas for 2+ and 3+ peptide precursors, all three backbone bonds (C-CO, C-N, and N-Cα) are cleaved. The type of backbone bond cleavage is indicative of possible dissociation channels involved in CTD process, including high-energy, kinetic-based, and ETD-like pathways. In addition to backbone cleavages, amino acid side-chain cleavages are observed in CTD, which are consistent with other high-energy and radical-mediated techniques. The unique dissociation pattern and supplementary information available from side-chain cleavages make CTD a potentially useful activation method for the structural study of gas-phase biomolecules.

  4. Influence of duration of phosphoric acid pre-etching on bond durability of universal adhesives and surface free-energy characteristics of enamel.

    Science.gov (United States)

    Tsujimoto, Akimasa; Barkmeier, Wayne W; Takamizawa, Toshiki; Watanabe, Hidehiko; Johnson, William W; Latta, Mark A; Miyazaki, Masashi

    2016-08-01

    The purpose of this study was to evaluate the influence of duration of phosphoric acid pre-etching on the bond durability of universal adhesives and the surface free-energy characteristics of enamel. Three universal adhesives and extracted human molars were used. Two no-pre-etching groups were prepared: ground enamel; and enamel after ultrasonic cleaning with distilled water for 30 s to remove the smear layer. Four pre-etching groups were prepared: enamel pre-etched with phosphoric acid for 3, 5, 10, and 15 s. Shear bond strength (SBS) values of universal adhesive after no thermal cycling and after 30,000 or 60,000 thermal cycles, and surface free-energy values of enamel surfaces, calculated from contact angle measurements, were determined. The specimens that had been pre-etched showed significantly higher SBS and surface free-energy values than the specimens that had not been pre-etched, regardless of the aging condition and adhesive type. The SBS and surface free-energy values did not increase for pre-etching times of longer than 3 s. There were no significant differences in SBS values and surface free-energy characteristics between the specimens with and without a smear layer. The results of this study suggest that phosphoric acid pre-etching of enamel improves the bond durability of universal adhesives and the surface free-energy characteristics of enamel, but these bonding properties do not increase for phosphoric acid pre-etching times of longer than 3 s.

  5. Bond energies of ThO+ and ThC+: A guided ion beam and quantum chemical investigation of the reactions of thorium cation with O2 and CO

    Science.gov (United States)

    Cox, Richard M.; Citir, Murat; Armentrout, P. B.; Battey, Samuel R.; Peterson, Kirk A.

    2016-05-01

    Kinetic energy dependent reactions of Th+ with O2 and CO are studied using a guided ion beam tandem mass spectrometer. The formation of ThO+ in the reaction of Th+ with O2 is observed to be exothermic and barrierless with a reaction efficiency at low energies of k/kLGS = 1.21 ± 0.24 similar to the efficiency observed in ion cyclotron resonance experiments. Formation of ThO+ and ThC+ in the reaction of Th+ with CO is endothermic in both cases. The kinetic energy dependent cross sections for formation of these product ions were evaluated to determine 0 K bond dissociation energies (BDEs) of D0(Th+-O) = 8.57 ± 0.14 eV and D0(Th+-C) = 4.82 ± 0.29 eV. The present value of D0 (Th+-O) is within experimental uncertainty of previously reported experimental values, whereas this is the first report of D0 (Th+-C). Both BDEs are observed to be larger than those of their transition metal congeners, TiL+, ZrL+, and HfL+ (L = O and C), believed to be a result of lanthanide contraction. Additionally, the reactions were explored by quantum chemical calculations, including a full Feller-Peterson-Dixon composite approach with correlation contributions up to coupled-cluster singles and doubles with iterative triples and quadruples (CCSDTQ) for ThC, ThC+, ThO, and ThO+, as well as more approximate CCSD with perturbative (triples) [CCSD(T)] calculations where a semi-empirical model was used to estimate spin-orbit energy contributions. Finally, the ThO+ BDE is compared to other actinide (An) oxide cation BDEs and a simple model utilizing An+ promotion energies to the reactive state is used to estimate AnO+ and AnC+ BDEs. For AnO+, this model yields predictions that are typically within experimental uncertainty and performs better than density functional theory calculations presented previously.

  6. CO dissociation on Ni: The effect of steps and of nickel carbonyl

    DEFF Research Database (Denmark)

    Engbæk, Jakob; Lytken, Ole; Nielsen, Jane Hvolbæk;

    2008-01-01

    The dissociation of CO was investigated on a stepped Ni(141313) crystal. The experiments show that the monoatomic steps completely dominate the dissociation of CO on the nickel surface. The activation energy for dissociation of CO along the steps is measured at 500 K to be 150 kJ/mol in the press...... and in the Fischer-Tropsch synthesis....

  7. Taming microwave plasma to beat thermodynamics in CO2 dissociation

    NARCIS (Netherlands)

    van Rooij, G.; van den Bekerom, D.; N. den Harder,; Minea, T.; G. Berden,; Bongers, W.; Engeln, R.; Graswinckel, M.; Zoethout, E.; M. C. M. van de Sanden,

    2015-01-01

    The strong non-equilibrium conditions provided by the plasma phase offer the opportunity to beat traditional thermal process energy efficiencies via preferential excitation of molecular vibrations. Simple molecular physics considerations are presented to explain potential dissociation pathways in a

  8. Probing the dynamics of dissociation of methane following core ionization using three-dimensional molecular-frame photoelectron angular distributions

    Science.gov (United States)

    Williams, J. B.; Trevisan, C. S.; Schöffler, M. S.; Jahnke, T.; Bocharova, I.; Kim, H.; Ulrich, B.; Wallauer, R.; Sturm, F.; Rescigno, T. N.; Belkacem, A.; Dörner, R.; Weber, Th; McCurdy, C. W.; Landers, A. L.

    2012-10-01

    We present experimental measurements and theoretical calculations for the photoionization of CH4 at the carbon K-edge. Measurements performed using cold target recoil ion momentum spectroscopy (COLTRIMS) combined with complex Kohn variational calculations of the photoelectron in the molecular frame demonstrate the surprising result that the low energy photoelectrons effectively image the molecule by emerging along the bond axes. Furthermore, we observe a dynamic breakdown of axial recoil behaviour in one of the dissociation pathways of the intermediate dication, which we interpret using electronic structure calculations.

  9. Theory of dissociative tunneling ionization

    CERN Document Server

    Svensmark, Jens; Madsen, Lars Bojer

    2016-01-01

    We present a theoretical study of the dissociative tunneling ionization process. Analytic expressions for the nuclear kinetic energy distribution of the ionization rates are derived. A particularly simple expression for the spectrum is found by using the Born-Oppenheimer (BO) approximation in conjunction with the reflection principle. These spectra are compared to exact non-BO ab initio spectra obtained through model calculations with a quantum mechanical treatment of both the electronic and nuclear degrees freedom. In the regime where the BO approximation is applicable imaging of the BO nuclear wave function is demonstrated to be possible through reverse use of the reflection principle, when accounting appropriately for the electronic ionization rate. A qualitative difference between the exact and BO wave functions in the asymptotic region of large electronic distances is shown. Additionally the behavior of the wave function across the turning line is seen to be reminiscent of light refraction. For weak fiel...

  10. Adsorption and dissociation of H2S on monometallic and monolayer bimetallic Ni/Pd(111) surfaces: A first-principles study

    Science.gov (United States)

    Li, Yi; Huang, Pan; Tao, Dandan; Wu, Juan; Qiu, Mei; Huang, Xin; Ding, Kaining; Chen, Wenkai; Su, Wenyue; Zhang, Yongfan

    2016-11-01

    Periodic density functional theory calculations have been performed to investigate the adsorption structures and dissociative reaction pathways for H2S molecule on Ni(111), Pd(111) and Ni/Pd(111) monolayer bimetallic surfaces with surface monolayer and subsurface monolayer structures. Our results indicate that, for the molecular adsorption mode, the introducing Pd atoms on Ni(111) can enhance the binding strength between H2S and the surface, while an opposite effect is achieved when the Ni monolayer is formed on Pd(111) surface. The decompositions of H2S molecule on all Ni/Pd(111) surfaces are exothermic, especially for the surfaces that the top layer is composed of Ni atoms. According to the predicted minimum energy paths that connect the molecular and dissociative states, two elementary steps are found for all Ni/Pd(111) metal surfaces, and the breaking of the first Hsbnd S bond is the rate-determining step for the H2S dissociation. Our results reveal that in most cases, the decomposition of H2S molecule on the monometallic and Ni/Pd(111) monolayer bimetallic surfaces is easy to happen. However, on the monolayer Ni-Pd(111) surface, there is a competition between the trapping-desorption channel and activated dissociation channel, which implies that depositing one monolayer Ni on a Pd(111) surface may help reducing sulfur poisoning by hindering the dissociation of H2S molecule.

  11. Direct assessment of quantum nuclear effects on hydrogen bond strength by constrained-centroid ab initio path integral molecular dynamics

    Science.gov (United States)

    Walker, Brent; Michaelides, Angelos

    2010-11-01

    The impact of quantum nuclear effects on hydrogen (H-) bond strength has been inferred in earlier work from bond lengths obtained from path integral molecular dynamics (PIMD) simulations. To obtain a direct quantitative assessment of such effects, we use constrained-centroid PIMD simulations to calculate the free energy changes upon breaking the H-bonds in dimers of HF and water. Comparing ab initio simulations performed using PIMD and classical nucleus molecular dynamics (MD), we find smaller dissociation free energies with the PIMD method. Specifically, at 50 K, the H-bond in (HF)2 is about 30% weaker when quantum nuclear effects are included, while that in (H2O)2 is about 15% weaker. In a complementary set of simulations, we compare unconstrained PIMD and classical nucleus MD simulations to assess the influence of quantum nuclei on the structures of these systems. We find increased heavy atom distances, indicating weakening of the H-bond consistent with that observed by direct calculation of the free energies of dissociation.

  12. Oxidative addition of the C-I bond on aluminum nanoclusters

    Science.gov (United States)

    Sengupta, Turbasu; Das, Susanta; Pal, Sourav

    2015-07-01

    Energetics and the in-depth reaction mechanism of the oxidative addition step of the cross-coupling reaction are studied in the framework of density functional theory (DFT) on aluminum nanoclusters. Aluminum metal in its bulk state is totally inactive towards carbon-halogen bond dissociation but selected Al nanoclusters (size ranging from 3 to 20 atoms) have shown a significantly lower activation barrier towards the oxidative addition reaction. The calculated energy barriers are lower than the gold clusters and within a comparable range with the conventional and most versatile Pd catalyst. Further investigations reveal that the activation energies and other reaction parameters are highly sensitive to the geometrical shapes and electronic structures of the clusters rather than their size, imposing the fact that comprehensive studies on aluminum clusters can be beneficial for nanoscience and nanotechnology. To understand the possible reaction mechanism in detail, the reaction pathway is investigated with the ab initio Born Oppenheimer Molecular Dynamics (BOMD) simulation and the Natural Bond Orbital (NBO) analysis. In short, our theoretical study highlights the thermodynamic and kinetic details of C-I bond dissociation on aluminum clusters for future endeavors in cluster chemistry.Energetics and the in-depth reaction mechanism of the oxidative addition step of the cross-coupling reaction are studied in the framework of density functional theory (DFT) on aluminum nanoclusters. Aluminum metal in its bulk state is totally inactive towards carbon-halogen bond dissociation but selected Al nanoclusters (size ranging from 3 to 20 atoms) have shown a significantly lower activation barrier towards the oxidative addition reaction. The calculated energy barriers are lower than the gold clusters and within a comparable range with the conventional and most versatile Pd catalyst. Further investigations reveal that the activation energies and other reaction parameters are highly

  13. Dissociation of deep-core-excited CH{sub 3}Cl

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, D.L.; Martin, R.; Vanderford, B. [Univ. of Nevada, Las Vegas, NV (United States)] [and others

    1997-04-01

    Using x-rays from B.L. 9.3.1, a space-focused time-of-flight (TOF) was used to study photofragmentation of CH{sub 3}Cl following excitation in the neighborhood of the Cl K-shell threshold ({approximately} 2.8 keV). Multi-ion coincidence measurements were used to search for selective dissociation of specific bonds in the molecule. Such selectivity has been observed for excitation near outer-core-level thresholds (e.g., Cl 2p), but this is the first study in deep core levels, where very-short core-hole lifetimes and Auger cascade effects may influence fragmentation. Both high-resolution time-of-flight spectroscopy and multi-coincidence photoelectron-photoion-photoion (PE-PIPICO), as well as photoelectron-photoion-photoion-photoion (PE3PICO) measurements were performed. Dramatic changes in the line shapes for different fragment ions are observed as a function of the excitation energy, and are attributed to selective dissociation of the CH{sub 3}Cl molecule along the C-Cl bond. In addition, pronounced angular distributions of the ejected ions are observed on resonance.

  14. Probing the segmental mobility and energy of the active zones of a protein chain (aspartic acid protease) by a coarse-grained bond-fluctuation Monte Carlo simulation

    Science.gov (United States)

    Pandey, Ras; Farmer, Barry

    2008-03-01

    A protein chain such as aspartic acid protease is described by a specific sequence of 99 residues each with its own specific characteristics. In a coarse-grained description, the backbone of a protein chain is described by nodes tethered together by peptide bonds where each node (the amino acid group) is characterized by molecular weight and hydrophobicity. A well-developed and somewhat mature computational modeling tool for the polymer chain such as the bond-fluctuation model is used to study such a specific protein chain with its constitutive amino groups and their sequence. The relative magnitude of hydrophobicity is used to develop appropriate interaction potentials for these amino acid groups in explicit solvent. The Metropolis algorithm is used to move each node and solvent constituent. Local energy and mobility of each amino group are analyzed along with global energy, mobility, and conformation of the protein chain. Effect of the solvent interaction and its concentration on these quantities will be presented.

  15. The Repeated Computation of the Bond Length and Ground- State Energy for H2 +%H2+键长和基态能量的再计算

    Institute of Scientific and Technical Information of China (English)

    李旭; 胡先权

    2002-01-01

    Ritz variation method was used to find the numerical relation bctween the energy near the ground - state of the hydrogenmolecular ion H2 + .and the changes of the variation parameter andthe bond length, the computation formula of bond length and ground- state energy for H2 * was also obtained by means of the method ofparabolie interpolation. The computation results were much closer toexperinental values than those of Refs. [ 1,2]' s.%用Ritz变分法求出了氢分子离子H2+基态能量附近的能量随变分参数和分子键长变化的数值关系,并用抛物线插值法获得了H2+键长和基态能量的值及其计算公式,比文献[1,2]更接近于实验值.

  16. Impact of deformation energy on the hydrogen bonding interactions in gas phase 3-X catechol ⋯ H2O complexes (X = H, F, Cl, Br): The effect of approach of a water molecule

    Science.gov (United States)

    Deb, Debojit Kumar; Sarkar, Biplab

    2016-06-01

    The conformations and nature of hydrogen bonding interactions for 3-X catechol ⋯ H2O (X = H, F, Cl, Br) has been investigated by ab initio MP2, CCSD(T), and density functional B3LYP, wB97XD and M06-2X methods. The changes in interaction energies due to deformation of the structures has been studied in detail. The intra- and intermolecular hydrogen bonding interactions due to the different direction of approach of water molecule have been discussed. A detailed natural bond orbital (NBO) analysis and the symmetry-adapted perturbation theory (SAPT) based energy decomposition analysis has been carried out to elucidate interaction strength and properties in these hydrogen bonded systems. The charge transfer percentage (CTP) has been derived which will be universally useful for correlating binding energy, deformation energy and the geometrical parameters such as angles, bond lengths, etc. for other systems as well.

  17. INFLUENCE OF ORGANIC SOLVENTS ON WATER DISSOCIATION IN BIPOLAR MEMBRANE

    Directory of Open Access Journals (Sweden)

    Sheldeshov N. V.

    2015-12-01

    Full Text Available The article discusses results of experimental research of the influence of aprotic and proton solvents on reaction rate of water molecules dissociation in the bipolar membrane MB-1 by the method of electrochemical impedance frequency spectrum. It was discovered, that addition of organic component in aqueous solutions results in significant influence on the parameters of water dissociation in a bipolar region of the membrane. The reason for this influence is the reduction of the mass fraction of water in solution and, consequently, in a bipolar region of the membrane, which itself reduces the rate of the dissociation reaction. Another reason for the influence of the organic solvent is its effect on the network of hydrogen bonds existing in water and aqueous solutions. Depending on the nature of organic solvent and its concentration, the network of hydrogen bonds may be strengthened, or destroyed, thus facilitating removal of the proton involved in the reactions between water molecules and catalytic centers in cation-exchange and anion-exchange layer of bipolar membrane, or retarding removal of proton. This leads respectively to speed up or slow down the rate of dissociation in the bipolar region of the membrane, as well as changing the constants of the dissociation reaction of water. Introduction of organic solvent in solutions, which are in the contact with bipolar membrane, is a convenient method of investigating the role of solution composition on the rate of proton transfer between water molecules and catalytic centers in the membranes

  18. Hydrogen Bonds in Excited State Proton Transfer

    Science.gov (United States)

    Horke, D. A.; Watts, H. M.; Smith, A. D.; Jager, E.; Springate, E.; Alexander, O.; Cacho, C.; Chapman, R. T.; Minns, R. S.

    2016-10-01

    Hydrogen bonding interactions between biological chromophores and their surrounding protein and solvent environment significantly affect the photochemical pathways of the chromophore and its biological function. A common first step in the dynamics of these systems is excited state proton transfer between the noncovalently bound molecules, which stabilizes the system against dissociation and principally alters relaxation pathways. Despite such fundamental importance, studying excited state proton transfer across a hydrogen bond has proven difficult, leaving uncertainties about the mechanism. Through time-resolved photoelectron imaging measurements, we demonstrate how the addition of a single hydrogen bond and the opening of an excited state proton transfer channel dramatically changes the outcome of a photochemical reaction, from rapid dissociation in the isolated chromophore to efficient stabilization and ground state recovery in the hydrogen bonded case, and uncover the mechanism of excited state proton transfer at a hydrogen bond, which follows sequential hydrogen and charge transfer processes.

  19. Energies of peptide peptide and peptide water hydrogen bonds in collagen: Evidences from infrared spectroscopy, quartz piezogravimetry and differential scanning calorimetry

    Science.gov (United States)

    Boryskina, O. P.; Bolbukh, T. V.; Semenov, M. A.; Gasan, A. I.; Maleev, V. Ya.

    2007-02-01

    The aim of the present work is a quantitative estimation of energies of peptide-peptide N 1sbnd H 1⋯O 2dbnd C 2 and peptide-water hydrogen bonds in collagen type I and model collagen polypeptide poly(Gly-Pro-Pro). Being a challenging theoretical task this is also an issue that can clarify the physical basis of stability of collagen structures that play a very important structural role in connective tissue. The study was performed on the basis of a complex approach of a number of experimental techniques, namely infrared spectroscopy, quartz piezogravimetry and differential scanning calorimetry. Our results indicate that binding of 3-4 water molecules of the internal hydration shell to each -Gly-X-Y- unit of poly(Gly-Pro-Pro) and collagen leads to simultaneous conformational reorganization of the triple helix and strengthening of the peptide-peptide hydrogen bonds. Enthalpies of hydration of poly(Gly-Pro-Pro) and collagen constitute -10.9 and -12.2 kJ/mol, respectively. Enthalpies of peptide-peptide N 1sbnd H 1⋯O 2dbnd C 2 hydrogen bonds are -7.6 and -6.0 kJ/mol in poly(Gly-Pro-Pro) and collagen, correspondently. The results obtained can be used for evaluation of the impacts of energies of different types of interactions into the total energy of stabilization of native triple helical collagen and poly(Gly-Pro-Pro).

  20. The Effect of Energy Densities on the Shear Bond Strength of Self-Adhering Flowable Composite to Er:YAG Pretreated Dentin.

    Science.gov (United States)

    Nahas, Paul; Zeinoun, Toni; Majzoub, Zeina; Corbani, Karim; Nammour, Samir

    2016-01-01

    Objective. To investigate the shear bond strength of self-adhering flowable resin composite, to dentin, after exposing it to Er:YAG laser radiation, at different energy densities. Materials and Methods. Sixty freshly extracted human third molars were randomly divided into five groups (n = 12). In the control group, dentin was left unirradiated, whereas, in the other four groups, dentin was irradiated with Er:YAG laser in noncontact mode (MSP mode = 100 µs; 10 Hz; beam diameter: 1.3 mm; speed of 1 mm/second; air 6 mL/min; and water 4 mL/min), and respectively, with the following level of energy (50 mJ, 60 mJ, 80 mJ, and 100 mJ). Then, self-adhering flowable resin composite was bonded to all prepared dentin surfaces. Shear bond strength (SBS) was applied and fractured surfaces were examined using scanning electron microscopy. Results. SBS values showed significant differences in 60 mJ (P flowable resin composite when it is used at the appropriate low level of energy density.

  1. Gas Phase Dissociative Electron Attachment to Formamide Derivatives NMF and DMF

    Science.gov (United States)

    Li, Zhou; Dawley, M. Michele; Ptasinska, Sylwia

    2015-09-01

    Fragmentation of biomolecules, such as nucleobases, induced by low energy electrons can lead to the break of DNA strands. Dissociative electron attachment (DEA), which can occur due to low energy interactions, is initiated with the formation of transient negative ions which exhibit characteristic resonant profiles in the product ion yield. The consequent fragmentation process can either be as simple as a single bond cleavage or a relatively complex process involving multiple bond rearrangements. Measurements of resonant peaks in ion yields and identification of ion products provide information of the resonant energies of the parent molecules as well as the fragmentation pathways. N-methylformamide (NMF) and dimethylformamide (DMF) are both derivatives of formamide which is the simplest structure containing the peptide bond linkage. In this work we identified anion fragments and measured resonance profiles of produced anions due to DEA to NMF and DMF. The anionic species produced from the two molecules were compared as well as the resonant positions and ion yields. Based on this comparison, the DEA process to the two molecules bears similarities such as leading to breaking of peptide bonds (C-N), as well as discrepancies such as absence of OCN- in DEA to DMF. The selective property of H atom loss, which is reported in the DEA to formamide, is also justified in our experiment since no dehydrogenated DMF anion was detected. This material is based upon work supported by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences under Award Number DE-FC02-04ER15533.

  2. Recurrent dissociative fugue

    Directory of Open Access Journals (Sweden)

    Abhishek Mamarde

    2013-01-01

    Full Text Available Dissociative fugue is a rarely reported diagnostic entity. It is one of the least understood and yet clinically one of the most fascinating disorders in mental health. Here, we describe a case of fugue in a 32-year-old man who was brought to mental hospital with complete loss of memory for events pertaining to identity of self. This case illustrates the nature of presentation in hospital setting like mental hospital and effort taken to reintegrate his identity and reunite with his family.

  3. Analytic potentials and vibrational energies for Li$_{2}$ states dissociating to $\\mbox{Li}\\left(2S\\right)+\\mbox{Li}\\left(3P\\right)$. Part 1: The $^{2S+1}\\Pi_{u/g}$ states

    CERN Document Server

    Dattani, Nikesh S

    2015-01-01

    Analytic potentials are built for all four $^{2S+1}\\Pi_{u/g}$ states of Li$_{2}$ dissociating to Li$(2S)$ + Li$(3P)$: $3b(3^{3}\\Pi_{u})$, $3B(3^{1}\\Pi_{u})$, $3C(3^{1}\\Pi_{g}),$ and $3d(3^{3}\\Pi_{g})$. These potentials include the effect of spin-orbit coupling for large internuclear distances, and include state of the art long-range constants. This is the first successful demonstration of fully analytic diatomic potentials that capture features that are usually considered too difficult to capture without a point-wise potential, such as multiple minima, and shelves. Vibrational energies for each potential are presented for the isotopologues $^{6,6}$Li$_{2}$, $^{6,7}$Li$_{2}$, $^{7,7}$Li$_{2}$, and the elusive `halo nucleonic molecule' $^{11,11}$Li$_{2}$. These energies are claimed to be accurate enough for new high-precision experimental setups such as the one presented in {[}Sebastian \\emph{et al.} Phys. Rev. A, \\textbf{90}, 033417 (2014){]} to measure and assign energy levels of these electronic states, all ...

  4. The electron-impact dissociative ionization of CCl{sub 2}F{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Sierra, Borja [Departamento de QuImica FIsica, Universidad del PaIs Vasco, Facultad de Ciencias, Apartado 644, 48080 Bilbao (Spain); MartInez, Roberto [Departamento de QuImica FIsica, Universidad del PaIs Vasco, Facultad de Ciencias, Apartado 644, 48080 Bilbao (Spain); Castano, Fernando [Departamento de QuImica FIsica, Universidad del PaIs Vasco, Facultad de Ciencias, Apartado 644, 48080 Bilbao (Spain)

    2004-01-14

    An investigation of the formation channels and properties of ion fragments following electron-impact dissociative ionization of the CCl{sub 2}F{sub 2} molecule using electron kinetic energies in the 0-100 eV range is reported. Measurements of ion appearance potentials (APs) and nascent translational energy distributions were made on a supersonic expansion of CCl{sub 2}F{sub 2} in a time-of-flight mass spectrometer. A discussion of the correlation between the channel APs, the precursor bond characters as calculated from the population analysis, and the low-resolution photoelectron spectrum of the CCl{sub 2}F{sub 2} molecule is presented.

  5. Theoretical Study of Nonclassical Platinum Complexes Bonding to Purine Bases: How the Long-lived Monofunctional Adducts Can Be in Existence?

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The B3LYP/6-31G* level of theory was used for the optimization of nonclassical platinum drugs with planar aromatic heterocycle ligands in addition to their monoaqua species, diaqua species and monofunctional adducts. Single point calculations were performed on optimized geometries using the MP2/6-31G** method, and the Lanl2dz pseudo potential for the Pt atom remained constant in all calculations. It can be easily seen that the trans effect can influence both geometrical structures and bond dissociating energies (BDEs). On the basis of our calculation, we get that the long-lived monofunctional adducts with chloride ligand may be in existence, because they possessed higher stability energies, easily dissociated chloride compared with the monoaqua species dissociating chloride and that replacement of the first chloride by bases became exothermic in solution. Our calculated results also demonstrate that the strongest H-bonds appear in the complexes of q-wG and t-wG using different methods. In comparison with adenine complexes, the corresponding guanine complexes possess larger interaction energies as well as higher stability energies either corrected by basis set superposition error (bsse) of Boys-Bernardi counterpoise method or uncorrected both in gas phase and in solution with one exception that the stability energy of q-ClA complex in solution is larger than that of q-ClG complex. Finally, the nature of bond was analyzed in terms of partial charges distribution based on NBO population.

  6. Reaction pathways of the dissociation of methylal: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Frey, H.-M.; Beaud, P.; Gerber, T.; Mischler, B.; Radi, P.P.; Tzannis, A.-P. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Schemata for modelling combustion processes do not yet include reaction rates for oxygenated fuels like methylal (DMM) which is considered as an additive or replacement for diesel due to its low sooting propensity. Density functional theory (DFT) studies of the possible reaction pathways for different dissociation steps of methylal are presented. Cleavage of a hydrogen bond to the methoxy group or the central carbon atom were simulated at the BLYP/6-311++G{sup **} level of theory. The results are compared to the experiment when dissociating and/or ionising DMM with femtosecond pulses. (author) 1 fig., 1 tab., 1 ref.

  7. Ground-state energy and entropy of the two-dimensional Edwards-Anderson spin-glass model with different bond distributions

    Science.gov (United States)

    Perez-Morelo, D. J.; Ramirez-Pastor, A. J.; Romá, F.

    2012-02-01

    We study the two-dimensional Edwards-Anderson spin-glass model using a parallel tempering Monte Carlo algorithm. The ground-state energy and entropy are calculated for different bond distributions. In particular, the entropy is obtained by using a thermodynamic integration technique and an appropriate reference state, which is determined with the method of high-temperature expansion. This strategy provides accurate values of this quantity for finite-size lattices. By extrapolating to the thermodynamic limit, the ground-state energy and entropy of the different versions of the spin-glass model are determined.

  8. A computational study on structure, stability and bonding in Noble Gas bound metal Nitrates, Sulfates and Carbonates (Metal = Cu, Ag, Au)

    Indian Academy of Sciences (India)

    MANAS GHARA; SUDIP PAN; JYOTIRMOY DEB; ANAND KUMAR; UTPAL SARKAR; PRATIM KUMAR CHATTARAJ

    2016-10-01

    A density functional theory based study is performed to investigate the noble gas (Ng = Ar-Rn) binding ability of nitrates, sulfates and carbonates of noble metal (M). Their ability to bind Ng atoms is assessed through bond dissociation energy and thermochemical parameters like dissociation enthalpy and dissociation free energy change corresponding to the dissociation of Ng bound compound producing Ngand the respective salt. The zero-point energy corrected dissociation energy values per Ng atom for the dissociation process producing Ng atom(s) and the corresponding salts range within 6.0–13.1 kcal/mol in NgCuNO₃, 3.1–9.8 kcal/mol in NgAgNO₃, 6.0–13.2 kcal/mol in NgCuSO₄, 3.2–10.1 kcal/mol in NgAgSO₄, 5.1–11.7 kcal/mol in Ng₂Cu₂SO₄, 2.5–8.6 kcal/mol in Ng₂Ag₂SO₂, 8.1–19.9 kcal/mol in Ng₂Au2SO₂, 5.7–12.4 kcal/mol in NgCuCO₃, 2.3–8.0 kcal/mol in Ng₂Ag₂CO₃ and 7.3–18.2 kcal/mol in Ng₂Au₂CO₃, with a gradual increase in moving from Ar to Rn. For a given type of system, the stability of Ng bound analogues follows the order as Au > Cu > Ag. All dissociation processes are endothermic in nature whereas they become endergonic as well in most of the cases of Kr-Rn bound analogues at 298 K. Natural population analysis along with the computation of Wiberg bond indices, and electron density analyses provide insights into the nature of the Ng-M bonds. The Ng-M bonds can be represented as partial covalent bonds as supported by the different electron density descriptors.

  9. Subliminal processes, dissociation and the 'I'.

    Science.gov (United States)

    Bob, Petr

    2003-06-01

    The study of unconscious processes leads to the hypothesis of the limit of consciousness, which involves two main kinds of psychic activity. The first represents psychic contents which are subliminal for their low energy, the second subliminal contents which are inaccessible to consciousness because they are dissociated in the subliminal region. Dissociation is a concept introduced by Pierre Janet for splitting consciousness due to traumatic events or during hypnosis. It takes a more general form in Hilgard's neo-dissociation theory of hypnotic phenomena and also in Jung's theory of the collective unconscious. Further generalization links it to the modern findings of explicit and implicit perception, leading to a shift in dissociation from hypothesis to clinical, experimental and theoretical reality. Studies in hypnosis also point to the existence of an integrative psychic entity, that comprises the conscious 'I'. Hilgard called this the hidden observer, and his findings represent empirical confirmation of Jung's term for the Self as mirror 'I', which leads to many important consequences for self-discovery and the meaning of life.

  10. Dissociative Experiences in Psychiatric Inpatients

    Directory of Open Access Journals (Sweden)

    Ali Firoozabadi

    2016-11-01

    Full Text Available Dissociative disorders are conditions that involve disruptions of memory, awareness, identity, or perception. Data collected in diverse geographic locations underline the consistency in clinical symptoms of dissociative disorders. In this cross-sectional descriptive study, prevalence of dissociative experiences has been screened in hospitalized patients in psychiatric wards of Shiraz University of Medical Sciences in Iran. One hundred and sixty patients in two hospitals entered the study. Our tool to screen the prevalence of dissociative experiences was Dissociative Experience Scale (DES. Linear regression analysis shows that gender and age are predictors of high DES scores to some extent while psychiatric disorders are not good predictors. Age, gender and psychiatric disorders are poor predictors (almost 7% of high DES scores in this study (R square=0.69. In this study, patients with Borderline Personality Disorder had higher dissociative experiences based on DES score (Mean: 56.44, followed by Schizophrenic patients (Mean: 28.22 and patients with Bipolar Personality Disorder (Mean: 25.18. This study showed that we might be able to create a new category in psychological disorders based on dissociative experiences. As age, gender and psychological disorders were poor predictors of dissociative experiences, stronger predictors such as positive childhood psychological traumas could be responsible for dissociative disorders.

  11. Effects of high angular momentum on the unimolecular dissociation of CD2CD2OH: theory and comparisons with experiment.

    Science.gov (United States)

    McKown, Benjamin G; Ceriotti, Michele; Womack, Caroline C; Kamarchik, Eugene; Butler, Laurie J; Bowman, Joel M

    2013-10-24

    This paper explores the dynamics of a highly rotationally and vibrationally excited radical, CD2CD2OH. The radical is produced from the 193 nm photodissociation of 2-bromoethanol-d4, so it is imparted with high angular momentum and high vibrational energy and subsequently dissociates to several product channels. This paper focuses on characterizing its angular momentum and modeling its effect on the product channels, including the HOD + vinyl-d3 product channel resulting from a frustrated dissociation of the radical originally en route to OH + ethene-d4 that instead results in D atom abstraction. Our impulsive model of the initial photodissociation shows that, for some cases, upward of 200 au of angular momentum is imparted, which greatly affects the dynamics of the competing product channels. Using a permutationally invariant potential energy surface and quasiclassical trajectories, we simulated the dissociation dynamics of CD2CD2OH and compared these results to those of Kamarchik et al. (J. Phys. Chem. Lett. 2010, 1, 3058-3065), who studied the dynamics of CH2CH2OH with zero angular momentum. We found that the recoil translational energy distribution for radicals that dissociated to OH + C2D4 matched experiment closely only when high angular momentum of the initial radical was explicitly included in the trajectory calculations. Similarly, the rate constant for dissociation changes when rotational energy was added to the vibrational energy in the initial conditions. Lastly, we applied the sketch-map dimensionality reduction technique to analyze mechanistic information leading to the vinyl + water product channel. Projecting the ab initio intrinsic reaction coordinates onto the lower dimensional space identified with sketch map offers new insight into the dynamics when one looks at the simulated trajectories in the lower dimensional space. Further analysis shows that the transition path resembles a frustrated dissociation of the OH + ethene radical adduct, followed

  12. Qgui: A high-throughput interface for automated setup and analysis of free energy calculations and empirical valence bond simulations in biological systems.

    Science.gov (United States)

    Isaksen, Geir Villy; Andberg, Tor Arne Heim; Åqvist, Johan; Brandsdal, Bjørn Olav

    2015-07-01

    Structural information and activity data has increased rapidly for many protein targets during the last decades. In this paper, we present a high-throughput interface (Qgui) for automated free energy and empirical valence bond (EVB) calculations that use molecular dynamics (MD) simulations for conformational sampling. Applications to ligand binding using both the linear interaction energy (LIE) method and the free energy perturbation (FEP) technique are given using the estrogen receptor (ERα) as a model system. Examples of free energy profiles obtained using the EVB method for the rate-limiting step of the enzymatic reaction catalyzed by trypsin are also shown. In addition, we present calculation of high-precision Arrhenius plots to obtain the thermodynamic activation enthalpy and entropy with Qgui from running a large number of EVB simulations.

  13. Experimental and computational investigation of the group 11-group 2 diatomic molecules: First determination of the AuSr and AuBa bond energies and thermodynamic stability of the copper- and silver-alkaline earth species

    Science.gov (United States)

    Ciccioli, A.; Gigli, G.; Lauricella, M.

    2012-05-01

    The dissociation energies of the intermetallic molecules AuSr and AuBa were for the first time determined by the Knudsen effusion mass spectrometry method. The two species were produced in the vapor phase equilibrated with apt mixtures of the constituent elements, and the dissociation equilibria were monitored mass-spectrometrically in the temperature range 1406-1971 K (AuSr) and 1505-1971 K (AuBa). The third-law analysis of the equilibrium data gives the following dissociation energies (D_0°, in kJ/mol): 244.4 ± 4.8 (AuSr) and 273.3 ± 6.3 (AuBa), so completing the series of D_0°s for the AuAE (AE = group 2 element) diatomics. The AuAE species were also studied computationally at the coupled cluster including single, double and perturbative triple excitation [CCSD(T)] level with basis sets of increasing zeta quality, and various complete basis set limit extrapolations were performed to calculate the dissociation energies. Furthermore, the entire series of the heteronuclear diatomic species formed from one group 11 (Cu, Ag) and one group 2 (Be, Mg, Ca, Sr, Ba) metal was studied by DFT with the hybrid meta-GGA TPSSh functional and the def2-QZVPP basis set, selected after screening a number of functional-basis set combinations using the AuAE species as benchmark. Dissociation energies, internuclear distances, vibrational frequencies, and anharmonic constants were determined for the CuAE and AgAE species and their thermal functions evaluated therefrom. On this basis, a thermodynamic evaluation of the formation of these species was carried out under various conditions.

  14. Bond selective chemistry beyond the adiabatic approximation

    Energy Technology Data Exchange (ETDEWEB)

    Butler, L.J. [Univ. of Chicago, IL (United States)

    1993-12-01

    One of the most important challenges in chemistry is to develop predictive ability for the branching between energetically allowed chemical reaction pathways. Such predictive capability, coupled with a fundamental understanding of the important molecular interactions, is essential to the development and utilization of new fuels and the design of efficient combustion processes. Existing transition state and exact quantum theories successfully predict the branching between available product channels for systems in which each reaction coordinate can be adequately described by different paths along a single adiabatic potential energy surface. In particular, unimolecular dissociation following thermal, infrared multiphoton, or overtone excitation in the ground state yields a branching between energetically allowed product channels which can be successfully predicted by the application of statistical theories, i.e. the weakest bond breaks. (The predictions are particularly good for competing reactions in which when there is no saddle point along the reaction coordinates, as in simple bond fission reactions.) The predicted lack of bond selectivity results from the assumption of rapid internal vibrational energy redistribution and the implicit use of a single adiabatic Born-Oppenheimer potential energy surface for the reaction. However, the adiabatic approximation is not valid for the reaction of a wide variety of energetic materials and organic fuels; coupling between the electronic states of the reacting species play a a key role in determining the selectivity of the chemical reactions induced. The work described below investigated the central role played by coupling between electronic states in polyatomic molecules in determining the selective branching between energetically allowed fragmentation pathways in two key systems.

  15. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  16. Communication: Enhanced dissociative chemisorption of CO2 via vibrational excitation

    Science.gov (United States)

    Jiang, Bin; Guo, Hua

    2016-03-01

    A fully coupled global nine-dimensional potential energy surface for the dissociative chemisorption of CO2 on Ni(100) is constructed from ˜18 000 density functional points. It reveals a complex reaction pathway dominated by two near iso-energetic transition states. The dissociation probabilities obtained by quasi-classical trajectories on the potential energy surface reproduced experimental trends, and indicate that vibrational excitations of CO2 significantly promote the dissociation. Using the sudden vector projection model, the behavior of the reactivity is rationalized by couplings with the reaction coordinate at each transition state. These results offer plausible rationalization for the observed enhancement of CO2 dissociation in non-thermal plasmas by metal surfaces.

  17. Empty-level structure and reactive species produced by dissociative electron attachment to tert-butyl peroxybenzoate.

    Science.gov (United States)

    Modelli, Alberto; Pshenichnyuk, Stanislav A

    2012-04-12

    The energy and nature of the gas-phase temporary anion states of tert-butylperoxybenzoate in the 0-6 eV energy range are determined for the first time by means of electron transmission spectroscopy (ETS) and appropriate theoretical calculations. The first anion state, associated with electron capture into a delocalized π* MO with mainly ring and carbonyl character, is found to lie close to zero energy, i.e., sizably more stable (about 2 eV) than the ground (σ*) anion state of saturated peroxides. Dissociative decay channels of the unstable parent molecular anions are detected with dissociative attachment spectroscopy (DEAS), as a function of the incident electron energy, in the 0-14 eV energy range. A large DEA cross-section, with maxima at zero energy, 0.7 and 1.3 eV, is found for production of the (m/e = 121) PhCOO(-) anion fragment, together with the corresponding tert-butoxy neutral radical, following cleavage of the O-O bond. Although with much smaller intensities, a variety of other negative currents are observed and assigned to the corresponding anion fragments with the support of density functional theory calculations.

  18. VB studies on bonding features of HNCHCN

    Institute of Scientific and Technical Information of China (English)

    LIAO; Xinli(

    2003-01-01

    [1]Skurski, P., Gutowski, M., Simons, J., Ab initio electronic structure of HCN- and HNC-dipole-bound anions and a description of electron loss upon tautomerization, J. Chem. Phys., 2001, 114(17): 7443-7449.[2]Jursic, B. S., Complete basis set ab initio study of potential energy surfaces of the dissociation recombination reaction HCNH++e(-), J. Mol. Struct., 1999, 487(3): 211-220.[3]Abashkin, Y., Russo, N., Toscano, M., Transition states and energy barriers from density functional studies: representative isomerization reactions, Int. J. Quantum Chem., 1994, 52: 695-704.[4]Bentley, J. A., Bowman, J. M., Gazdy, B. et al., A global ab initio potential for HCN/HNC exact vibrational energies and comparision to experiment, Chem. Phys. Lett., 1992, 198(6): 563-569.[5]Bentley, J. A., Huang, C. M., Wyatt, R. E., Highly vibrationally excited HCN/HNC: eigenvalues, wave functions, and stimulated emission pumping spectra, J. Chem. Phys., 1992, 98(7): 5207-5221.[6]Peric, M., Mladrenovic, M., Peyerimhoff, S. D. et al., Ab initio study of the isomerization HNC-HCN, 1. Ab initio calculation of the HNV reversible HCN potential surface and the corresponding energy-levels, Chem. Phys., 1983, 82: 317-336.[7]Zhang, Q. E., Li, X. Z., Bonded tableau method for many-electron systems, J. Mol. Struct. (Theochem.), 1989, 198: 413-425.[8]Li, X. Z., Zhang, Q. E., Bonded tableau unitary group approach to the many-electron correlation problem, Int. J. Quantum Chem., 1989, 36: 599-632.[9]Li, J. B., Wu, W., New algorithm for nonorthogonal ab initio valence-bond calculations, Theor. Chim. Acta, 1994, 89: 105-121.[10]Wu, W., Mo, Y. R., Zhang, Q. E., On the resonance theory, J. Mol. Struct., 1993, 283: 227-236.[11]Mo, Y. R., Wu, W., Zhang, Q. E., Valence bond description for the ground state and several low-lying excited states of LiH, J. Mol. Struct., 1993, 283: 237-249.[12]Pauling, L., The Nature of Chemical Bond, 3rd ed., Ithaca, New York: Cornell

  19. STUDY ON PHYSICAL CONNOTATION OF AVERAGE BOND ENERGY Em%平均键能Em的物理内涵探讨

    Institute of Scientific and Technical Information of China (English)

    王仁智; 郑永梅; 李书平

    2001-01-01

    在面心立方(fcc)、体心立方(bcc)和六角密堆积(hcp)3种不同结构晶体的自由电子能带模型中,发现4个最低能带与5个次低能带本征值的平均能量(称为平均键能,Em)与费米能级(EF)相当接近;并进一步在hcp结构的钛(Ti)、锆(Zr)和铪(Hf)以及bcc结构的铁(Fe)等金属中,采用从头赝势能带计算方法和平均键能计算方法,证实在这些金属的实际能带中,平均键能(Em)值仍然非常接近于费米能级(EF)值.该发现有助于进一步了解平均键能(Em)的物理内涵.%In free electron band model of three different crystal structures,face-centered cubic (fcc),body-centered cubic (bcc),and hexagonal close-packed (hcp) structures,we fine that the average energy of the four lowest band eigenvalues and the five sub-low band eigenvalues (called as average bond energy Em) is rather close to Fermi level EF.Meanwhile,we also confirm that this conclusion still holds for the practical band in some metals,such as Ti,Zr and Hf with hcp structure as well as Fe with bcc structure etc.,using ab initio pseudopotential and average bond energy methods.Thereby one can further understand the physical connotation of average bond energy Em.

  20. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  1. DFT Study of H2 Dissociation on MoxSy Clusters

    Institute of Scientific and Technical Information of China (English)

    Wang Wei; Zhao Xiaoguang; Li Huifeng; Zhou Han; Li Mingfeng

    2015-01-01

    A DFT study of H2 dissociation on a series of MoxSy clusters was performed, including homolytic and heterolytic dissociation. The preference for the two pathways on these models show much difference, as the Mo coordination number increases, the homolytic dissociation becomes easier, whereas the heterolytic dissociation becomes more dififcult. Further-more, frontier orbital theory was used to analyze the dissociation mechanisms of these two pathways. It was found that the symmetry and energy gap of MoxSy’s HOMO and H2’s LUMO are the decisive factors in H2 activation.

  2. High energy efficiency in syngas and hydrocarbon production from dissociation of CH{sub 4}-CO{sub 2} mixture in a non-equilibrium pulsed plasma

    Energy Technology Data Exchange (ETDEWEB)

    Ghorbanzadeh, A M; Norouzi, S; Mohammadi, T [Department of Physics, Sharif University of Technology, PO Box 11365-9161, Tehran (Iran, Islamic Republic of)

    2005-10-21

    The efficient production of syngas from a CH{sub 4}+CO{sub 2} mixture in an atmospheric pulsed glow discharge, sustained by corona pre-ionization, has been investigated. The products were mainly syngas (CO, H{sub 2}) and hydrocarbons up to C{sub 4}, with acetylene having the highest selectivity. The energy efficiency was within 15-40% for different experimental conditions, which demonstrates a comprehensive improvement relative to the achievements of other types of non-equilibrium plasma. These values are, however, comparable with the efficiencies obtained by gliding arc plasmas but this plasma operates at near room temperature. Furthermore, it has been shown that the energy efficiency is increased by decreasing the effective residence time. The effects of molar ratio CH{sub 4} : CO{sub 2}, voltage, repetition rate and gas flow rate on conversion, energy efficiencies and the selectivities have also been investigated. The higher efficiency obtained in this kind of plasma is discussed and attributed to the short pulse regime and electric field uniformity.

  3. Trajectory dynamics study of the Ar + CH4 dissociation reaction at high temperatures: the importance of zero-point-energy effects.

    Science.gov (United States)

    Marques, J M C; Martínez-Núñez, E; Fernandez-Ramos, A; Vazquez, S A

    2005-06-23

    Large-scale classical trajectory calculations have been performed to study the reaction Ar + CH4--> CH3 +H + Ar in the temperature range 2500 energy surface used for ArCH4 is the sum of the nonbonding pairwise potentials of Hase and collaborators (J. Chem. Phys. 2001, 114, 535) that models the intermolecular interaction and the CH4 intramolecular potential of Duchovic et al. (J. Phys. Chem. 1984, 88, 1339), which has been modified to account for the H-H repulsion at small bending angles. The thermal rate coefficient has been calculated, and the zero-point energy (ZPE) of the CH3 product molecule has been taken into account in the analysis of the results; also, two approaches have been applied for discarding predissociative trajectories. In both cases, good agreement is observed between the experimental and trajectory results after imposing the ZPE of CH3. The energy-transfer parameters have also been obtained from trajectory calculations and compared with available values estimated from experiment using the master equation formalism; in general, the agreement is good.

  4. Hydrolyzable polyureas bearing hindered urea bonds.

    Science.gov (United States)

    Ying, Hanze; Cheng, Jianjun

    2014-12-10

    Hydrolyzable polymers are widely used materials that have found numerous applications in biomedical, agricultural, plastic, and packaging industrials. They usually contain ester and other hydrolyzable bonds, such as anhydride, acetal, ketal, or imine, in their backbone structures. Here, we report the first design of hydrolyzable polyureas bearing dynamic hindered urea bonds (HUBs) that can reversibly dissociate to bulky amines and isocyanates, the latter of which can be further hydrolyzed by water, driving the equilibrium to facilitate the degradation of polyureas. Polyureas bearing 1-tert-butyl-1-ethylurea bonds that show high dynamicity (high bond dissociation rate), in the form of either linear polymers or cross-linked gels, can be completely degraded by water under mild conditions. Given the simplicity and low cost for the production of polyureas by simply mixing multifunctional bulky amines and isocyanates, the versatility of the structures, and the tunability of the degradation profiles of HUB-bearing polyureas, these materials are potentially of very broad applications.

  5. On the structure and bonding of first row transition metal ozone carbonyl hydrides.

    Science.gov (United States)

    Venter, Gerhard A; Raubenheimer, Helgard G; Dillen, Jan

    2007-08-23

    Model complexes of the general form M(CO)m(H)n(O3) (m = 1-5, n = 0 or 1) between ozone and the transition metals Ti to Cu were studied by density functional theory (DFT) calculations. The CDA charge decomposition method was used to analyze the interaction between the metal atom and the ozone ligand in terms of the traditional donation-back-donation mechanisms. Information about bond strengths was extracted from an analysis of the electron density in terms of the theory of atoms in molecules (AIM). The bonding in the ozone-metal complex was also studied within the NBO paradigm. Bond dissociation energies were calculated to be positive for all the complexes studied. Considering all the criteria employed in this study to analyze the interaction between the ozone and the transition metal, the Fe-complex is predicted to be the most stable, whereas the copper complex has the weakest metal-ozone interaction.

  6. Mechanisms for O2 dissociation over the BaO (100) surface

    Science.gov (United States)

    Lu, Nai-Xia; Fu, Gang; Xu, Xin; Wan, Hui-Lin

    2008-01-01

    We have investigated the atomic and molecular oxygen adsorptions on the various sites of the BaO (100) surface with both cluster models and the periodic slab models. We found that the atomic oxygen prefers to adsorb on the surface O2- to form the closed-shell peroxides with the binding energies of 83-88kcal/mol. Such a high exothermicity provides a large driving force for the dissociation of molecular O2 on the BaO surfaces. As molecular oxygen approaches the BaO surfaces, the triplet ground state O2 molecule first binds electrostatically on top of the surface Ba2+ site. It further quenches to the singlet potential energy surface to form a covalently bonded O32- species. We proposed a plausible pathway in which the O32- species acts as the key precursor for further dissociation, leading eventually to the formation of surface peroxides O22-. This mechanism is helpful for the understanding of a series of related catalytic processes such as the oxidative coupling of methane, the NOx storage reduction, etc.

  7. The origin of unequal bond lengths in the $\\mathrm{\\tilde{C}}$ $^1$B$_2$ state of SO$_2$: Signatures of high-lying potential energy surface crossings in the low-lying vibrational structure

    CERN Document Server

    Park, G Barratt; Field, Robert W

    2016-01-01

    The $\\mathrm{\\tilde{C}}$ $^1$B$_2$ state of SO$_2$ has a double-minimum potential in the antisymmetric stretch coordinate, such that the minimum energy geometry has nonequivalent SO bond lengths. The asymmetry in the potential energy surface is expressed as a staggering in the energy levels of the $\

  8. Coordination-resolved local bond strain and 3p energy entrapment of K atomic clusters and K(1 1 0) skin

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ting; Bo, Maolin; Guo, Yongling [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Chen, Hefeng [United Superconductive Institution, Shanghai Jiaotong University, Shanghai 200240 (China); Wang, Yan [School of Information and Electronic Engineering, Hunan University of Science and Technology, Hunan 411201 (China); Huang, Yongli, E-mail: huangyongli@xtu.edu.cn [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Sun, Chang Q., E-mail: ecqsun@ntu.edu.sg [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); School of Information and Electronic Engineering, Hunan University of Science and Technology, Hunan 411201 (China); NOVITAS, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore)

    2015-09-15

    Graphical abstract: - Highlights: • Coordination environment resolves electron binding-energy shift of K{sub 44}, K{sub 46}, K{sub 55} clusters. • Predict the effective coordination number of K nanoclusters when we get the atomic number N. • Atomic under coordination shortens the local bonds and entrapment. • XPS derives core level of an isolated atom and its bulk shift. - Abstract: We have examined the atomic coordination effect on the local bond strain and the 3p core-level shift of K(1 1 0) skin and nanoclusters using a combination of the bond order–length–strength correlation notion, tight-binding approach, density functional theory calculations, and photoelectron spectroscopy measurements. It turns out that: (i) the 3p core-level shifts from 15.595 ± 0.003 eV for an isolated K atom by 2.758 eV to the bulk value of 18.353 eV; (ii) the effective atomic coordination number reduces from the bulk value of 12 to 3.93 for the first layer and to 5.81 for the second layer of K(1 1 0) skin associated with the local lattice strain of 12.76%, a binding energy density 72.67%, and atomic cohesive energy −62.46% for the skin; and (iii) K cluster size reduction lowers the effective atomic coordination number and enhances further the skin electronic attribution. Results have revealed that the 3p core-level shifts of K(1 1 0) and nanoclusters originate from perturbation of the Hamiltonian by under-coordination induced charge densification and quantum entrapment.

  9. The Effect of Energy Densities on the Shear Bond Strength of Self-Adhering Flowable Composite to Er:YAG Pretreated Dentin

    Science.gov (United States)

    Corbani, Karim

    2016-01-01

    Objective. To investigate the shear bond strength of self-adhering flowable resin composite, to dentin, after exposing it to Er:YAG laser radiation, at different energy densities. Materials and Methods. Sixty freshly extracted human third molars were randomly divided into five groups (n = 12). In the control group, dentin was left unirradiated, whereas, in the other four groups, dentin was irradiated with Er:YAG laser in noncontact mode (MSP mode = 100 µs; 10 Hz; beam diameter: 1.3 mm; speed of 1 mm/second; air 6 mL/min; and water 4 mL/min), and respectively, with the following level of energy (50 mJ, 60 mJ, 80 mJ, and 100 mJ). Then, self-adhering flowable resin composite was bonded to all prepared dentin surfaces. Shear bond strength (SBS) was applied and fractured surfaces were examined using scanning electron microscopy. Results. SBS values showed significant differences in 60 mJ (P < 0.05) compared to other groups. Morphological evaluation revealed tags or plugs in dentinal tubules, especially when 60 mJ and 80 mJ were used. All four groups tended to leave more residues on the dentin surface, than the control group. Conclusion. Er:YAG dentin irradiation may enhance SBS of the self-adhering flowable resin composite when it is used at the appropriate low level of energy density. PMID:27830151

  10. The Effect of Energy Densities on the Shear Bond Strength of Self-Adhering Flowable Composite to Er:YAG Pretreated Dentin

    Directory of Open Access Journals (Sweden)

    Paul Nahas

    2016-01-01

    Full Text Available Objective. To investigate the shear bond strength of self-adhering flowable resin composite, to dentin, after exposing it to Er:YAG laser radiation, at different energy densities. Materials and Methods. Sixty freshly extracted human third molars were randomly divided into five groups (n=12. In the control group, dentin was left unirradiated, whereas, in the other four groups, dentin was irradiated with Er:YAG laser in noncontact mode (MSP mode = 100 µs; 10 Hz; beam diameter: 1.3 mm; speed of 1 mm/second; air 6 mL/min; and water 4 mL/min, and respectively, with the following level of energy (50 mJ, 60 mJ, 80 mJ, and 100 mJ. Then, self-adhering flowable resin composite was bonded to all prepared dentin surfaces. Shear bond strength (SBS was applied and fractured surfaces were examined using scanning electron microscopy. Results. SBS values showed significant differences in 60 mJ (P<0.05 compared to other groups. Morphological evaluation revealed tags or plugs in dentinal tubules, especially when 60 mJ and 80 mJ were used. All four groups tended to leave more residues on the dentin surface, than the control group. Conclusion. Er:YAG dentin irradiation may enhance SBS of the self-adhering flowable resin composite when it is used at the appropriate low level of energy density.

  11. Quantum chemical study of mechanisms of dissociation and isomerization reactions in some molecules and radicals of astrophysical significance: Cyanides and related molecules

    Indian Academy of Sciences (India)

    V P Gupta; Archina Sharma

    2006-09-01

    A theoretical study of the mechanism of photodecomposition in carbonyl cyanide, diethynyl ketone, acetyl cyanide and formyl cyanide has been conducted using density functional and MP2 theories. A complete analysis of the electronic spectra of these molecules in terms of nature, energy and intensity of electronic transitions has been provided by time-dependent density functional theory. Mixing coefficients and main configurations of the electronic states have been used to identify the states leading to the photodecomposition process. While the Rydberg state 1(n,3s) is involved in the dissociation of formyl cyanide and acetyl cyanide, the $^{*}_{CC} / ^{*}_{CN}$ states are involved in the case of carbonyl cyanide and diethynyl ketone. In all cases, however, stepwise decomposition process is preferred over the concerted reaction process. Based on potential energy curves for bond dissociation and the transition state and IRC studies, it is found that besides the direct dissociation of carbonyl cyanide, a photoisomerization process through a non-planar transition state may also occur resulting in the formation of a stable and planar isomer CNC(O)CN. A complete vibrational analysis of the higher energy isomer has been conducted and several new fundamental bands are predicted. Some of the earlier experimental results on the photodecomposition mechanism and energies of photofragments in carbonyl cyanide and acetyl cyanide have also been rationalized.

  12. Alkali Metal-Glucose Interaction Probed with Infrared Pre-Dissociation Spectroscopy

    Science.gov (United States)

    Kregel, Steven J.; Marsh, Brett; Zhou, Jia; Garand, Etienne

    2015-06-01

    The efficient extraction of cellulose from biomass and its subsequent conversion to glucose derivatives is an attractive goal in the field of energy science. However, current industrial methods require high ionic strength and harsh conditions. Ionic liquids (IL's) are a class of "green" compounds that have been shown to dissolve cellulose in concentrations of up to 25 wt%. In order to understand IL's extraordinary cellulose dissolving power, a molecular level understanding of the IL-cellulose interaction is needed. Toward that end, we have acquired infrared pre-dissociation spectra of M+-glucose, where M+=Li+, Na+, or K+. Through comparisons with density functional theory calculations, we have determined the relative abundances of various M+-glucose binding motifs in both the thermodynamic and kinetic limits. These results provide insight on the hydrogen bonding dynamics of glucose and are a step towards a fuller understanding of cellulose interactions with ionic liquids.

  13. Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Andrew J.; Iglesia, Enrique

    2014-11-03

    Mechanistic interpretations of rates and in situ IR spectra combined with density functionals that account for van der Waals interactions of intermediates and transition states within confining voids show that associative routes mediate the formation of dimethyl ether from methanol on zeolitic acids at the temperatures and pressures of practical dehydration catalysis. Methoxy-mediated dissociative routes become prevalent at higher temperatures and lower pressures, because they involve smaller transition states with higher enthalpy, but also higher entropy, than those in associative routes. These enthalpy–entropy trade-offs merely reflect the intervening role of temperature in activation free energies and the prevalence of more complex transition states at low temperatures and high pressures. This work provides a foundation for further inquiry into the contributions of H-bonded methanol and methoxy species in homologation and hydrocarbon synthesis reactions from methanol.

  14. Kinetic, spectroscopic, and theoretical assessment of associative and dissociative methanol dehydration routes in zeolites.

    Science.gov (United States)

    Jones, Andrew J; Iglesia, Enrique

    2014-11-01

    Mechanistic interpretations of rates and in situ IR spectra combined with density functionals that account for van der Waals interactions of intermediates and transition states within confining voids show that associative routes mediate the formation of dimethyl ether from methanol on zeolitic acids at the temperatures and pressures of practical dehydration catalysis. Methoxy-mediated dissociative routes become prevalent at higher temperatures and lower pressures, because they involve smaller transition states with higher enthalpy, but also higher entropy, than those in associative routes. These enthalpy-entropy trade-offs merely reflect the intervening role of temperature in activation free energies and the prevalence of more complex transition states at low temperatures and high pressures. This work provides a foundation for further inquiry into the contributions of H-bonded methanol and methoxy species in homologation and hydrocarbon synthesis reactions from methanol.

  15. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  16. CO dissociation on magnetic Fen clusters

    KAUST Repository

    Jedidi, Abdesslem

    2014-01-01

    This work theoretically investigates the CO dissociation on Fen nanoparticles, for n in the range of 1-65, focusing on size dependence in the context of the initial step of the Fischer-Tropsch reaction. CO adsorbs molecularly through its C-end on a triangular facet of the nanoparticle. Dissociation becomes easier when the cluster size increases. Then, the C atom is bonded to a square facet that is generated as a result of the adsorption if it does not yet exist in the bare cluster, while the O atom is adsorbed on a triangular facet. In the most stable situation, the two adsorbed atoms remain close together, both having in common one shared first-neighbor iron atom. There is a partial spin quenching of the neighboring Fe atoms, which become more positively charged than the other Fe atoms. The shared surface iron atom resembles a metal-cation from a complex. Despite the small size of the iron cluster considered, fluctuations due to specific configurations do not influence properties for n > 25 and global trends seem significant.

  17. Chemical bonding in transition metal complexes with beryllium ligands [(PMe(3))(2)M-BeCl(2)], [(PMe(3))(2)M-BeClMe], and [(PMe(3))(2)M-BeMe(2)] (M = Ni, Pd, Pt).

    Science.gov (United States)

    Parameswaran, Pattiyil; Frenking, Gernot

    2010-08-26

    The equilibrium geometries and bond dissociation energies of the 14 valence electron (VE) complexes [(PMe(3))(2)M-BeCl(2)], [(PMe(3))(2)M-BeClMe], and [(PMe(3))(2)M-BeMe(2)] with M = Ni, Pd, and Pt have been calculated using density functional theory at the BP86/TZ2P level. The nature of the M-Be bond was analyzed with the NBO charge decomposition analysis and the EDA energy decomposition analysis. The theoretical results predict the equilibrium structures with a T-shaped geometry at the transition metal where the PMe(3) ligands are in the axial positions. The calculated bond dissociation energies show that the M-E bond strengths are in the range of donor-acceptor complexes of divalent beryllium compounds with ammonia. The bond strength decreases when the substituent at beryllium changes from Cl to CH(3). The NBO analysis shows a negative charge at the BeX(2) fragment, which indicates a net charge flow from the transition metal fragment to the beryllium fragment. The energy decomposition analysis of the M-Be bonds suggests two donor-acceptor bonds with sigma and pi symmetry where the transition metal fragment is a double donor with respect to the beryllium ligand. The pi component of the [Ni]-->BeXX' donation is much smaller than the sigma component.

  18. Dissociation and reconstruction of double-decker bis(phthalocyaninato) terbium(III) complex (TbPc2) on Pd(001): A theoretical investigation

    Science.gov (United States)

    Liu, Heng; Hu, Yujie; Wang, Hao; Jiang, Bo; Xu, Xuechun; Cai, Yingxiang

    2017-01-01

    The study of molecule dissociation is helpful to disclose the nature of chemical bonds and to extend molecular functions. The double-decker bis(phthalocyaninato) terbium(III) complex (TbPc2) is a promising single-molecule magnet (SMM) which exhibits potential applications in spin-devices. In this study, we investigate the dissociation and reconstruction of TbPc2 on Pd(001) surface. The results show that a single TbPc2 adsorbed on Pd(001) tends to split into Pc/Pd(001)+TbPc. However, the TbPc/Pd(001)+Pc might also be observed in an experimental study due to only a slight difference in their dissociation energy. The TbPc2 molecules on Pd(001) will form a (5×3) reconstruction which is different from the (3×4) reconstruction of PbPc on Pd(001). If the TbPc2 molecules with (5×3) reconstruction is dissociated, this reconstruction will be inherited by its daughter molecules due to strong molecule-substrate interaction. In addition, nudged elastic band (NEB) calculation shows that Tb-down is the stable state of TbPc/Pd(001) and Tb-up is a metastable state. The transition between two states might be utilized to realize TbPc's switch or storage functions.

  19. Dissociation path for H2 on Al(110)

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Jacobsen, Karsten Wedel; Nørskov, Jens Kehlet

    1992-01-01

    The minimum energy path is calculated for an H2 molecule dissociating on an Al(110) surface within local density functional theory. The properties of the potential energy surface along the five H2 ionic coordinates perpendicular to the reaction path are also determined and shown to be essential...

  20. Theoretical Analysis of the Effect of C═C Double Bonds on the Low-Temperature Reactivity of Alkenylperoxy Radicals.

    Science.gov (United States)

    You, Xiaoqing; Chi, Yawei; He, Tanjin

    2016-08-04

    Biodiesel contains a large proportion of unsaturated fatty acid methyl esters. Its combustion characteristics, especially its ignition behavior at low temperatures, have been greatly affected by these C═C double bonds. In this work, we performed a theoretical analysis of the effect of C═C double bonds on the low-temperature reactivity of alkenylperoxy radicals, the key intermediates from the low-temperature combustion of biodiesel. To understand how double bonds affect the fate of peroxy radicals, we selected three representative peroxy radicals from heptane, heptene, and heptadiene having zero, one, and two double C═C bonds, respectively, for study. The potential energy surfaces were explored at the CBS-QB3 level, and the reaction rate constants were computed using canonical/variational transition state theories. We have found that the double bond is responsible for the very different bond dissociation energies of the various types of C-H bonds, which in turn affect significantly the reaction kinetics of alkenylperoxy radicals.

  1. Dissociative and non-dissociative photoionization of molecular fluorine from inner and valence shells

    Energy Technology Data Exchange (ETDEWEB)

    Ayuso, D.; Palacios, A. [Departamento de Química, Módulo 13, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Decleva, P. [Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste, 34127 Trieste (Italy); CNR-IOM, Trieste (Italy); Martín, F., E-mail: fernando.martin@uam.es [Departamento de Química, Módulo 13, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Instituto Madrileño de Estudios Avanzados en Nanociencia, Cantoblanco, 28049 Madrid (Spain)

    2014-08-15

    Highlights: • We theoretically analyze the angle-integrated photoionization cross sections of the fluorine molecule, which have been computed up to hundreds of eV using a DFT-like methodology that takes into account the nuclear degrees of freedom. • We have considered electron ejection from all the molecular orbitals and found that the corresponding cross sections show an oscillatory behavior as a function of the photoelectron momentum, which is the result of the double-slit type interferences. • We further compute dissociative and non-dissociative ionization channels. • Dissociative ionization is negligible in other diatomic molecules such N{sub 2} or CO, whereas is visible for F{sub 2} when the electron is ejected from the 1u or the 3σ{sub g} molecular orbitals. - Abstract: We present a theoretical study of F{sub 2} photoionization in the range 0–40 a.u. of photoelectron energy, where the undulatory behavior of the corresponding angle-integrated cross sections due to electron emission from equivalent centers is apparent. These double-slit type interferences are observed in both inner- and valence-shell ionization. We analyze confinement effects that appear at given energies when the electron is ejected parallel to the molecular axis. Since we account for the nuclear degrees of freedom, we evaluate and discuss the vibrationally resolved cross sections, including both dissociative and non-dissociative ionization channels. We also analyze the ratios between the latter cross sections and the relationship between the observed oscillations and the structure of the molecule.

  2. Investigation of the energy barrier to the rotation of amide CN bonds in ACE inhibitors by NMR, dynamic HPLC and DFT.

    Science.gov (United States)

    Bouabdallah, S; Ben Dhia, M T; Driss, M R; Touil, S

    2016-09-01

    The isomerizations of Enalapril, Perindopril, Enalaprilat and Lisinopril have been investigated using NMR spectroscopic, dynamic chromatographic, unified equation and DFT theoretical calculations. The thermodynamic parameters (ΔH, ΔS and ΔG) were determined by varying the temperature in the NMR experiments. At the coalescence temperature, we can evaluate the isomerization barrier to the rotation (ΔG(≠)) around the amide bond. Using dynamics chromatography and an unified equation introduced by Trap, we can determine isomerization rate constants and Gibbs activation energies. Molecular mechanics calculations also provided evidence for the presence of low energy conformers for the ACE due to restricted amide rotation. With the value of barriers (ΔE) between them of the order of (20kJmol(-1)), which is in agreement with the dynamic NMR results and DFT calculations.

  3. Hydrogen Bonding in Thermoplastic Polyurethane Elastomers: IR Thermal Analysis

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The hydrogen bond percentage and its temperature dependence of the three TPU samples synthesized from polytetrahydrofuran, 4,4-diphenylmethane diisocyanate, N-methyl diethanol amine or 1,4-butane diol were studied by means of IR thermal analysis. The enthalpy and the entropy of the hydrogen bond dissociation were determined by the Vant Hoff plot.

  4. Bond-selective fragmentation of water molecules with intense, ultrafast, carrier envelope phase stabilized laser pulses

    CERN Document Server

    Mathur, D; Dharmadhikari, J A; Dharmadhikari, A K

    2013-01-01

    Carrier envelope phase (CEP) stabilized pulses of intense 800 nm light of 5 fs duration are used to probe the dissociation dynamics of dications of isotopically-substituted water, HOD. HOD$^{2+}$ dissociates into either H$^+$ + OD$^+$ or D$^+$ + OH$^+$. The branching ratio for these two channels is CEP-dependent; the OD$^+$/OH$^+$ ratio (relative to that measured with CEP-unstabilized pulses) varies from 150% to over 300% at different CEP values, opening prospects of isotope-dependent control over molecular bond breakage. The kinetic energy released as HOD$^{2+}$ Coulomb explodes is also CEP-dependent. Formidable theoretical challenges are identified for proper insights into the overall dynamics which involve non-adiabatic field ionization from HOD to HOD$^+$ and, thence, to HOD$^{2+}$ via electron rescattering.

  5. Dissociative Disorder Presenting as Catatonia

    OpenAIRE

    Sarkar, P; Patra, B.; Sattar, F.A.; Chatterjee, K.; Gupta, A; Walia, T.S.

    2004-01-01

    Three cases of dissociative disorder presenting with catatonia are described. Catatonia is generally believed to be associated with schizophrenia. However, many other conditions are also known to cause catatonia. A brief review of literature is provided. All the cases improved rapidly with a few ECTs. This report aims to highlight the presentation of dissociative disorders with catatonia. It also seeks to bring to notice the need to avoid lumping all non-organic catatonics under the rubric of...

  6. Experimental bond critical point and local energy density properties determined for Mn-O, Fe-O, and Co-O bonded interactions for tephroite, Mn2SiO4, fayalite, Fe2SiO4, and Co2SiO4 olivine and selected organic metal complexes: comparison with properties calculated for non-transition and transition metal M-O bonded interactions for silicates and oxides.

    Science.gov (United States)

    Gibbs, G V; Downs, R T; Cox, D F; Rosso, K M; Ross, N L; Kirfel, A; Lippmann, T; Morgenroth, W; Crawford, T D

    2008-09-18

    Bond critical point (bcp) and local energy density properties for the electron density (ED) distributions, calculated with first-principle quantum mechanical methods for divalent transition metal Mn-, Co-, and Fe-containing silicates and oxides are compared with experimental model ED properties for tephroite, Mn 2SiO 4, fayalite, Fe 2SiO 4, and Co 2SiO 4 olivine, each determined with high-energy synchrotron single-crystal X-ray diffraction data. Trends between the experimental bond lengths, R(M-O), (M = Mn, Fe, Co), and the calculated bcp properties are comparable with those observed for non-transition M-O bonded interactions. The bcp properties, local total energy density, H( r c), and bond length trends determined for the Mn-O, Co-O, and Fe-O interactions are also comparable. A comparison is also made with model experimental bcp properties determined for several Mn-O, Fe-O, and Co-O bonded interactions for selected organometallic complexes and several oxides. Despite the complexities of the structures of the organometallic complexes, the agreement between the calculated and model experimental bcp properties is fair to good in several cases. The G( r c)/rho( r c) versus R(M-O) trends established for non-transition metal M-O bonded interactions hold for the transition metal M-O bonded interactions with G( r c)/rho( r c) increasing in value as H( r c) becomes progressively more negative in value, indicating an increasing shared character of the interaction as G( r c)/rho( r c) increases in value. As observed for the non-transition metal M-O bonded interactions, the Laplacian, nabla (2)rho( r c), increases in value as rho( r c) increases and as H( r c) decreases and becomes progressive more negative in value. The Mn-O, Fe-O, and Co-O bonded interactions are indicated to be of intermediate character with a substantial component of closed-shell character compared with Fe-S and Ni-S bonded interactions, which show greater shared character based on the | V( r c)|/ G( r c

  7. Reaction heats and bond strengths based on a series of lectures given to postgraduate students at the University of Keele, 1960

    CERN Document Server

    Mortimer, C T

    1962-01-01

    Reaction Heats and Bond Strengths presents the variations in the heats of particular types of reaction. This book covers a variety of topics, including the hydrogenation and polymerization of olefinic compounds, the dissociation of organic and organo-metallic compounds, and the molecular-addition compounds. Organized into 10 chapters, this book begins with an overview of the concept of bond energy that can be very useful where a comparison is being made between two dissimilar molecules. This text then examines the strain in cyclopropane and cyclobutane, which is largely a result of angular str

  8. Mechatronic modeling of a 750kW fixed-speed wind energy conversion system using the Bond Graph Approach.

    Science.gov (United States)

    Khaouch, Zakaria; Zekraoui, Mustapha; Bengourram, Jamaa; Kouider, Nourreeddine; Mabrouki, Mustapha

    2016-11-01

    In this paper, we would like to focus on modeling main parts of the wind turbines (blades, gearbox, tower, generator and pitching system) from a mechatronics viewpoint using the Bond-Graph Approach (BGA). Then, these parts are combined together in order to simulate the complete system. Moreover, the real dynamic behavior of the wind turbine is taken into account and with the new model; final load simulation is more realistic offering benefits and reliable system performance. This model can be used to develop control algorithms to reduce fatigue loads and enhance power production. Different simulations are carried-out in order to validate the proposed wind turbine model, using real data provided in the open literature (blade profile and gearbox parameters for a 750 kW wind turbine).

  9. Investigation of intense femto-second laser ionization and dissociation of methane with time-dependent density-functional approach

    Science.gov (United States)

    Irani, E.; Sadighi-Bonabi, R.; Anvari, A.

    2014-06-01

    Three dimensional calculations of electronic dynamics of CH4 in a strong laser field are presented with time-dependent density-functional theory. Time evolution of dipole moment and electron localization function is presented. The dependence of dissociation rate on the laser characters is shown and optimal effective parameters are evaluated. The optimum field leads to 76% dissociation probability for GAUSSIAN envelope and 40 fs (FWHM) at 1016 W cm-2. The dissociation probability is calculated by optimum convolution of dual short pulses. By combining of field assisted dissociation process and Ehrenfest molecular dynamics, time variation of bond length, velocity and orientation effect are investigated.

  10. Dissociation of deuteron, 6He and 11Be from Coulomb dissociation reaction cross-section

    Indian Academy of Sciences (India)

    Ramendra Nath Majumdar

    2008-05-01

    The fragmentation of deuteron, 6He and 11Be have been studied during interaction with the 208Pb nucleus at various projectile energies. The Coulomb dissociation cross-sections and the momentum distribution of the break-up fragments have been analysed within the framework of the direct fragmentation model. The post-acceleration effect of deuteron during break-up and the halo structures of both the 6He and 11Be have been investigated.

  11. CO2 Dissociation using the Versatile Atmospheric Dielectric Barrier Discharge Experiment (VADER

    Directory of Open Access Journals (Sweden)

    Michael Allen Lindon

    2014-09-01

    Full Text Available Dissociation of CO2 is investigated in an atmospheric pressure dielectric barrier discharge (DBD with a simple, zero dimensional (0-D chemical model and through experiment. The model predicts that the primary CO2 dissociation pathway within a DBD is electron impact dissociation and electron-vibrational excitation. The relaxation kinetics following dissociation are dominated by atomic oxygen chemistry. The experiments included investigating the energy efficiencies and dissociation rates of CO2 within a planar DBD, while the gas flow rate, voltage, gas composition, driving frequency, catalyst, and pulse modes were varied. Some of the VADER results include a maximum CO2 dissociation energy efficiency of 2.5 +/- 0.5%, a maximum CO$_2$ dissociation rate of 4 +/- 0.4*10^-6 mol CO2/s (5 +/- 0.5% percent dissociation, discovering that a resonant driving frequency of ~30 kHz, dependent on both applied voltage and breakdown voltage, is best for efficient CO2 dissociation and that TiO2, a photocatalyst, improved dissociation efficiencies by an average of 18% at driving frequencies above 5 kHz.

  12. CO adsorption and dissociation on Pt(111) and Ni(111) surfaces

    DEFF Research Database (Denmark)

    Morikawa, Y.; Mortensen, Jens Jørgen; Hammer, Bjørk

    1997-01-01

    CO adsorption and dissociation processes have been studied using first-principles total energy and force calculations. The adsorption energies, atomic structures and vibrational modes of molecularly chemisorbed states are well reproduced in the present calculations. We have examined several...

  13. Scaling of the critical free length for progressive unfolding of self-bonded graphene

    Energy Technology Data Exchange (ETDEWEB)

    Kwan, Kenny; Cranford, Steven W., E-mail: s.cranford@neu.edu [Laboratory of Nanotechnology in Civil Engineering (NICE), Department of Civil and Environmental Engineering, Northeastern University, 400 Snell Engineering, 360 Huntington Avenue, Boston, Massachusetts 02115 (United States)

    2014-05-19

    Like filled pasta, rolled or folded graphene can form a large nanocapsule surrounding a hollow interior. Use as a molecular carrier, however, requires understanding of the opening of such vessels. Here, we investigate a monolayer sheet of graphene as a theoretical trial platform for such a nanocapsule. The graphene is bonded to itself via aligned disulfide (S-S) bonds. Through theoretical analysis and atomistic modeling, we probe the critical nonbonded length (free length, L{sub crit}) that induces fracture-like progressive unfolding as a function of folding radius (R{sub i}). We show a clear linear scaling relationship between the length and radius, which can be used to determine the necessary bond density to predict mechanical opening/closing. However, stochastic dissipated energy limits any exact elastic formulation, and the required energy far exceeds the dissociation energy of the S-S bond. We account for the necessary dissipated kinetic energy through a simple scaling factor (Ω), which agrees well with computational results.

  14. Dipolar dissociation dynamics in electron collisions with carbon monoxide

    CERN Document Server

    Chakraborty, Dipayan; Nandi, Dhananjay

    2016-01-01

    Dipolar dissociation processes in the electron collisions with carbon monoxide have been studied using time of flight (TOF) mass spectroscopy in combination with the highly differential velocity slice imaging (VSI) technique. Probing ion-pair states both positive and/or negative ions may be detected. The ion yield curve of negative ions provides the threshold energy for the ion-pair production. On the other hand, the kinetic energy distributions and angular distributions of the fragment anion provide detailed dynamics of the dipolar dissociation process. Two ion-pair states have been identified based on angular distribution measurements using VSI technique.

  15. Photogenerated Exciton Dissociation in Highly Coupled Lead Salt Nanocrystal Assemblies

    KAUST Repository

    Choi, Joshua J.

    2010-05-12

    Internanocrystal coupling induced excitons dissociation in lead salt nanocrystal assemblies is investigated. By combining transient photoluminescence spectroscopy, grazing incidence small-angle X-ray scattering, and time-resolved electric force microscopy, we show that excitons can dissociate, without the aid of an external bias or chemical potential gradient, via tunneling through a potential barrier when the coupling energy is comparable to the exciton binding energy. Our results have important implications for the design of nanocrystal-based optoelectronic devices. © 2010 American Chemical Society.

  16. Dissociative experiences and dissociative minds: Exploring a nomological network of dissociative functioning.

    Science.gov (United States)

    Schimmenti, Adriano

    2016-01-01

    In this study, the psychometric properties of the Dissociative Experiences Scale-II (DES-II) were tested in a sample of Italian adults, and a nomological network of dissociative functioning based on current psychodynamic research was examined. A total of 794 participants (55% females) ranging in age from 18 to 64 completed the DES-II and other measures of theory of mind, alexithymia, attachment style, and empathy. The Italian translation of the DES-II showed high internal consistency, adequate item-to-scale homogeneity, and good split-half reliability. A single-factor solution including the 8 items of pathological dissociation (DES-T) adequately fit the data. Participants who reported higher levels of dissociative experiences showed significantly lower scores on theory of mind and empathy than other participants. They also showed significantly higher scores on alexithymia, preoccupied attachment, and fearful attachment. Results of the study support the view that people who suffer from severe dissociative experiences may also have difficulties mentalizing and regulating affects and that they may feel uncomfortable in close relationships because they have a negative view of the self. This can inform clinical work with dissociative individuals, who could benefit from therapies that consider their potential problems with mentalization, empathy, affect regulation, and attachment.

  17. O-H···S hydrogen bonds conform to the acid-base formalism.

    Science.gov (United States)

    Bhattacharyya, Surjendu; Bhattacherjee, Aditi; Shirhatti, Pranav R; Wategaonkar, Sanjay

    2013-08-29

    Hydrogen bonding interaction between the ROH hydrogen bond donor and sulfur atom as an acceptor has not been as well characterized as the O-H···O interaction. The strength of O-H···O interactions for a given donor has been well documented to scale linearly with the proton affinity (PA) of the H-bond acceptor. In this regard, O-H···O interactions conform to the acid-base formalism. The importance of such correlation is to be able to estimate molecular property of the complex from the known thermodynamic data of its constituents. In this work, we investigate the properties of O-H···S interaction in the complexes of the H-bond donor and sulfur containing acceptors of varying proton affinity. The hydrogen bonded complexes of p-Fluorophenol (FP) with four different sulfur containing acceptors and their oxygen analogues, namely H2O/H2S, MeOH/MeSH, Me2O/Me2S and tetrahydrofuran (THF)/tetrahydrothiophene (THT) were characterized in regard to its S1-S0 excitation spectra and the IR spectra. Two-color resonantly enhanced multiphoton ionization (2c-R2PI), resonant ion-dip infrared (RIDIR) spectroscopy, and IR-UV hole burning spectroscopic techniques were used to probe the hydrogen bonds in the aforementioned complexes. The spectroscopic data along with the ab initio calculations were used to deduce the strength of the O-H···S hydrogen bonding interactions in these system relative to that in the O-H···O interactions. It was found that, despite being dominated by the dispersion interaction, the O-H···S interactions conform to the acid-base formalism as in the case of more conventional O-H···O interactions. The dissociation energies and the red shifts in the O-H stretching frequencies correlated very well with the proton affinity of the acceptors. However, the O-H···S interaction did not follow the same correlation as that in the O-H···O H-bond. The energy decomposition analysis showed that the dissociation energies and the red shifts in the O

  18. A Strategy Combining Higher Energy C-Trap Dissociation with Neutral Loss- and Product Ion-Based MSn Acquisition for Global Profiling and Structure Annotation of Fatty Acids Conjugates

    Science.gov (United States)

    Bi, Qi-rui; Hou, Jin-jun; Yang, Min; Shen, Yao; Qi, Peng; Feng, Rui-hong; Dai, Zhuo; Yan, Bing-peng; Wang, Jian-wei; Shi, Xiao-jian; Wu, Wan-ying; Guo, De-an

    2016-12-01

    Fatty acids conjugates (FACs) are ubiquitous but found in trace amounts in the natural world. They are composed of multiple unknown substructures and side chains. Thus, FACs are difficult to be analyzed by traditional mass spectrometric methods. In this study, an integrated strategy was developed to global profiling and targeted structure annotation of FACs in complex matrix by LTQ Orbitrap. Dicarboxylic acid conjugated bufotoxins (DACBs) in Venenum bufonis (VB) were used as model compounds. The new strategy (abbreviated as HPNA) combined higher-energy C-trap dissociation (HCD) with product ion- (PI), neutral loss- (NL) based MSn (n ≥ 3) acquisition in both positive-ion mode and negative-ion mode. Several advantages are presented. First, various side chains were found under HCD in negative-ion mode, which included both known and unknown side chains. Second, DACBs with multiple side chains were simultaneously detected in one run. Compared with traditional quadrupole-based mass method, it greatly increased analysis throughput. Third, the fragment ions of side chain and steroids substructure could be obtained by PI- and NL-based MSn acquisition, respectively, which greatly increased the accuracy of the structure annotation of DACBs. In all, 78 DACBs have been discovered, of which 68 were new compounds; 25 types of substructure formulas and seven dicarboxylic acid side chains were found, especially five new side chains, including two saturated dicarboxylic acids [(azelaic acid (C9) and sebacic acid (C10)] and three unsaturated dicarboxylic acids (u-C8, u-C9, and u-C10). All these results greatly enriched the structures of DACBs in VB.

  19. A Strategy Combining Higher Energy C-Trap Dissociation with Neutral Loss- and Product Ion-Based MS(n) Acquisition for Global Profiling and Structure Annotation of Fatty Acids Conjugates.

    Science.gov (United States)

    Bi, Qi-Rui; Hou, Jin-Jun; Yang, Min; Shen, Yao; Qi, Peng; Feng, Rui-Hong; Dai, Zhuo; Yan, Bing-Peng; Wang, Jian-Wei; Shi, Xiao-Jian; Wu, Wan-Ying; Guo, De-An

    2017-03-01

    Fatty acids conjugates (FACs) are ubiquitous but found in trace amounts in the natural world. They are composed of multiple unknown substructures and side chains. Thus, FACs are difficult to be analyzed by traditional mass spectrometric methods. In this study, an integrated strategy was developed to global profiling and targeted structure annotation of FACs in complex matrix by LTQ Orbitrap. Dicarboxylic acid conjugated bufotoxins (DACBs) in Venenum bufonis (VB) were used as model compounds. The new strategy (abbreviated as HPNA) combined higher-energy C-trap dissociation (HCD) with product ion- (PI), neutral loss- (NL) based MS(n) (n ≥ 3) acquisition in both positive-ion mode and negative-ion mode. Several advantages are presented. First, various side chains were found under HCD in negative-ion mode, which included both known and unknown side chains. Second, DACBs with multiple side chains were simultaneously detected in one run. Compared with traditional quadrupole-based mass method, it greatly increased analysis throughput. Third, the fragment ions of side chain and steroids substructure could be obtained by PI- and NL-based MS(n) acquisition, respectively, which greatly increased the accuracy of the structure annotation of DACBs. In all, 78 DACBs have been discovered, of which 68 were new compounds; 25 types of substructure formulas and seven dicarboxylic acid side chains were found, especially five new side chains, including two saturated dicarboxylic acids [(azelaic acid (C9) and sebacic acid (C10)] and three unsaturated dicarboxylic acids (u-C8, u-C9, and u-C10). All these results greatly enriched the structures of DACBs in VB. Graphical Abstract ᅟ.

  20. A Strategy Combining Higher Energy C-Trap Dissociation with Neutral Loss- and Product Ion-Based MSn Acquisition for Global Profiling and Structure Annotation of Fatty Acids Conjugates

    Science.gov (United States)

    Bi, Qi-rui; Hou, Jin-jun; Yang, Min; Shen, Yao; Qi, Peng; Feng, Rui-hong; Dai, Zhuo; Yan, Bing-peng; Wang, Jian-wei; Shi, Xiao-jian; Wu, Wan-ying; Guo, De-an

    2017-03-01

    Fatty acids conjugates (FACs) are ubiquitous but found in trace amounts in the natural world. They are composed of multiple unknown substructures and side chains. Thus, FACs are difficult to be analyzed by traditional mass spectrometric methods. In this study, an integrated strategy was developed to global profiling and targeted structure annotation of FACs in complex matrix by LTQ Orbitrap. Dicarboxylic acid conjugated bufotoxins (DACBs) in Venenum bufonis (VB) were used as model compounds. The new strategy (abbreviated as HPNA) combined higher-energy C-trap dissociation (HCD) with product ion- (PI), neutral loss- (NL) based MSn (n ≥ 3) acquisition in both positive-ion mode and negative-ion mode. Several advantages are presented. First, various side chains were found under HCD in negative-ion mode, which included both known and unknown side chains. Second, DACBs with multiple side chains were simultaneously detected in one run. Compared with traditional quadrupole-based mass method, it greatly increased analysis throughput. Third, the fragment ions of side chain and steroids substructure could be obtained by PI- and NL-based MSn acquisition, respectively, which greatly increased the accuracy of the structure annotation of DACBs. In all, 78 DACBs have been discovered, of which 68 were new compounds; 25 types of substructure formulas and seven dicarboxylic acid side chains were found, especially five new side chains, including two saturated dicarboxylic acids [(azelaic acid (C9) and sebacic acid (C10)] and three unsaturated dicarboxylic acids (u-C8, u-C9, and u-C10). All these results greatly enriched the structures of DACBs in VB.

  1. Coherent Behavior and the Bound State of Water and K(+) Imply Another Model of Bioenergetics: Negative Entropy Instead of High-energy Bonds.

    Science.gov (United States)

    Jaeken, Laurent; Vasilievich Matveev, Vladimir

    2012-01-01

    Observations of coherent cellular behavior cannot be integrated into widely accepted membrane (pump) theory (MT) and its steady state energetics because of the thermal noise of assumed ordinary cell water and freely soluble cytoplasmic K(+). However, Ling disproved MT and proposed an alternative based on coherence, showing that rest (R) and action (A) are two different phases of protoplasm with different energy levels. The R-state is a coherent metastable low-entropy state as water and K(+) are bound to unfolded proteins. The A-state is the higher-entropy state because water and K(+) are free. The R-to-A phase transition is regarded as a mechanism to release energy for biological work, replacing the classical concept of high-energy bonds. Subsequent inactivation during the endergonic A-to-R phase transition needs an input of metabolic energy to restore the low entropy R-state. Matveev's native aggregation hypothesis allows to integrate the energetic details of globular proteins into this view.

  2. A force-activated trip switch triggers rapid dissociation of a colicin from its immunity protein.

    Directory of Open Access Journals (Sweden)

    Oliver E Farrance

    Full Text Available Colicins are protein antibiotics synthesised by Escherichia coli strains to target and kill related bacteria. To prevent host suicide, colicins are inactivated by binding to immunity proteins. Despite their high avidity (K(d ≈ fM, lifetime ≈ 4 days, immunity protein release is a pre-requisite of colicin intoxication, which occurs on a timescale of minutes. Here, by measuring the dynamic force spectrum of the dissociation of the DNase domain of colicin E9 (E9 and immunity protein 9 (Im9 complex using an atomic force microscope we show that application of low forces (<20 pN increases the rate of complex dissociation 10(6-fold, to a timescale (lifetime ≈ 10 ms compatible with intoxication. We term this catastrophic force-triggered increase in off-rate a trip bond. Using mutational analysis, we elucidate the mechanism of this switch in affinity. We show that the N-terminal region of E9, which has sparse contacts with the hydrophobic core, is linked to an allosteric activator region in E9 (residues 21-30 whose remodelling triggers immunity protein release. Diversion of the force transduction pathway by the introduction of appropriately positioned disulfide bridges yields a force resistant complex with a lifetime identical to that measured by ensemble techniques. A trip switch within E9 is ideal for its function as it allows bipartite complex affinity, whereby the stable colicin:immunity protein complex required for host protection can be readily converted to a kinetically unstable complex whose dissociation is necessary for cellular invasion and competitor death. More generally, the observation of two force phenotypes for the E9:Im9 complex demonstrates that force can re-sculpt the underlying energy landscape, providing new opportunities to modulate biological reactions in vivo; this rationalises the commonly observed discrepancy between off-rates measured by dynamic force spectroscopy and ensemble methods.

  3. Ultrafast studies of photodissociation in solution: Dissociation, recombination and relaxation

    Energy Technology Data Exchange (ETDEWEB)

    King, Jason Christopher [Univ. of California, Berkeley, CA (United States)

    1995-05-01

    Photodissociation of M(CO)6 (M=Cr,Mo,W) and the formation of solvated M(CO)5•S complex was studied in cyclohexane; rate-limiting step is vibrational energy relaxation from the new bond to the solvent. For both M=Cr and Mo, the primary relaxation occurs in 18 ps; for Cr, there is an additional vibrational relaxation (150 ps time scale) of a CO group poorly coupled to other modes. Relaxation of M=W occurs in 42 ps; several possible mechanisms for the longer cooling are discussed. Vibrational relaxation is also investigated for I2- and IBr- in nonpolar and slightly polar solvents. Attempts were made to discover the mechanism for the fast energy transfer in nonpolar solvent. The longer time scale dynamics of I3- and IBr2- were also studied; both formed a metastable complex following photodissociation and 90-95% return to ground state in 100 ps, implying a barrier to recombination of 4.3 kcal/mol and a barrier to escape of ≥5.5 kcal/mol. The more complex photochemistry of M3(CO)12 (M=Fe,Ru) is also investigated, using visible and ultraviolet radiations, dissociation, geminate recombination, vibrational relaxation, and bridging structures and their reactions were studied. Attempts were made to extend ultrafast spectroscopy into the mid-infrared, but signal-to-noise was poor.

  4. Structure, bonding and energetics of N-heterocyclic carbene (NHC) stabilized low oxidation state group 2 (Be, Mg, Ca, Sr and Ba) metal complexes: A theoretical study

    Indian Academy of Sciences (India)

    Ashim Baishya; V Rao Mundlapati; Sharanappa Nembenna; Himansu S Biswal

    2014-11-01

    A series of N-heterocyclic carbene stabilized low oxidation state group 2 metal halide and hydrides with metal-metal bonds ([L(X) M-M(X) L]; L = NHC ((CHNH)2C:), M = Be, Mg, Ca, Sr and Ba, and X = Cl or H) has been studied by computational methods. The main objective of this study is to predict whether it is possible to stabilize neutral ligated low oxidation state alkaline-earth metal complexes with metal-metal bonds. The homolytic metal-metal Bond Dissociation Energy (BDE) calculation, Natural Bond Orbital (NBO) and Energy Decomposition Analyses (EDA) on density functional theory (DFT) optimized [L(X)M-M(X)L] complexes revealed that they are as stable as their -diketiminate, guanidinate and -diimine counterparts. The optimized structures of the complexes are in trans-linear geometries. The bond order analyses such as Wiberg Bond Indices (WBI) and Fuzzi Bond Order (FBO) confirm the existence of single bond between two metal atoms, and it is covalent in nature.

  5. Probing molecular interaction in ionic liquids by low frequency spectroscopy: Coulomb energy, hydrogen bonding and dispersion forces.

    Science.gov (United States)

    Fumino, Koichi; Reimann, Sebastian; Ludwig, Ralf

    2014-10-28

    Ionic liquids are defined as salts composed solely of ions with melting points below 100 °C. These remarkable liquids have unique and fascinating properties and offer new opportunities for science and technology. New combinations of ions provide changing physical properties and thus novel potential applications for this class of liquid materials. To a large extent, the structure and properties of ionic liquids are determined by the intermolecular interaction between anions and cations. In this perspective we show that far infrared and terahertz spectroscopy are suitable methods for studying the cation-anion interaction in these Coulomb fluids. The interpretation of the measured low frequency spectra is supported by density functional theory calculations and molecular dynamics simulations. We present results for selected aprotic and protic ionic liquids and their mixtures with molecular solvents. In particular, we focus on the strength and type of intermolecular interaction and how both parameters are influenced by the character of the ions and their combinations. We show that the total interaction between cations and anions is a result of a subtle balance between Coulomb forces, hydrogen bonds and dispersion forces. For protic ionic liquids we could measure distinct vibrational modes in the low frequency spectra indicating clearly the cation-anion interaction characterized by linear and medium to strong hydrogen bonds. Using isotopic substitution we have been able to dissect frequency shifts related to pure interaction strength between cations and anions and to different reduced masses only. In this context we also show how these different types of interaction may influence the physical properties of ionic liquids such as the melting point, viscosity or enthalpy of vaporization. Furthermore we demonstrate that low frequency spectroscopy can also be used for studying ion speciation. Low vibrational features can be assigned to contact ion pairs and solvent separated

  6. Selective breaking of bonds in water with intense, 2-cycle, infrared laser pulses

    Energy Technology Data Exchange (ETDEWEB)

    Mathur, D., E-mail: atmol1@tifr.res.in; Dharmadhikari, A. K. [Tata Institute of Fundamental Research, 1 Homi Bhabha Road, Mumbai 400 005 (India); Dota, K. [Tata Institute of Fundamental Research, 1 Homi Bhabha Road, Mumbai 400 005 (India); Centre for Atomic and Molecular Physics, Manipal University, Manipal 576 104 (India); Dey, D.; Tiwari, A. K. [Indian Institute of Science Education and Research Kolkata, Mohanpur 741 246 (India); Dharmadhikari, J. A. [Centre for Atomic and Molecular Physics, Manipal University, Manipal 576 104 (India); De, S. [Saha Institute of Nuclear Physics, Bidhan Nagar, Kolkata 700 064 (India); Vasa, P. [Department of Physics, Indian Institute of Technology Bombay, Mumbai 400 076 (India)

    2015-12-28

    One of the holy grails of contemporary science has been to establish the possibility of preferentially breaking one of several bonds in a molecule. For instance, the two O–H bonds in water are equivalent: given sufficient energy, either one of them is equally likely to break. We report bond-selective molecular fragmentation upon application of intense, 2-cycle pulses of 800 nm laser light: we demonstrate up to three-fold enhancement for preferential bond breaking in isotopically substituted water (HOD). Our experimental observations are rationalized by means of ab initio computations of the potential energy surfaces of HOD, HOD{sup +}, and HOD{sup 2+} and explorations of the dissociation limits resulting from either O–H or O–D bond rupture. The observations we report present a formidable theoretical challenge that need to be taken up in order to gain insights into molecular dynamics, strong field physics, chemical physics, non-adiabatic processes, mass spectrometry, and time-dependent quantum chemistry.

  7. Selective breaking of bonds in water with intense, 2-cycle, infrared laser pulses.

    Science.gov (United States)

    Mathur, D; Dota, K; Dey, D; Tiwari, A K; Dharmadhikari, J A; Dharmadhikari, A K; De, S; Vasa, P

    2015-12-28

    One of the holy grails of contemporary science has been to establish the possibility of preferentially breaking one of several bonds in a molecule. For instance, the two O-H bonds in water are equivalent: given sufficient energy, either one of them is equally likely to break. We report bond-selective molecular fragmentation upon application of intense, 2-cycle pulses of 800 nm laser light: we demonstrate up to three-fold enhancement for preferential bond breaking in isotopically substituted water (HOD). Our experimental observations are rationalized by means of ab initio computations of the potential energy surfaces of HOD, HOD(+), and HOD(2+) and explorations of the dissociation limits resulting from either O-H or O-D bond rupture. The observations we report present a formidable theoretical challenge that need to be taken up in order to gain insights into molecular dynamics, strong field physics, chemical physics, non-adiabatic processes, mass spectrometry, and time-dependent quantum chemistry.

  8. Selective breaking of bonds in water with intense, 2-cycle, infrared laser pulses

    Science.gov (United States)

    Mathur, D.; Dota, K.; Dey, D.; Tiwari, A. K.; Dharmadhikari, J. A.; Dharmadhikari, A. K.; De, S.; Vasa, P.

    2015-12-01

    One of the holy grails of contemporary science has been to establish the possibility of preferentially breaking one of several bonds in a molecule. For instance, the two O-H bonds in water are equivalent: given sufficient energy, either one of them is equally likely to break. We report bond-selective molecular fragmentation upon application of intense, 2-cycle pulses of 800 nm laser light: we demonstrate up to three-fold enhancement for preferential bond breaking in isotopically substituted water (HOD). Our experimental observations are rationalized by means of ab initio computations of the potential energy surfaces of HOD, HOD+, and HOD2+ and explorations of the dissociation limits resulting from either O-H or O-D bond rupture. The observations we report present a formidable theoretical challenge that need to be taken up in order to gain insights into molecular dynamics, strong field physics, chemical physics, non-adiabatic processes, mass spectrometry, and time-dependent quantum chemistry.

  9. Why the complete fusion of weakly bond nuclei is enhanced at sub-barrier energies and suppressed above the barrier?

    Energy Technology Data Exchange (ETDEWEB)

    Lubian, J.; Gomes, P.R.S. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil); Canto, L.F. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil); Hussein, M.S. [Universidade de Sao Paulo (USP), SP (Brazil)

    2012-07-01

    Full text: In the last two decades one has asked whether the complete fusion of weakly bound systems is enhanced or suppressed when compared with the situation where there is no break process. Recent systematic results [1] based on the reduction of cross section and the comparison to the Universal Fusion Function have shown that the complete fusion cross section is indeed enhanced at sub-barrier energies and suppressed at energies above the barrier, when compared with calculations which do not take into account the couplings to breakup channels. In this contribution we discuss and propose a method to explain this conclusion. We point out the importance of direct transfer and breakup processes and also the recently observed sequential breakup that follows the transfer. Different behaviors of the dynamic polarization potentials at different energy regions are used to explain the observed fusion excitation functions for several weakly bound systems. While the breakup polarization is the main reaction channel at above the Coulomb barrier energy regime, leading to repulsive polarization, the sequential breakup (transfer followed by breakup) seems to be the main reaction mechanism at below barrier energies. This last mechanism produces attractive polarization and for this reason it enhances the complete fusion cross section. [1] L.F. Canto et al., Nucl. Phys. A 821, 51 (2009); J. of Phys. G 36, 015109 (2009). (author)

  10. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  11. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  12. Dissociative electron transfer in polychlorinated aromatics. Reduction potentials from convolution analysis and quantum chemical calculations.

    Science.gov (United States)

    Romańczyk, Piotr P; Rotko, Grzegorz; Kurek, Stefan S

    2016-08-10

    Formal potentials of the first reduction leading to dechlorination in dimethylformamide were obtained from convolution analysis of voltammetric data and confirmed by quantum chemical calculations for a series of polychlorinated benzenes: hexachlorobenzene (-2.02 V vs. Fc(+)/Fc), pentachloroanisole (-2.14 V), and 2,4-dichlorophenoxy- and 2,4,5-trichlorophenoxyacetic acids (-2.35 V and -2.34 V, respectively). The key parameters required to calculate the reduction potential, electron affinity and/or C-Cl bond dissociation energy, were computed at both DFT-D and CCSD(T)-F12 levels. Comparison of the obtained gas-phase energies and redox potentials with experiment enabled us to verify the relative energetics and the performance of various implicit solvent models. Good agreement with the experiment was achieved for redox potentials computed at the DFT-D level, but only for the stepwise mechanism owing to the error compensation. For the concerted electron transfer/C-Cl bond cleavage process, the application of a high level coupled cluster method is required. Quantum chemical calculations have also demonstrated the significant role of the π*ring and σ*C-Cl orbital mixing. It brings about the stabilisation of the non-planar, C2v-symmetric C6Cl6˙(-) radical anion, explains the experimentally observed low energy barrier and the transfer coefficient close to 0.5 for C6Cl5OCH3 in an electron transfer process followed by immediate C-Cl bond cleavage in solution, and an increase in the probability of dechlorination of di- and trichlorophenoxyacetic acids due to substantial population of the vibrational excited states corresponding to the out-of-plane C-Cl bending at ambient temperatures.

  13. Difference of Electron Capture and Transfer Dissociation Mass Spectrometry on Ni2+-, Cu2+-, and Zn2+-Polyhistidine Complexes in the Absence of Remote Protons

    Science.gov (United States)

    Asakawa, Daiki; De Pauw, Edwin

    2016-07-01

    Electron capture dissociation (ECD) and electron transfer dissociation (ETD) in metal-peptide complexes are dependent on the metal cation in the complex. The divalent transition metals Ni2+, Cu2+, and Zn2+ were used as charge carriers to produce metal-polyhistidine complexes in the absence of remote protons, since these metal cations strongly bind to neutral histidine residues in peptides. In the case of the ECD and ETD of Cu2+-polyhistidine complexes, the metal cation in the complex was reduced and the recombination energy was redistributed throughout the peptide to lead a zwitterionic peptide form having a protonated histidine residue and a deprotonated amide nitrogen. The zwitterion then underwent peptide bond cleavage, producing a and b fragment ions. In contrast, ECD and ETD induced different fragmentation processes in Zn2+-polyhistidine complexes. Although the N-Cα bond in the Zn2+-polyhistidine complex was cleaved by ETD, ECD of Zn2+-polyhistidine induced peptide bond cleavage accompanied with hydrogen atom release. The different fragmentation modes by ECD and ETD originated from the different electronic states of the charge-reduced complexes resulting from these processes. The details of the fragmentation processes were investigated by density functional theory.

  14. Dissociative excitation and fragmentation of S8 by electron impact.

    Science.gov (United States)

    Brotton, S J; McConkey, J W

    2011-05-28

    The vacuum-ultraviolet emission spectrum from 136 nm to 168 nm following the dissociative excitation of a predominantly S(8) target by electron impact at 100 eV incident energy was measured. The relative cross sections for the dominant multiplets at 138.9, 142.9, 147.9, and 166.7 nm are presented. Excitation functions are shown for electron-impact energies from below threshold to 360 eV for the two most prominent emissions at 142.5 nm and 147.4 nm. Five thresholds are clearly apparent in both excitation functions. For the four highest energy channels, the energy separation between the adjacent thresholds is approximately constant and the cross sections reduce regularly as the threshold energies increase. We suggest possible fragmentation pathways of the dissociating S(8) molecule that reproduce the energies of our observed thresholds.

  15. Charge transfer and polarization for chloride ions bound in ClC transport proteins: natural bond orbital and energy decomposition analyses.

    Science.gov (United States)

    Church, Jonathan; Pezeshki, Soroosh; Davis, Christal; Lin, Hai

    2013-12-19

    ClC transport proteins show a distinct "broken-helix" architecture, in which certain α-helices are oriented with their N-terminal ends pointed toward the binding sites where the chloride ions are held extensively by the backbone amide nitrogen atoms from the helices. To understand the effectiveness of such binding structures, we carried out natural bond orbital analysis and energy decomposition analysis employing truncated active-site model systems for the bound chloride ions along the translocation pore of the EcClC proteins. Our results indicated that the chloride ions are stabilized in such a binding environment by electrostatic, polarization, and charge-transfer interactions with the backbone and a few side chains. Up to ~25% of the formal charges of the chloride ions were found smeared out to the surroundings primarily via charge transfer from the chloride's lone pair n(Cl) orbitals to the protein's antibonding σ*(N-H) or σ*(O-H) orbitals; those σ* orbitals are localized at the polar N-H and O-H bonds in the chloride's first solvation shells formed by the backbone amide groups and the side chains of residues Ser107, Arg147, Glu148, and Tyr445. Polarizations by the chloride ions were dominated by the redistribution of charge densities among the π orbitals and lone pair orbitals of the protein atoms, in particular the atoms of the backbone peptide links and of the side chains of Arg147, Glu148, and Tyr445. The substantial amounts of electron density involved in charge transfer and in polarization were consistent with the large energetic contributions by the two processes revealed by the energy decomposition analysis. The significant polarization and charge-transfer effects may have impacts on the mechanisms and dynamics of the chloride transport by the ClC proteins.

  16. Dissociation of methanol in intense femtosecond laser field

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Methanol was irradiated by 80 fs laser pulse, intensity range of 1013-1014 W/cm2. A TOF-mass spectrometer was coupled to the laser system and used to detect the ions produced. The parent ions CH3OH+ appeared firstly at the laser intensity of 1.4×1013 W/cm2. While the laser intensity was gradually increased, the parent ions were dissociated and the primary ions CH2OH+ were given as verified from the irradiation of deuterated methanol (CH3OD) showing the C-H bond cracking firstly. While the laser intensity was further increased to 2.0 ×1013 W/cm2, the C-O bonds of the parent ions also broke to give CH3+. When the laser intensity was higher, smaller fragment ions like CH+, C+, OH+ and O+ also appeared. Among the fragment ions, only H+ ion yield had anisotropic angular distribution dependence on the laser polarization vector in the dissociation of methanol. All the experimental observations show that the dissociation of methanol proceeds through stepwise mechanism but not Coulomb explosion.

  17. Intense 2-cycle laser pulses induce time-dependent bond-hardening in a polyatomic molecule

    CERN Document Server

    Dota, K; Tiwari, A K; Dharmadhikari, J A; Dharmadhikari, A K; Mathur, D

    2012-01-01

    A time-dependent bond-hardening process is discovered in a polyatomic molecule (tetramethyl silane, TMS) using few-cycle pulses of intense 800 nm light. In conventional mass spectrometry, symmetrical molecules like TMS do not exhibit a prominent molecular ion (TMS$^+$) as unimolecular dissociation into [Si(CH$_3$)$_3]^+$ proceeds very fast. Under strong field and few-cycle conditions, this dissociation channel is defeated by time-dependent bond-hardening: a field-induced potential well is created in the TMS$^+$ potential energy curve that effectively traps a wavepacket. The time-dependence of this bond hardening process is verified using longer-duration ($\\geq$ 100 fs) pulses; the relatively "slower" fall-off of optical field in such pulses allows the initially trapped wavepacket to leak out, thereby rendering TMS$^+$ unstable once again. Our results are significant as they demonstrate (i) optical generation of polyatomic ions that are normally inaccessible and (ii) optical control of dynamics in strong field...

  18. Dissociative electron attachment and electron-impact resonant dissociation of vibrationally excited O2 molecules

    CERN Document Server

    Laporta, V; Tennyson, J

    2015-01-01

    State-by-state cross sections for dissociative electron attachment and electron-impact dissociation for molecular oxygen are computed using ab initio resonance curves calculated with the R-matrix method. When O2 is in its vibrational ground state, the main contribution for both processes comes from the $^2\\Pi_u$ resonance state of $O_2^-$ but with a significant contribution from the $^4\\Sigma$ resonant state. Vibrational excitation leads to an increased contribution from the low-lying $^2\\Pi_{g}$ resonance, greatly increased cross sections for both processes, and the threshold moving to lower energies. These results provide important input for models of O2-containing plasmas in nonequilibrium conditions.

  19. Environmentally dependent bond-order potentials: New developments and applications

    Indian Academy of Sciences (India)

    D Nguyen-Manh; D G Pettifor; D J H Cockayne; M Mrovec; S Znam; V Vitek

    2003-01-01

    The bond-order potentials (BOPs) idea employs the orthogonal two-centre tight-binding (TB) representation for the bond energy and the Harris–Foulkes approximation for the repulsive pairwise contribution. In the last ten years, although many efforts have been focused on theoretical calculations of the bond order expression, the BOPs still suffers from the uncertainty of how best to choose the semi-empirical TB parameters that enter the scheme. In this paper, we review recent developments to obtain the reliable and transferable BOPs which help to extend the accuracy and applicability to technologically important multicomponent systems. Firstly, we have found that a simple pair potential is unsuitable for describing the environmental screening effects due to the and orbital overlap repulsion in transition metal alloys and therefore the inability to reproduce the negative Cauchy pressures exhibiting in strong covalent systems. By adding the environmental dependent repulsive term, the Cauchy pressure problem has been removed and we are now able to get the BOPs for studying dislocations, extended defects and mechanical properties of hightemperature intermetallic Ti–Al alloys. In particular, new results on the core structures and possible dissociation of different type of dislocations will be discussed. Secondly, we present the first derivation of explicit analytic expressions for environmental dependence of , and bond integrals by inverting the non-orthogonal matrix. We illustrate the power of this new formalism by showing that it not only captures the transferability of bond integrals between Mo, Si and MoSi2 but also predicts the large discontinuities between first and second nearest neighbours for $pp\\sigma, pp\\pi$ and $dd\\pi$ even though absence of any discontinuity for the $dd\\sigma$ bond integral. A new environmentally dependent BOPs has been developed for bcc-Mo indicating that the core structure of 1/2$\\langle$111$\\rangle$ screw dislocations is

  20. Neutral dissociation of methane in the ultra-fast laser pulse

    Institute of Scientific and Technical Information of China (English)

    SONG Di; LIU Kai; KONG FanAo; XIA AnDong

    2008-01-01

    Neutral fragments of methane were performed using femetoeecond laser at an intensity of 1013-14 W/cm2. A new mechanism of neutral dissociation is proposed in this work. The methane molecule is excited to super-excited states, in which it would dissociate into neutral fragments. We made Morse type potential energy surfaces for the super-excited molecules. Furthermore, we investigated the dissociation dy-namics of the super-excited states by using quasi-classical trajectory (QCT) method. The results thus interpret the neutral dissociation of the methane molecule in the ultra-fast laser pulse.

  1. Photochemical tissue bonding

    Science.gov (United States)

    Redmond, Robert W.; Kochevar, Irene E.

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  2. Dissociation of N2, NO, and CO on transition metal surfaces

    DEFF Research Database (Denmark)

    Mavrikakis, Manos; Hansen, Lars Bruno; Mortensen, Jens Jørgen;

    1999-01-01

    Using density functional theory we study the dissociation of N2, NO, and CO on transition metal surfaces. We discuss an efficient method to locate the minimum energy path and the transition state, and review recent calculations using this method to determine the transition state for dissociation...

  3. Effect of dissociation pulse circuit inductance on the CuCl laser

    Science.gov (United States)

    Vetter, A. A.; Nerheim, N. M.

    1978-01-01

    The performance of the double-pulsed CuCl laser is improved by a decrease in the inductance of the dissociation pulse circuit. Higher efficiency is obtained due to a larger ground-state copper atom population and lower optimum dissociation energy.

  4. Unusual dissociative adsorption of H2 over stoichiometric MgO thin film supported on molybdenum

    CERN Document Server

    Song, Zhenjun

    2015-01-01

    The dissociation of a hydrogen molecule on MgO(001) films deposited on Mo(001) surface is investigated systematically using periodic density-functional theory method. The unusual adsorption behavior of heterolytic dissociative hydrogen molecule at neighboring surface oxygen and surface magnesium, is clarified here. To my knowledge, this heterolytic dissociative state has never been found before on bulk MgO(001) or metal supported MgO(001) surfaces. The results confirm that, in all cases, the heterolytic dissociation is much more favorable that homolytic dissociation both energetically and kinetically. The energy difference between two dissociative states are very large, in the range of 1.1 eV ~ 1.5 eV for Mo supported 1 ML ~ 3 ML oxide films, which inhibits, to a great extent, the homolytic dissociation in the respect of reaction thermodynamics. The energy barrier of heterolytic dissociation are about 0.5 eV, much lower that the barrier of homolytic dissociation. The transformation reaction on thick films wil...

  5. Molecular Dissociation Induced by Electron Collisions

    Science.gov (United States)

    Wolf, Andreas

    2009-05-01

    Free electrons can efficiently break molecules or molecular ions in low-energy collisions by the processes of dissociative recombination or attachment. These processes make slow electrons efficient chemical agents in many environments. For dissociative recombination, in particular, studies of the underlying reaction paths and mechanisms have become possible on a uniquely elementary level in recent years both for theory and experiment. On the experimental side, collisions can be prepared at resolved collision energies down to the meV (10 Kelvin) level, increasingly gaining control also over the initial molecular quantum level, and individual events are detected and kinematically analyzed by fast-beam coincidence fragment imaging. Experiments are reported from the ion cooler ring TSR in Heidelberg. Stored beams of molecular ions cooled in their external and internal degrees of freedom are collinearly merged with intense and cold electron beams from cryogenic GaAs photocathodes, recently shown to yield fast cooling of the center-of-mass motion also for heavy and correspondingly slow molecular ion beams. To reconstruct the molecular fragmentation events multiparticle imaging can now be used systematically with collision energies set a wide range, especially aiming at specific electron capture resonances. Thus, for CF^+ it is found that the electronic state of the C fragment (^3P or ^1D) switches resonantly when the collision energy is changed by only a small fraction. As a new powerful tool, an energy-sensitive multi-strip surface-barrier detector (EMU) has been set up to measure with near-unity efficiency the masses of all fragments together with their hit positions in high-multiplicity events. Among many uses, this device allows internal molecular excitations to be derived for individual chemical channels in polyatomic fragmentation. New results will be presented in particular on the breakup of the hydronium ion (D3O^+).

  6. Extreme population inversion in the fragments formed by UV photoinduced S-H bond fission in 2-thiophenethiol.

    Science.gov (United States)

    Ingle, Rebecca A; Karsili, Tolga N V; Dennis, Gregg J; Staniforth, Michael; Stavros, Vasilios G; Ashfold, Michael N R

    2016-04-28

    H atom loss following near ultraviolet photoexcitation of gas phase 2-thiophenethiol molecules has been studied experimentally, by photofragment translational spectroscopy (PTS) methods, and computationally, by ab initio electronic structure calculations. The long wavelength (277.5 ≥ λ(phot) ≥ 240 nm) PTS data are consistent with S-H bond fission after population of the first (1)πσ* state. The partner thiophenethiyl (R) radicals are formed predominantly in their first excited Ã(2)A' state, but assignment of a weak signal attributable to H + R(X˜(2)A'') products allows determination of the S-H bond strength, D0 = 27,800 ± 100 cm(-1) and the Ã-X˜ state splitting in the thiophenethiyl radical (ΔE = 3580 ± 100 cm(-1)). The deduced population inversion between the à and X˜ states of the radical reflects the non-planar ground state geometry (wherein the S-H bond is directed near orthogonal to the ring plane) which, post-photoexcitation, is unable to planarise sufficiently prior to bond fission. This dictates that the dissociating molecules follow the adiabatic fragmentation pathway to electronically excited radical products. π* ← π absorption dominates at shorter excitation wavelengths. Coupling to the same (1)πσ* potential energy surface (PES) remains the dominant dissociation route, but a minor yield of H atoms attributable to a rival fragmentation pathway is identified. These products are deduced to arise via unimolecular decay following internal conversion to the ground (S0) state PES via a conical intersection accessed by intra-ring C-S bond extension. The measured translational energy disposal shows a more striking change once λ(phot) ≤ 220 nm. Once again, however, the dominant decay pathway is deduced to be S-H bond fission following coupling to the (1)πσ* PES but, in this case, many of the evolving molecules are deduced to have sufficiently near-planar geometries to allow passage through the conical intersection at extended S-H bond

  7. Plasma-driven dissociation of CO2 for fuel synthesis

    NARCIS (Netherlands)

    Bongers, Waldo; Bouwmeester, Henny J.M.; Wolf, Bram; Peeters, Floran; Welzel, Stefan; Bekerom, van den Dirk; Harder, den Niek; Goede, Adelbert; Graswinckel, Martijn; Groen, Pieter Willem; Kopecki, Jochen; Leins, Martina; Rooij, van Gerard; Schulz, Andreas; Walker, Matthias; Sanden, van de Richard

    2016-01-01

    Power-to-gas is a storage technology aiming to convert surplus electricity from renewable energy sources like wind and solar power into gaseous fuels compatible with the current network infrastructure. Results of CO2 dissociation in a vortexstabilized microwave plasma reactor are presented. The micr

  8. Nucleon-x sub c sub J dissociation cross sections

    CERN Document Server

    Feng You Ceng; Xu Xiao Ming

    2002-01-01

    Nucleon-x sub c sub J dissociation cross sections are calculated in a constituent inter-exchange model in which quark-quark potential is derived from the Buchmueller-Type quark-anti-quark potential. These new cross sections for dominant reaction channels depend on the centre-of-mass energy of the nucleon and the charmonium

  9. DISSOCIATIVE DISORDERS IN DSM-5

    NARCIS (Netherlands)

    Spiegel, David; Loewenstein, Richard J.; Lewis-Fernandez, Roberto; Sar, Vedat; Simeon, Daphne; Vermetten, Eric; Cardena, Etzel; Dell, Paul F.

    2011-01-01

    Background: We present recommendations for revision of the diagnostic criteria for the Dissociative Disorders (DDs) for DSM-5. The periodic revision of the DSM provides an opportunity to revisit the assumptions underlying specific diagnoses and the empirical support, or lack of it, for the defining

  10. Dissociative disorders in DSM-5

    NARCIS (Netherlands)

    Spiegel, David; Loewenstein, Richard J.; Lewis-Fernandez, Roberto; Sar, Vedat; Simeon, Daphne; Vermetten, Eric; Cardena, Etzel; Dell, Paul F.

    2011-01-01

    Background: We present recommendations for revision of the diagnostic criteria for the Dissociative Disorders (DDs) for DSM-5. The periodic revision of the DSM provides an opportunity to revisit the assumptions underlying specific diagnoses and the empirical support, or lack of it, for the defining

  11. Geometrical criteria versus quantum chemical criteria for assessment of intramolecular hydrogen bond (IMHB) interaction: A computational comparison into the effect of chlorine substitution on IMHB of salicylic acid in its lowest energy ground state conformer

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Bijan Kumar [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Calcutta 700009 (India); Guchhait, Nikhil, E-mail: nikhil.guchhait@rediffmail.com [Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Calcutta 700009 (India)

    2013-02-01

    Highlights: ► Intramolecular hydrogen bonding (IMHB) in salicylic acid and its chloro derivatives. ► A complex effect of +R and −I effect of chlorine substituents on IMHB energy. ► Interplay between IMHB energy and aromaticity. ► Directional nature of IMHB from quantum chemical assessment. ► Quantum chemical treatment vs. geometrical criteria to assess weak interaction. - Abstract: Density functional theory based computational study has been performed to characterize intramolecular hydrogen bonding (IMHB) interaction in a series of salicylic acid derivatives varying in chlorine substitution on the benzene ring. The molecular systems studied are salicylic acid, 5-chlorosalicylic acid, 3,5-dichlorosalicylic acid and 3,5,6-tricholorosalicylic acid. Major emphasis is rendered on the analysis of IMHB interaction by calculation of electron density ρ(r) and Laplacian ∇{sup 2}ρ(r) at the bond critical point using atoms-in-molecule theory. Topological features, energy densities based on ρ(r) through perturbing the intramolecular H-bond distances suggest that at equilibrium geometry the IMHB interaction develops certain characteristics typical of covalent interaction. The interplay between aromaticity and resonance-assisted hydrogen bonding (RAHB) is discussed using both geometrical and magnetic criteria as the descriptors of aromaticity. The optimized geometry features, molecular electrostatic potential map analysis are also found to produce a consensus view in relation with the formation of RAHB in these systems.

  12. Cooperative dissociations of misfit dislocations at bimetal interfaces

    Science.gov (United States)

    Liu, K.; Zhang, R. F.; Beyerlein, I. J.; Chen, X. Y.; Yang, H.; Germann, T. C.

    2016-11-01

    Using atomistic simulations, several semi-coherent cube-on-cube bimetal interfaces are comparatively investigated to unravel the combined effect of the character of misfit dislocations, the stacking fault energy difference between bimetal pairs, and their lattice mismatch on the dissociation of interfacial misfit dislocations. Different dissociation paths and features under loadings provide several unique deformation mechanisms that are critical for understanding interface strengthening. In particular, applied strains can cause either the formation of global interface coherency by the migration of misfit dislocations from an interface to an adjoining crystal interior or to an alternate packing of stacking faults connected by stair-rod dislocations.

  13. Electron-driven excitations and dissociation of molecules

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Greg [Univ. of California, Davis, CA (United States); Orel, Ann E. [Univ. of California, Davis, CA (United States)

    2015-02-13

    This program studied how energy is interchanged in electron and photon collisions with molecules leading to ex-citation and dissociation. Modern ab initio techniques, both for the photoionization and electron scattering, and the subsequent nuclear dynamics studies, are used to accurately treat these problems. This work addresses vibrational ex-citation and dissociative attachment following electron impact, and the dynamics following inner shell photoionzation. These problems are ones for which a full multi-dimensional treatment of the nuclear dynamics is essential and where non-adiabatic effects are expected to be important.

  14. Detection of sub-GeV Dark Matter and Solar Neutrinos via Chemical-Bond Breaking

    CERN Document Server

    Essig, Rouven; Slone, Oren; Volansky, Tomer

    2016-01-01

    We explore a new low-threshold direct-detection concept for dark matter, based on the breaking of chemical bonds between atoms. This includes the dissociation of molecules and the creation of defects in a lattice. With thresholds of a few to 10's of eV, such an experiment could probe the nuclear couplings of dark matter particles as light as a few MeV. We calculate the expected rates for dark matter to break apart diatomic molecules, which we take as a case study for more general systems. We briefly mention ideas for how chemical-bond breaking might be detected in practice. We also discuss the possibility of detecting solar neutrinos, including pp neutrinos, with this experimental concept. With an event rate of $\\mathcal{O}$(0.1/kg-year), large exposures are required, but measuring low-energy solar neutrinos would provide a crucial test of the solar model.

  15. Stacked and H-Bonded Cytosine Dimers. Analysis of the Intermolecular Interaction Energies by Parallel Quantum Chemistry and Polarizable Molecular Mechanics.

    Science.gov (United States)

    Gresh, Nohad; Sponer, Judit E; Devereux, Mike; Gkionis, Konstantinos; de Courcy, Benoit; Piquemal, Jean-Philip; Sponer, Jiri

    2015-07-30

    Until now, atomistic simulations of DNA and RNA and their complexes have been executed using well calibrated but conceptually simple pair-additive empirical potentials (force fields). Although such simulations provided many valuable results, it is well established that simple force fields also introduce errors into the description, underlying the need for development of alternative anisotropic, polarizable molecular mechanics (APMM) potentials. One of the most abundant forces in all kinds of nucleic acids topologies is base stacking. Intra- and interstrand stacking is assumed to be the most essential factor affecting local conformational variations of B-DNA. However, stacking also contributes to formation of all kinds of noncanonical nucleic acids structures, such as quadruplexes or folded RNAs. The present study focuses on 14 stacked cytosine (Cyt) dimers and the doubly H-bonded dimer. We evaluate the extent to which an APMM procedure, SIBFA, could account quantitatively for the results of high-level quantum chemistry (QC) on the total interaction energies, and the individual energy contributions and their nonisotropic behaviors. Good agreements are found at both uncorrelated HF and correlated DFT and CCSD(T) levels. Resorting in SIBFA to distributed QC multipoles and to an explicit representation of the lone pairs is essential to respectively account for the anisotropies of the Coulomb and of the exchange-repulsion QC contributions.

  16. Dissociating Prediction Failure: Considerations from Music Perception

    DEFF Research Database (Denmark)

    Ross, Suzi; Hansen, Niels Christian

    2016-01-01

    Dissociating Prediction Failure: Considerations from Music Perception The Journal of Neuroscience, 16 March 2016, 36(11): 3103-3105;......Dissociating Prediction Failure: Considerations from Music Perception The Journal of Neuroscience, 16 March 2016, 36(11): 3103-3105;...

  17. Potential energy curves for P2 and P2+ constructed from a strictly N-representable natural orbital functional

    CERN Document Server

    Piris, Mario

    2016-01-01

    The potential energy curves of P2 and P2+ have been calculated using an approximate, albeit strictly N-representable, energy functional of the one-particle reduced density matrix: PNOF5. Quite satisfactory accord is found for the equilibrium bond lengths and dissociation energies for both species. The predicted vertical ionization energy for P2 by means of the extended Koopmans' theorem is 10.57 eV in good agreement with the experimental data. Comparison of the vibrational energies and anharmonicities with their corresponding experimental values supports the quality of the resultant potential energy curves.

  18. Reaction paths of phosphine dissociation on silicon (001)

    Energy Technology Data Exchange (ETDEWEB)

    Warschkow, O.; McKenzie, D. R. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); Curson, N. J. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052 (Australia); London Centre for Nanotechnology and Department of Electronic and Electrical Engineering, University College London, 17-19 Gordon Street, London WC1H 0AH (United Kingdom); Schofield, S. R. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052 (Australia); London Centre for Nanotechnology and Department of Physics and Astronomy, University College, 17-19 Gordon Street, London WC1H 0AH (United Kingdom); Marks, N. A. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); Discipline of Physics & Astronomy, Curtin University, GPO Box U1987, Perth, WA (Australia); Wilson, H. F. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006 (Australia); CSIRO Virtual Nanoscience Laboratory, Parkville, VIC 3052 (Australia); School of Applied Sciences, RMIT University, Melbourne, VIC 3000 (Australia); Radny, M. W.; Smith, P. V. [School of Mathematical and Physical Sciences, The University of Newcastle, Callaghan, NSW 2308 (Australia); Reusch, T. C. G.; Simmons, M. Y. [Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052 (Australia)

    2016-01-07

    Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH{sub 3}) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH{sub 2}+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH{sub 2} fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH{sub 3} stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.

  19. Reaction paths of phosphine dissociation on silicon (001)

    Science.gov (United States)

    Warschkow, O.; Curson, N. J.; Schofield, S. R.; Marks, N. A.; Wilson, H. F.; Radny, M. W.; Smith, P. V.; Reusch, T. C. G.; McKenzie, D. R.; Simmons, M. Y.

    2016-01-01

    Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH3) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH2+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH2 fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH3 stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.

  20. TD-DFT Insight into Photodissociation of Co-C Bond in Coenzyme B12

    Science.gov (United States)

    Kozlowski, Pawel; Liu, Hui; Kornobis, Karina; Lodowski, Piotr; Jaworska, Maria

    2013-12-01

    Coenzyme B12 (AdoCbl) is one of the most biologically active forms of vitamin B12, and continues to be a topic of active research interest. The mechanism of Co-C bond cleavage in AdoCbl, and the corresponding enzymatic reactions are however, not well understood at the molecular level. In this work, time-dependent density functional theory (TD-DFT) has been applied to investigate the photodissociation of coenzyme B12. To reduce computational cost, while retaining the major spectroscopic features of AdoCbl, a truncated model based on ribosylcobalamin (RibCbl) was used to simulate Co-C photodissociation. Equilibrium geometries of RibCbl were obtained by optimization at the DFT/BP86/TZVP level of theory, and low-lying excited states were calculated by TD-DFT using the same functional and basis set. The calculated singlet states, and absorption spectra were simulated in both the gas phase, and water, using the polarizable continuum model (PCM). Both spectra were in reasonable agreement with experimental data, and potential energy curves based on vertical excitations were plotted to explore the nature of Co-C bond dissociation. It was found that a repulsive 3(σCo-C → σ*Co-C) triplet state became dissociative at large Co-C bond distance, similar to a previous observation for methylcobalamin (MeCbl). Furthermore, potential energy surfaces (PESs) obtained as a function of both Co-CRib and Co-NIm distances, identify the S1 state as a key intermediate generated during photoexcitation of RibCbl, attributed to a mixture of a MLCT (metal-to-ligand charge transfer) and a σ bonding-ligand charge transfer (SBLCT) states.

  1. Carrier-Envelope-Phase Dependent Dissociation of Hydrogen

    CERN Document Server

    Xu, Han; Laban, D E; Wallace, W C; Kielpinski, D; Sang, R T; Litvinyuk, I V

    2012-01-01

    We studied dependence of dissociative ionization in H2 on carrier-envelope phase (CEP) of few-cycle (6fs) near-infrared (NIR) laser pulses. For low-energy channels, we present the first experimental observation of CEP dependence for total dissociation yield and the highest dwgree of asymmetry reported to date (40%). The observed modulations in both asymmetry and total yield could be understood in terms of interference between different n-photon dissociation pathways - n and (n+1) photon channels for asymmetry, n and (n+2) photon channels for yield - as suggested by the general theory of CEP effects (Roudnev and Esry, Phys. Rev. Lett. 99, 220406 (2007), [1]). The yield modulation is found to be Pi-periodic in CEP, with its phase strongly dependent on fragment kinetic energy (and reversing its sign within the studied energy range), indicating that the dissociation does not simply follow the CEP dependence of maximum electric field, as a naive intuition might suggest. We also find that a positively chirped pulse...

  2. The dissociative recombination of fluorocarbon ions: II. CF{sup +}

    Energy Technology Data Exchange (ETDEWEB)

    Novotny, O [PALMS, UMR No 6627 du CNRS, Universite de Rennes I, 35042 Rennes (France); Mitchell, J B A [PALMS, UMR No 6627 du CNRS, Universite de Rennes I, 35042 Rennes (France); LeGarrec, J L [PALMS, UMR No 6627 du CNRS, Universite de Rennes I, 35042 Rennes (France); Florescu-Mitchell, A I [PALMS, UMR No 6627 du CNRS, Universite de Rennes I, 35042 Rennes (France); Rebrion-Rowe, C [PALMS, UMR No 6627 du CNRS, Universite de Rennes I, 35042 Rennes (France); Svendsen, A [Department of Physics and Astronomy, University of Aarhus, DK-8000 Aarhus C (Denmark); El Ghazaly, M A [Department of Physics and Astronomy, University of Aarhus, DK-8000 Aarhus C (Denmark); Andersen, L H [Department of Physics and Astronomy, University of Aarhus, DK-8000 Aarhus C (Denmark); Ehlerding, A [Department of Physics, Stockholm University, Alba Nova, SE-106 91, Stockholm (Sweden); Viggiano, A A [Air Force Research Laboratory, Space Vehicles Directorate, 29 Randolph Road, Hanscom AFB, MA 01731 (United States); Hellberg, F [Department of Physics, Stockholm University, Alba Nova, SE-106 91, Stockholm (Sweden); Thomas, R D [Department of Physics, Stockholm University, Alba Nova, SE-106 91, Stockholm (Sweden); Zhaunerchyk, V [Department of Physics, Stockholm University, Alba Nova, SE-106 91, Stockholm (Sweden); Geppert, W D [Department of Physics, Stockholm University, Alba Nova, SE-106 91, Stockholm (Sweden); Montaigne, H [Department of Physics, Stockholm University, Alba Nova, SE-106 91, Stockholm (Sweden); Kaminska, M [Swietokrzyska Academy, 25-406 Kielce (Poland); Oesterdahl, F [Department of Physics, Royal Institute of Technology, Alba Nova, SE-106 91, Stockholm (Sweden); Larsson, M [Department of Physics, Stockholm University, Alba Nova, SE-106 91, Stockholm (Sweden)

    2005-05-28

    The dissociative recombination and excitation of CF{sup +} have been measured at the ASTRID and CRYRING storage rings. Though examination of the available potential energy curves would suggest that the recombination rate would be large for this ion, in fact a rate constant of 5.2 {+-} 1.0 x 10{sup -8} (T{sub e}/300){sup -0.8} cm{sup 3} s{sup -1} was found. The recombination cross section at low energies falls off to a minimum at 0.5 eV centre-of-mass collision energy but exhibits resonances at energies above this. The dissociative excitation cross section leading to C{sup +} + F was also measured and this displays an onset beginning at about 7 eV.

  3. Acid-Base Formalism Extended to Excited State for O-H···S Hydrogen Bonding Interaction.

    Science.gov (United States)

    Bhattacharyya, Surjendu; Roy, Ved Prakash; Wategaonkar, Sanjay

    2016-09-08

    Hydrogen bond can be regarded as an interaction between a base and a proton covalently bound to another base. In this context the strength of hydrogen bond scales with the proton affinity of the acceptor base and the pKa of the donor, i.e., it follows the acid-base formalism. This has been amply demonstrated in conventional hydrogen bonds. Is this also true for the unconventional hydrogen bonds involving lesser electronegative elements such as sulfur atom? In our previous work, we had established that the strength of O-H···S hydrogen bonding (HB) interaction scales with the proton affinity (PA) of the acceptor. In this work, we have investigated the other counterpart, i.e., the H-bonding interaction between the photoacids with different pKa values with a common base such as the H2O and H2S. The 1:1 complexes of five para substituted phenols p-aminophenol, p-cresol, p-fluorophenol, p-chlorophenol, and p-cyanophenol with H2O and H2S were investigated experimentally and computationally. The investigations were also extended to the excited states. The experimental observations of the spectral shifts in the O-H stretching frequency and the S1-S0 band origins were correlated with the pKa of the donors. Ab initio calculations at the MP2 and various dispersion corrected density functional levels of theory were performed to compute the dissociation energy (D0) of the complexes. The quantum theory of atoms in molecules (QTAIM), noncovalent interaction (NCI) method, natural bonding orbital (NBO) analysis, and natural decomposition analysis (NEDA) were carried out for further characterization of HB interaction. The O-H stretching frequency red shifts and the dissociation energies were found to be lower for the O-H···S hydrogen bonded systems compared to those for the O-H···O H-bound systems. Despite being dominated by the dispersion interaction the O-H···S interaction in the H2S complexes also conformed to the acid-base formalism, i.e., the D0 and the O-H red shift

  4. Extraction Behaviors of Heavy Rare Earths with Organophosphoric Extractants: The Contribution of Extractant Dimer Dissociation, Acid Ionization, and Complexation. A Quantum Chemistry Study.

    Science.gov (United States)

    Jing, Yu; Chen, Ji; Chen, Li; Su, Wenrou; Liu, Yu; Li, Deqian

    2017-03-30

    Heavy rare earths (HREs), namely Ho(3+), Er(3+), Tm(3+), Yb(3+) and Lu(3+), are rarer and more exceptional than light rare earths, due to the stronger extraction capacity for 100 000 extractions. Therefore, their incomplete stripping and high acidity of stripping become problems for HRE separation by organophosphoric extractants. However, the theories of extractant structure-performance relationship and molecular design method of novel HRE extractants are still not perfect. Beyond the coordination chemistry of the HRE-extracted complex, the extractant dimer dissociation, acid ionization, and complexation behaviors can be crucial to HRE extraction and reactivity of ionic species for understanding and further improving the extraction performance. To address the above issues, three primary fundamental processes, including extractant dimer dissociation, acid ionization, and HRE complexation, were identified and investigated systematically. The intrinsic extraction performances of HRE cations with four acidic organophosphoric extractants (P507, P204, P227 and Cyanex 272) were studied by using relativistic energy-consistent 4f core pseudopotentials, combined with density functional theory and a solvation model. Four acidic organophosphoric extractants have been qualified quantitatively from microscopic structures to chemical properties. It has been found that the Gibbs free energy changes of the overall extraction process (sequence: P204 > P227 > P507 > Cyanex 272) and their differences as a function of HREs (sequence: Ho/Er > Er/Tm > Tm/Yb > Yb/Lu) are in good agreement with the experimental maximum extraction capacities and separation factors. These results could provide an important approach to evaluate HRE extractants by the comprehensive consideration of dimer dissociation, acid ionization, and complexation processes. This paper also demonstrates the importance of the P-O bond, the P-C bond, isomer substituent, and solvation effects on the structure

  5. Direct Determination of the Ionization Energies of PtC, PtO, and PtO2 with VUVRadiation

    Energy Technology Data Exchange (ETDEWEB)

    Citir, Murat; Metz, Ricardo B.; Belau, Leonid; Ahmed, Musahid

    2008-07-21

    Photoionization efficiency curves were measured for gas-phase PtC, PtO, and PtO2 using tunable vacuum ultraviolet (VUV) radiation at the Advanced Light Source. The molecules were prepared by laser ablation of a platinum tube, followed by reaction with CH4 or N2O and supersonic expansion. These measurements providethe first directly measured ionization energy for PtC, IE(PtC) = 9.45 +- 0.05 eV. The direct measurement also gives greatly improved ionization energies for the platinum oxides, IE(PtO) = 10.0 +- 0.1 eV and IE(PtO2) = 11.35 +- 0.05 eV. The ionization energy connects the dissociation energies of the neutral and cation, leading to greatly improved 0 K bond dissociation energies for the neutrals: D0(Pt-C) = 5.95 +- 0.07 eV, D0(Pt-O)= 4.30 +- 0.12 eV, and D0(OPt-O) = 4.41 +- 0.13 eV, as well as enthalpies of formation for the gas-phase molecules Delta H0 f,0(PtC(g)) = 701 +- 7 kJ/mol, Delta H0f,0(PtO(g)) = 396 +- 12 kJ/mol, and Delta H0f,0(PtO2(g)) = 218 +- 11 kJ/mol. Much of the error in previous Knudsen cell measurements of platinum oxide bond dissociation energies is due to the use of thermodynamic second law extrapolations. Third law values calculated using statistical mechanical thermodynamic functions are in much better agreement with values obtained from ionization energies and ion energetics. These experiments demonstrate that laser ablation production with direct VUV ionization measurements is a versatile tool to measure ionization energies and bond dissociation energies for catalytically interesting species such as metal oxides and carbides.

  6. Mechanisms of Bond Cleavage during Manganese Oxide and UV Degradation of Glyphosate: Results from Phosphate Oxygen Isotopes and Molecular Simulations.

    Science.gov (United States)

    Jaisi, Deb P; Li, Hui; Wallace, Adam F; Paudel, Prajwal; Sun, Mingjing; Balakrishna, Avula; Lerch, Robert N

    2016-11-16

    Degradation of glyphosate in the presence of manganese oxide and UV light was analyzed using phosphate oxygen isotope ratios and density function theory (DFT). The preference of C-P or C-N bond cleavage was found to vary with changing glyphosate/manganese oxide ratios, indicating the potential role of sorption-induced conformational changes on the composition of intermediate degradation products. Isotope data confirmed that one oxygen atom derived solely from water was incorporated into the released phosphate during glyphosate degradation, and this might suggest similar nucleophilic substitution at P centers and C-P bond cleavage both in manganese oxide- and UV light-mediated degradation. The DFT results reveal that the C-P bond could be cleaved by water, OH(-) or (•)OH, with the energy barrier opposing bond dissociation being lowest in the presence of the radical species, and that C-N bond cleavage is favored by the formation of both nitrogen- and carbon-centered radicals. Overall, these results highlight the factors controlling the dominance of C-P or C-N bond cleavage that determines the composition of intermediate/final products and ultimately the degradation pathway.

  7. The dissociative chemisorption of CO2 on Ni(100): A quantum dynamics study

    Science.gov (United States)

    Farjamnia, Azar; Jackson, Bret

    2017-02-01

    A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. Our computed dissociative sticking probabilities on Ni(100) for molecules in the ground state are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). We predict that the dissociative sticking behavior is similar on the two surfaces.

  8. Electron photodetachment dissociation for structural characterization of synthetic and bio-polymer anions.

    Science.gov (United States)

    Antoine, Rodolphe; Lemoine, Jérôme; Dugourd, Philippe

    2014-01-01

    Tandem mass spectrometry (MS-MS) is a generic term evoking techniques dedicated to structural analysis, detection or quantification of molecules based on dissociation of a precursor ion into fragments. Searching for the most informative fragmentation patterns has led to the development of a vast array of activation modes that offer complementary ion reactivity and dissociation pathways. Collisional activation of ions using atoms, molecules or surface resulting in unimolecular dissociation of activated ions still plays a key role in tandem mass spectrometry. The discovery of electron capture dissociation (ECD) and then the development of other electron-ion or ion/ion reaction methods, constituted a significant breakthrough, especially for structural analysis of large biomolecules. Similarly, photon activation opened promising new frontiers in ion fragmentation owing to the ability of tightly controlled internal energy deposition and easy implementation on commercial instruments. Ion activation by photons includes slow heating methods such as infrared multiple photon dissociation (IRMPD) and black-body infrared radiative dissociation (BIRD) and higher energy methods like ultra-violet photodissociation (UVPD) and electron photo detachment dissociation (EPD). EPD occurs after UV irradiation of multiply negatively charged ions resulting in the formation of oxidized radical anions. The present paper reviews the hypothesis regarding the mechanisms of electron photo-detachment, radical formation and direct or activated dissociation pathways that support the observation of odd and even electron product ions. Finally, the value of EPD as a complementary structural analysis tool is illustrated through selected examples of synthetic polymers, oligonucleotides, polypeptides, lipids, and polysaccharides.

  9. A theoretical study of nitric oxide adsorption and dissociation on copper-exchanged zeolites SSZ-13 and SAPO-34: the impact of framework acid-base properties.

    Science.gov (United States)

    Uzunova, Ellie L; Mikosch, Hans

    2016-04-28

    The adsorption of nitric oxide as dinitrosyls and the deNOx proton-mediated reaction mechanism are assessed using electronic structure methods and transition state theory. Dinitrosyls bind to copper cations either via a N-atom or via an O-atom, with N-binding being more stable. In their ground states, dinitrosyls reach a planar configuration with the metal cation. The two nitric oxide molecules are kept together in O-bonded dinitrosyls by the N-N bond and the adsorption complex obtains a cyclic planar structure, while N-bonded dinitrosyls have out-of-plane conformations with low energy barriers. An asymmetric structure ZCu(ON)(NO) with one N-bonded nitrosyl and the other O-bonded is of the lowest stability. The cyclic hyponitrite ZCu(ON)2 adsorption complex undergoes O-N bond breaking upon protonation of one oxygen atom and this lowers the energy barrier of the first reaction step of nitric oxide dissociation to yield N2O and a hydroxylated copper site ZCu(OH) by 45 kJ mol(-1) for Cu-SAPO-34 and by 46 kJ mol(-1) for Cu-SSZ-13. The more stable N-bonded dinitrosyl ZCu(NO)2 provides less favorable reaction which passes through the asymmetric ZCu(ON)(NO) intermediate structure. Brønsted acid sites facilitate the reversal of one nitrosyl group. The role of proton transfer from a Brønsted acid site to dinitrosyls is not limited to the initial step of facilitating the N-O bond cleavage, but it also contributes to the stabilization of intermediate oxygen species formed at the copper site as hydroxide ZCu(OH) and hydroperoxide, ZCuOOH. Without protonation, the unstable ZCuO intermediate causes structural deformation with strongly lengthened T-O bonds in the framework. The rate determining step is N2O decomposition to N2 and O2, whether starting with a ZCu(NO)2 or a ZCu(ON)2 adsorption complex, and Cu-SSZ-13 has a clear advantage with an energy barrier of 195 kJ mol(-1)vs. 265 kJ mol(-1) for Cu-SAPO-34. In the final step the Brønsted acid site is restored by proton

  10. Pseudospectral calculation of near-dissociative local mode states for the bifluoride anion HF - 2

    Science.gov (United States)

    Bramley, M. J.; Corey, G. C.; Hamilton, I. P.

    1995-12-01

    Using a recently reported global potential energy surface, we calculate all vibrational levels of the HF-2 anion up to the dissociation threshold. The equilibrium geometry of the bifluoride anion is linear with the H atom between the F atoms. The vibrational wave functions are symmetric or antisymmetric with respect to reflection in a plane bisecting the F-F axis. We focus on nearly degenerate pairs of symmetric and antisymmetric levels lying close to the dissociation energy. Sums and differences of these levels are local mode states for which the H atom is localized on one of the F atoms. These near-dissociative local mode states, which can exist above the threshold for dissociation into F- and HF or FH and F- fragments, have been proposed as candidates for spectroscopic experiments which probe the dynamics and structure of the transition state in the unimolecular dissociation of polyatomic molecules. Energies of the low-lying vibrational levels, as well as those around the dissociation energy, are presented. Wave functions of highly vibrationally excited states, lying slightly below and slightly above the dissociation threshold, are analyzed graphically.

  11. 25 CFR 214.4 - Bonds.

    Science.gov (United States)

    2010-04-01

    ... 25 Indians 1 2010-04-01 2010-04-01 false Bonds. 214.4 Section 214.4 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR ENERGY AND MINERALS LEASING OF OSAGE RESERVATION LANDS, OKLAHOMA, FOR... reserved to change the amount of the bond in any particular case, or to require a new bond in...

  12. The Nature of the Hydrogen Bond Outline of a Comprehensive Hydrogen Bond Theory

    CERN Document Server

    Gilli, Gastone

    2009-01-01

    Hydrogen bond (H-bond) effects are known: it makes sea water liquid, joins cellulose microfibrils in trees, shapes DNA into genes and polypeptide chains into wool, hair, muscles or enzymes. Its true nature is less known and we may still wonder why O-H...O bond energies range from less than 1 to more than 30 kcal/mol without apparent reason. This H-bond puzzle is re-examined here from its very beginning and presented as an inclusive compilation of experimental H-bond energies andgeometries.New concepts emerge from this analysis: new classes of systematically strong H-bonds (CAHBs and RAHBs: cha

  13. Coulomb dissociation of light unstable nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Kido, Toshihiko [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Yabana, Kazuhiro; Suzuki, Yoshiyuki

    1997-05-01

    The aim of this study is that a simulation method applicable to the atomic nucleus with neutron halo structure developed till now is applied to a wider range unstable nucleus containing proton excess nucleus to also attribute understanding of nuclear reaction with interest in astronomical nuclear reaction. The proton dissociation energy in {sup 8}B nucleus is small value of 138 eV, which is thought to have a structure of proton at the most outer shell bound much weakly by core nucleus and spread in thinner thickness. For the coulomb excitation of such weak bound system, quantum theoretical and non-perturbational treatment is important. Therefore, 3-dimensional time-dependent Schroedinger equation on relative wave function of the core nucleus {sup 7}Be and halo proton p will be dissolved in time space and will execute a time developmental simulation. (G.K.)

  14. Properties and reactions of manganese methylene complexes in the gas phase. The importance of strong metal: carbene bonds for effective olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Stevens, A.E.; Beauchamp, J.L.

    1979-10-10

    In this communication the formation, properties and reactions of the gas phase carbenes MnCH/sub 2//sup +/, (CO)/sub 5/MnCH/sub 2//sup +/, and (CO)/sub 4/MnCH/sub 2//sup +/ are described. Reported results include observation of metathesis and abstraction reactions of the methylene ligand with olefins and the first experimental determination of metal-carbene bond dissociation energies. Important points are that: (a) metal-methylene bond energies are extremely strong; and (b) the Mn/sup +/-methylene bond energy is decreased substantially on addition of five carbonyls to the metal center. If the metal-carbene bond energy exceeds 100 kcal/mol, then transfer of the carbene to an olefin to give a cyclopropane or new olefin will be endothermic and thus will not compete with the metathesis reaction. In order to avoid low turnover numbers resulting from consumption of carbene intermediates, strong metal-carbene bonds are a desirable feature of practical metathesis catalysts. (DP)

  15. Acetylene C-H bond dissociation energy using 193. 3-nm photolysis and sub-doppler resolution H-atom spectroscopy: 127 + 1. 5 kcal mol sup minus 1

    Energy Technology Data Exchange (ETDEWEB)

    Segall, J. Lavi, R.; Wen, Y.; Wittig, C. (Univ. of Southern California, Los Angeles (USA))

    1989-10-19

    H atoms are produced by 193.3-nm C{sub 2}H{sub 2} photolysis and probed spectroscopically with sub-Doppler resolution at Lyman-{alpha} by using two-photon, two-frequency ionization, for both expansion-cooled and effusive samples. The maximum Doppler shifts are in agreement with D{sub 0}(C{sub 2}H-H) = 127 {plus minus} 1.5 kcal mol{sup {minus}1}, assuming (i) that the fastest H atoms are produced concomitantly with unexcited C{sub 2}H and (ii) that vibrationally excited C{sub 2}H{sub 2} parent is not the source of these fast H atoms. In the sense that higher detection sensitivity might allow observation of faster H atoms, 127 {plus minus} 1.5 kcal mol{sup {minus}1} is an upper limit.

  16. The Calculation of Bond Dissociation Energies for Azide Group in Some Azido Compounds%对一些叠氮化合物的叠氮自由基键离解能的计算

    Institute of Scientific and Technical Information of China (English)

    邵菊香; 程新路; 杨向东; 葛素红

    2007-01-01

    用4个高精度的完全基组CBS(CBS-Q,CBS-QB3,CBS-Lq和CBS-4M),B3LYP/6-311G**,B3LYP/6-311+G**和MP2配合6-311G**与6-31+G**等多个不同大小的基组的计算方法,对HN3、CH3N3、C2H5N3、NCN3、C2H3N3和NH2CH2N3中离解掉叠氮自由基(·N3)时的键离解能进行计算.将计算的键离解能与实验值进行比较,发现B3LYP和4种完全基组计算方法都不能为这些叠氮化合物计算出满意的键离解能,而MP2方法,尤其配合6-31+G**基组时,能够计算出与实验值吻合得很好的R-N3键离解能.因此,当计算这些中小型叠氮化合物中离解掉叠氮基的键离解能时,用MP2/6-31+G**是一种可靠的计算方法.

  17. Interference Effects in Strong-Field Dissociative Ionization

    CERN Document Server

    Yue, Lun

    2015-01-01

    We theoretically study dissociative ionization of H$_2^+$ exposed to strong linearly polarized few-cycle visible, near-infrared and midinfrared laser pulses. We find rich energy-sharing structures in the combined electron and nuclear kinetic energy spectra with features that are a priori at odds with simple energy conservation arguments. We explain the structures as interferences between wave packets released during different optical cycles, and during the same optical cycle, respectively. Both inter- and intracycle interference structures are clearly visible in the joint energy spectra. The shapes of the interference structures depend on the dynamics leading to the double continuum, and carry sub-femtosecond information.

  18. Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 1. Preparation, dissociations, and energetics of 2-hydroxyoxolan-2-yl radical, neutral isomers, and cations.

    Science.gov (United States)

    Vivekananda, Shetty; Sadílek, Martin; Chen, Xiaohong; Turecek, Frantisek

    2004-07-01

    Collisional neutralization of several isomeric C(4)H(7)O(2) cations is used to generate radicals that share some structural features with transient species that are thought to be produced by radiolysis of 2-deoxyribose. The title 2-hydroxyoxolan-2-yl radical (1) undergoes nearly complete dissociation when produced by femtosecond electron transfer from thermal organic electron donors dimethyl disulfide and N,N-dimethylaniline in the gas phase. Product analysis, isotope labeling ((2)H and (18)O), and potential energy surface mapping by ab initio calculations at the G2(MP2) and B3-PMP2 levels of theory and in combination with Rice-Ramsperger-Kassel-Marcus (RRKM) kinetic calculations are used to assign the major and some minor pathways for 1 dissociations. The major (approximately 90%) pathway is initiated by cleavage of the ring C-5[bond]O bond in 1 and proceeds to form ethylene and *CH(2)COOH as main products, whereas loss of a hydrogen atom forms 4-hexenoic acid as a minor product. Loss of the OH hydrogen atom forming butyrolactone (2, approximately 9%) and cleavage of the C-3[bond]C-4 bonds (<1%) in 1 are other minor pathways. The major source of excitation in 1 is by Franck-Condon effects that cause substantial differences between the adiabatic and vertical ionization of 1 (5.40 and 6.89 eV, respectively) and vertical recombination in the precursor ion 1(+) (4.46 eV). (+)NR(+) mass spectra distinguish radical 1 from isomeric radicals 2-oxo-(1H)oxolanium (3), 1,3-dioxan-2-yl (9), and 1,3-dioxan-4-yl (10) that were generated separately from their corresponding ion precursors.

  19. Monitoring hydrate formation and dissociation in sandstone and bulk with magnetic resonance imaging.

    Science.gov (United States)

    Baldwin, B A; Moradi-Araghi, A; Stevens, J C

    2003-11-01

    Magnetic resonance imaging (MRI) has been shown to be a very effective tool for monitoring the formation and dissociation of hydrates because of the large intensity contrast between the images of the liquid components and the solid hydrate. Tetrahydrofuran/water hydrate was used because the two liquid components are miscible and form hydrate at ambient pressure. These properties made this feasibility study proceed much faster than using methane/water, which requires high pressure to form the hydrate. The formation and dissociation was monitored first in a THF/water-saturated Berea sandstone plug and second in the bulk. In both cases it appeared that nucleation was needed to begin the formation process, i.e., the presence of surfaces in the sandstone and shaking of the bulk solution. Dissociation appeared to be dominated by the rate of thermal energy transfer. The dissociation temperature of hydrate formed in the sandstone plug was not significantly different from the dissociation temperature in bulk.

  20. Trajectory study of dissociation reactions. The single-ensemble method. II

    Science.gov (United States)

    Kutz, H. Douglas; Burns, George

    1981-04-01

    The single uniform ensemble method was previously employed in 3D classical trajectory calculations [H. D. Kutz and G. Burns, J. Chem. Phys. 72, 3652 (1980)]. Presently it is applied to the Br2+Ar system to study nonequilbrium effects in diatom dissociation over a wide temperature range. It was found that, for a given large set of trajectories, observables, such as reaction cross sections or rate constants, are indepedent within four significant figures of the initial distribution function. This indicates a high degree of reliability of the single uniform ensemble method, once the choice of a set of trajectories is made. In order to study dissociation from the low lying energy states, the uniform velocity selection method in trajectory calculations was used. It was found that dissociation from these states contributes but little to the overall dissociation reaction. The latter finding is consistent with the attractive nature of the potential energy surface used, and constitutes an argument against those current theories of diatom dissociation reaction which explains experimental data by postulating a high probability of dissociation from low lying energy states of diatoms. It was found that the contribution from the low lying states to dissociation can be estimated with good accuracy using information theory expressions. Temperature dependence of nonequilibrium effects was investigated between 1 500 and 6 000 °K. In this range the nonequilibrium correction factor varies between 0.2 and 0.5. Angular momentum dependence of such observables as reaction rate constant and reaction cross section was investigated.

  1. Charge-dependent dissociation of insulin cations via ion/ion electron transfer

    Science.gov (United States)

    Liu, Jian; Gunawardena, Harsha P.; Huang, Teng-Yi; McLuckey, Scott A.

    2008-10-01

    The dissociation reactions of various charge states of insulin cations obtained directly from nano-electrospray were investigated as a result of ion/ion electron transfer from azobenzene anions. Data were collected with and without simultaneous ion trap collisional excitation of the first generation charge-reduced product during the ion/ion reaction period. Neither separation of the two constituent chains nor cleavages within the loop defined by the disulfide bridges were observed under normal electron transfer dissociation (ETD) conditions for any of the charge states studied. However, substantial sequence coverage (exocyclic region: 82.6%; entire protein: 38.8%) outside the ring structure was obtained for insulin +6, while only limited coverage (exocyclic: 43.5%; entire protein: 20.4%) was observed for insulin +5 and no dissociation, aside from low abundance side-chain losses, was noted for insulin +4 and +3 in the normal ETD spectra. When the first generation charge-reduced precursor ions were subjected to collisional activation during the ion/ion reaction period, higher sequence coverages were obtained for both insulin +5 (entire protein: 34.7%) and +4 (entire protein: 20.4%) with backbone cleavages occurring within the loop defined by the disulfide bonds. Dissociation of insulin +3 was not significantly improved by the additional activation. Separation of the two constituent chains resulting from cleavages of both of the two disulfide bridges that link the chains was observed for insulin +6, +5, and +4 when the charge-reduced species were activated. The dissociation of disulfide linkages in this study suggests that as the charge state decreases, disulfide bond cleavages dominate over N-C[alpha] bond cleavages in the electron transfer dissociation process.

  2. Density Functional Theory Based on the Electron Distribution on the Energy Coordinate

    CERN Document Server

    Takahashi, Hideaki

    2016-01-01

    We introduced a new electron density n({\\epsilon}) by projecting the spatial electron density n(r) onto the energy coordinate {\\epsilon} defined with the external potential \\upsion (r) of interest. Then, a density functional theory (DFT) was formulated, where n({\\epsilon}) serves as a fundamental variable for the electronic energy. It was demonstrated that the Kohn-Sham equation can also be adapted to the DFT that employs the density n({\\epsilon}) as an argument to the exchange energy functional. An important attribute of the energy density is that it involves the spatially non-local population of the spin-adapted density n(r) at the bond dissociation. By taking advantage of this property we developed a prototype of the static correlation functional employing no empirical parameters, which realized a reasonable dissociation curve for H2 molecule.

  3. Cyanobacterial phycobilisomes: selective dissociation monitored by fluorescence and circular dichroism

    Energy Technology Data Exchange (ETDEWEB)

    Rigbi, M.; Rosinski, J.; Siegelman, H.W.; Sutherland, J.C.

    1980-04-01

    Phycobilisomes are supramolecular assemblies of phycobiliproteins responsible for photosynthetic light collection in red algae and cyanobacteria. They can be selectively dissociated by reduction of temperature and buffer concentration. Phycobilisomes isolated from Fremyella diplosiphon transfer energy collected by C-phycoerythrin and C-phycocyanin to allophycocyanin. The energy transfer to allophycocyanin is nearly abolished at 2/sup 0/C, as indicated by a blue shift in fluorescence emission, and is accompanied by a decrease in the circular dichroism in the region of allophycocyanin absorbance. Further dissociation of the phycobilisomes can be attained by reduction of buffer concentration and holding at 2/sup 0/C. Energy transfer to C-phycocyanin is nearly abolished, and decreases occur in the circular dichroism in the region of C-phycocyanin and C-phycoerythrin absorbance. Complete dissociation of the phycobilisomes at low buffer concentration and 2/sup 0/C requires extended time. Energy transfer to C-phycocyanin is further reduced and the circular dichroism maximum of C-phycoerythrin at 575 nm is lost. Circular dichroism provides information on the hexamer-monomer transitions of the phycobiliproteins, whereas fluorescence is indicative of hexamer-hexamer interactions. We consider that hydrophobic interactions are fundamental to the maintenance of the structure and function of phycobilisomes.

  4. Surface Induced Dissociation Yields Quaternary Substructure of Refractory Noncovalent Phosphorylase B and Glutamate Dehydrogenase Complexes

    Science.gov (United States)

    Ma, Xin; Zhou, Mowei; Wysocki, Vicki H.

    2014-03-01

    Ion mobility (IM) and tandem mass spectrometry (MS/MS) coupled with native MS are useful for studying noncovalent protein complexes. Collision induced dissociation (CID) is the most common MS/MS dissociation method. However, some protein complexes, including glycogen phosphorylase B kinase (PHB) and L-glutamate dehydrogenase (GDH) examined in this study, are resistant to dissociation by CID at the maximum collision energy available in the instrument. Surface induced dissociation (SID) was applied to dissociate the two refractory protein complexes. Different charge state precursor ions of the two complexes were examined by CID and SID. The PHB dimer was successfully dissociated to monomers and the GDH hexamer formed trimeric subcomplexes that are informative of its quaternary structure. The unfolding of the precursor and the percentages of the distinct products suggest that the dissociation pathways vary for different charge states. The precursors at lower charge states (+21 for PHB dimer and +27 for GDH hexamer) produce a higher percentage of folded fragments and dissociate more symmetrically than the precusors at higher charge states (+29 for PHB dimer and +39 for GDH hexamer). The precursors at lower charge state may be more native-like than the higher charge state because a higher percentage of folded fragments and a lower percentage of highly charged unfolded fragments are detected. The combination of SID and charge reduction is shown to be a powerful tool for quaternary structure analysis of refractory noncovalent protein complexes, as illustrated by the data for PHB dimer and GDH hexamer.

  5. The effect of pi-stacking, h-bonding, and electrostatic interactions on the ionization energies of nucleic acid bases: adenine-adenine, thymine-thymine and adenine-thymine dimers

    Energy Technology Data Exchange (ETDEWEB)

    Bravaya, Ksenia B.; Kostko, Oleg; Ahmed, Musahid; Krylov, Anna I.

    2009-09-02

    A combined theoretical and experimental study of the ionized dimers of thymine and adenine, TT, AA, and AT, is presented. Adiabatic and vertical ionization energies(IEs) for monomers and dimers as well as thresholds for the appearance of the protonated species are reported and analyzed. Non-covalent interactions stronglyaffect the observed IEs. The magnitude and the nature of the effect is different for different isomers of the dimers. The computations reveal that for TT, the largestchanges in vertical IEs (0.4 eV) occur in asymmetric h-bonded and symmetric pi- stacked isomers, whereas in the lowest-energy symmetric h-bonded dimer the shiftin IEs is much smaller (0.1 eV). The origin of the shift and the character of the ionized states is different in asymmetric h-bonded and symmetric stacked isomers. Inthe former, the initial hole is localized on one of the fragments, and the shift is due to the electrostatic stabilization of the positive charge of the ionized fragment by thedipole moment of the neutral fragment. In the latter, the hole is delocalized, and the change in IE is proportional to the overlap of the fragments' MOs. The shifts in AAare much smaller due to a less effcient overlap and a smaller dipole moment. The ionization of the h-bonded dimers results in barrierless (or nearly barrierless) protontransfer, whereas the pi-stacked dimers relax to structures with the hole stabilized by the delocalization or electrostatic interactions.

  6. Multiphoton dissociation and ionization of nickelocene

    Science.gov (United States)

    Leutwyler, Samuel; Even, Uzi; Jortner, Joshua

    1981-01-01

    In this paper we report the results of an experimental study of collision-free molecular multiphoton dissociation (MPD) and molecular multiphoton ionization (MPI) of nickelocene (NiC 10H 10), induced by the light of a tunable dye laser in the wavelength region 3750-5200 A. The spectral dependence of the ion signal reveals a multitude of narrow (fwhm from <0.5 cm -1 to 1.5 cm -1) intense peaks superimposed on a very weak background (relative amplitude ratio for peaks/background ≈ 10 3). The sharp resonances in the ion signal are attributed, on the basis of spectroscopic analysis, to two-photon resonant three-photon ionization of Ni(I) and to one-photon resonant three-photon ionization of Ni(I), the Ni(I) being produced by MPD of nickelocene. The ion signal in the spectral range 3750-3950 A reveals enhanced continuous background due to MPI of nickelocene. This ion signal spectra, together with studies of the intensity dependence of the overall (nickelocene MPD) - (Ni(I) MPI) processes, as well as the (nickelocene molecular MPI) reaction, reveal four reactive processes. (a) Two-photon molecular MPI for hω ⩾ 3.10 eV photons. (b) Three-photon molecular MPI for hω = 3.10-2.10 eV. (c) Two-photon MPD at hω ⩾ 2.86 eV. (d) Three-photon MPD for hω = 2.8-1.9 eV. The overall dissociation energy of nickelocene (Nicp 2) to give Ni + 2cp was determined to be 5.76 ± 0.60 eV and the two-photon ionization potential of this molecule is 6.29 ± 0.015 eV. Our results provide dynamic evidence concerning a simultaneous "explosive" photodissociation mechanism of Nicp 2 by process (c) and for the dominating role of the dissociative channel, characterized by a branching ratio of ⩾50 in favor of predissociation over autoionization, for process (c) at 6.3-6.6 eV. The MPD processes (c) and (d) are expected to exhibit intramolecular erosion of phase coherence effects. Processes (c) and (d) are of high efficiency ≈0.01 ions/molecule at saturation exhibited at laser power of ≈ 10

  7. Comprehensive analysis of individual pulp fiber bonds quantifies the mechanisms of fiber bonding in paper

    Science.gov (United States)

    Hirn, Ulrich; Schennach, Robert

    2015-05-01

    The process of papermaking requires substantial amounts of energy and wood consumption, which contributes to larger environmental costs. In order to optimize the production of papermaking to suit its many applications in material science and engineering, a quantitative understanding of bonding forces between the individual pulp fibers is of importance. Here we show the first approach to quantify the bonding energies contributed by the individual bonding mechanisms. We calculated the impact of the following mechanisms necessary for paper formation: mechanical interlocking, interdiffusion, capillary bridges, hydrogen bonding, Van der Waals forces, and Coulomb forces on the bonding energy. Experimental results quantify the area in molecular contact necessary for bonding. Atomic force microscopy experiments derive the impact of mechanical interlocking. Capillary bridges also contribute to the bond. A model based on the crystal structure of cellulose leads to values for the chemical bonds. In contrast to general believe which favors hydrogen bonding Van der Waals bonds play the most important role according to our model. Comparison with experimentally derived bond energies support the presented model. This study characterizes bond formation between pulp fibers leading to insight that could be potentially used to optimize the papermaking process, while reducing energy and wood consumption.

  8. 3c/4e [small sigma, Greek, circumflex]-type long-bonding competes with ω-bonding in noble-gas hydrides HNgY (Ng = He, Ne, Ar, Kr, Xe, Rn; Y = F, Cl, Br, I): a NBO/NRT perspective.

    Science.gov (United States)

    Zhang, Guiqiu; Li, Hong; Weinhold, Frank; Chen, Dezhan

    2016-03-21

    Noble-gas hydrides HNgY are frequently described as a single ionic form (H-Ng)(+)Y(-). We apply natural bond orbital (NBO) and natural resonance theory (NRT) analyses to a series of noble-gas hydrides HNgY (Ng = He, Ne, Ar, Kr, Xe, Rn; Y = F, Cl, Br, I) to gain quantitative insight into the resonance bonding of these hypervalent molecules. We find that each of the studied species should be better represented as a resonance hybrid of three leading resonance structures, namely, H-Ng(+ -):Y (I), H:(- +)Ng-Y (II), and H^Y (III), in which the "ω-bonded" structures I and II arise from the complementary donor-acceptor interactions nY → σ*HNg and nH → σ*NgY, while the "long-bond" ([small sigma, Greek, circumflex]-type) structure III arises from the nNg → [small sigma, Greek, circumflex]*HY/[small sigma, Greek, circumflex]HY interaction. The bonding for all of the studied molecules can be well described in terms of the continuously variable resonance weightings of 3c/4e ω-bonding and [small sigma, Greek, circumflex]-type long-bonding motifs. Furthermore, we find that the calculated bond orders satisfy a generalized form of "conservation of bond order" that incorporates both ω-bonding and long-bonding contributions [viz., (bHNg + bNgY) + bHY = bω-bonding + blong-bonding = 1]. Such "conservation" throughout the title series implies a competitive relationship between ω-bonding and [small sigma, Greek, circumflex]-type long-bonding, whose variations are found to depend in a chemically reasonable manner on the electronegativity of Y and the outer valence-shell character of the central Ng atom. The calculated bond orders are also found to exhibit chemically reasonable correlations with bond lengths, vibrational frequencies, and bond dissociation energies, in accord with Badger's rule and related empirical relationships. Overall, the results provide electronic principles and chemical insight that may prove useful in the rational design of noble-gas hydrides of

  9. Physical Nature of Hydrogen Bond

    CERN Document Server

    Zhyganiuk, I V

    2015-01-01

    The physical nature and the correct definition of hydrogen bond (H-bond) are considered.\\,\\,The influence of H-bonds on the thermodynamic, kinetic, and spectroscopic properties of water is analyzed.\\,\\,The conventional model of H-bonds as sharply directed and saturated bridges between water molecules is incompatible with the behavior of the specific volume, evaporation heat, and self-diffusion and kinematic shear viscosity coefficients of water. On the other hand, it is shown that the variation of the dipole moment of a water molecule and the frequency shift of valence vibrations of a hydroxyl group can be totally explained in the framework of the electrostatic model of H-bond.\\,\\,At the same time, the temperature dependences of the heat capacity of water in the liquid and vapor states clearly testify to the existence of weak H-bonds.\\,\\,The analysis of a water dimer shows that the contribution of weak H-bonds to its ground state energy is approximately 4--5 times lower in comparison with the energy of electr...

  10. Gas-phase energies of actinide oxides -- an assessment of neutral and cationic monoxides and dioxides from thorium to curium

    Energy Technology Data Exchange (ETDEWEB)

    Marcalo, Joaquim; Gibson, John K.

    2009-08-10

    An assessment of the gas-phase energetics of neutral and singly and doubly charged cationic actinide monoxides and dioxides of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium is presented. A consistent set of metal-oxygen bond dissociation enthalpies, ionization energies, and enthalpies of formation, including new or revised values, is proposed, mainly based on recent experimental data and on correlations with the electronic energetics of the atoms or cations and with condensed-phase thermochemistry.

  11. Cell Dissociation : A Cohesive Force of Hydrodynamic Origin

    CERN Document Server

    Vasseur, Hugues

    2007-01-01

    When an experimentalist or a biological mechanism applies an external force onto a cell chemically sticking to its substrate, a reacting 'suction' force, due to the slow penetration of the surrounding fluid between the cell and the substrate, opposes to the dissociation. This force can overcome other known adhesive forces when the process is sufficiently violent (typically 100000pN). Its maximal contribution to the total adhesive energy of the cell can then be estimated to 0.002 J/m2. The physical origin of this effect is quite simple, and it may be compared with that leaning a 'suction-cup' against a bathroom wall. We address the consequences of this effect on (i) the dissociation energy, (ii) the motion of the fluid surrounding the cell, more especially, on the pumping of the fluid by moving cells, and (iii) the inhibition of cell motion.

  12. A valence bond study of three-center four-electron pi bonding: electronegativity vs electroneutrality.

    Science.gov (United States)

    DeBlase, Andrew; Licata, Megan; Galbraith, John Morrison

    2008-12-18

    Three-center four-electron (3c4e) pi bonding systems analogous to that of the ozone molecule have been studied using modern valence bond theory. Molecules studied herein consist of combinations of first row atoms C, N, and O with the addition of H atoms where appropriate in order to preserve the 3c4e pi system. Breathing orbital valence bond (BOVB) calculations were preformed at the B3LYP/6-31G**-optimized geometries in order to determine structural weights, pi charge distributions, resonance energies, and pi bond energies. It is found that the most weighted VB structure depends on atomic electronegativity and charge distribution, with electronegativity as the dominant factor. By nature, these systems are delocalized, and therefore, resonance energy is the main contributor to pi bond energies. Molecules with a single dominant VB structure have low resonance energies and therefore low pi bond energies.

  13. Comparison of dissociation mechanism between collisionally activated dissociation and charge inversion using alkali metal targets for chlorophenol isomers

    Science.gov (United States)

    Hayakawa, Shigeo; Kawamura, Yoshiaki; Takahashi, Yutaka

    2005-11-01

    Chlorinated aromatic compounds are well-known environmental pollutants whose toxicities depend dramatically on the chlorine substitution pattern, making differentiation of chlorophenol isomers important for environmental analysis. Collisionally activated dissociation (CAD) spectra and charge inversion spectra of ortho-, meta-, and para-chlorophenols (ClC6H4OH) and their partially deuterated forms (ClC6H4OD) were measured using alkali metal targets. The peaks associated with C6H4O+ and C5H5Cl+ ions observed in the CAD spectra result from the loss of HCl and CO fragments, respectively, after the re-arrangement of the hydroxyl hydrogen atom. The peaks associated with C6H4OH- and ClC6H4O- ions observed in the charge inversion spectra result from Cl loss and from hydroxyl bond dissociation, respectively. Isomeric differentiation is possible based on the clear differences observed in the relative intensities of these pairs of peaks. Although the intensities of the peaks associated with C6H4O+ relative to those of C5H5Cl+ in the CAD spectra are independent of the target species, the intensities of the peaks associated with C6H4OH- relative to those of ClC6H4O- in the charge inversion spectra are target dependent. The isomeric dependence of the positive ion distribution patterns in the CAD spectra is proposed to be due to the differences in the rate of the hydrogen atom re-arrangement process. In contrast, the isomeric dependence of the negative ion distribution patterns in the charge inversion spectra is attributed to differences in the bond strength involved in the direct dissociation process in the neutral intermediate species.

  14. Charmonium dissociation cross sections and charmonium dissociation rates in hadronic matter

    CERN Document Server

    Liu, Feng-Rong; Xu, Xiao-Ming

    2016-01-01

    K*-charmonium dissociation reactions in hadronic matter are studied in the Born approximation, in the quark-interchange mechanism, and with a temperature-dependent quark potential. We obtain the temperature dependence of unpolarized cross sections for K*-charmonium dissociation reactions which produce charmed mesons and charmed strange mesons. We use the cross sections for charmonium dissociation in collisions with pion, rho meson, kaon, vector kaon, and eta meson to calculate dissociation rates of charmonium with the five types of mesons. Because of the temperature dependence of the meson masses, dissociation cross sections, a