Dissociation of acetaldehyde in intense laser field: Coulomb explosion or field-assisted dissociation?

Science.gov (United States)

Elshakre, Mohamed E.; Gao, Lirong; Tang, Xiaoping; Wang, Sufan; Shu, Yafei; Kong, Fanao

2003-09-01

Dissociation of acetaldehyde in moderate strong laser field of 1013-1014W/cm2 was investigated. Singly charged parent ion CH3CHO+ and fragmental ions CH3+, CHO+, C2H4+, O+, CH2CHO+, and H+ were produced by 800 nm laser of 100 fs pulse duration and recorded by time-of-flight mass spectrometer. The CH3+ fragment further dissociated to CH2+, CH+, and C+ ions at higher intensity. Ab initio calculated results show that the singly-, doubly-, and triply charged parent ions are stable. So, the dissociation mechanism was not due to Coulomb explosion of multicharged ion. A field-assisted dissociation (FAD) theory, which assumes that only one bond undergoes dissociation while the rest of the molecular geometry stays unchanged, was employed to treat the dissociation dynamics. Accordingly, the dressed potential energy surfaces of the ground state for the parent and the fragment ions were calculated. Corresponding quasiclassical trajectory calculations show that the bond ruptures take place in the order of C-C, C-O, and C-H, agreeing with the observation. The observed angular dependence and charge distribution of the product ions can also be interpreted by the FAD theory.

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.

Cross-Dehydrogenative Coupling Reactions Between P(O)-H and X-H (X = S, N, O, P) Bonds.

Science.gov (United States)

Hosseinian, Akram; Farshbaf, Sepideh; Fekri, Leila Zare; Nikpassand, Mohammad; Vessally, Esmail

2018-05-26

P(O)-X (X = S, N, O, P) bond-containing compounds have extensive application in medicinal chemistry, agrochemistry, and material chemistry. These useful organophosphorus compounds also have many applications in organic synthesis. In light of the importance of titled compounds, there is continuing interest in the development of synthetic methods for P(O)-X bonds construction. In the last 4 years, the direct coupling reaction of P(O)-H compounds with thiols, alcohols, and amines/amides has received much attention because of the atom-economic character. This review aims to give an overview of new developments in cross-dehydrogenative coupling reactions between P(O)-H and X-H (X = S, N, O, P) bonds, with special emphasis on the mechanistic aspects of the reactions.

Strain effect on the adsorption, diffusion, and molecular dissociation of hydrogen on Mg (0001) surface

Energy Technology Data Exchange (ETDEWEB)

Lei, Huaping; Wang, Caizhuang; Yao, Yongxin; Hupalo, Myron [Ames Laboratory, USDOE, Ames, Iowa 50011 (United States); Wang, Yangang [Ames Laboratory, USDOE, Ames, Iowa 50011 (United States); Supercomputing Center of Computer Network Information Center, CAS, Beijing 100190 (China); McDougall, Dan; Tringides, Michael; Ho, Kaiming [Ames Laboratory, USDOE, Ames, Iowa 50011 (United States); Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011 (United States)

2013-12-14

The adsorption, diffusion, and molecular dissociation of hydrogen on the biaxially strained Mg (0001) surface have been systematically investigated by the first principle calculations based on density functional theory. When the strain changes from the compressive to tensile state, the adsorption energy of H atom linearly increases while its diffusion barrier linearly decreases oppositely. The dissociation barrier of H{sub 2} molecule linearly reduces in the tensile strain region. Through the chemical bonding analysis including the charge density difference, the projected density of states and the Mulliken population, the mechanism of the strain effect on the adsorption of H atom and the dissociation of H{sub 2} molecule has been elucidated by an s-p charge transfer model. With the reduction of the orbital overlap between the surface Mg atoms upon the lattice expansion, the charge transfers from p to s states of Mg atoms, which enhances the hybridization of H s and Mg s orbitals. Therefore, the bonding interaction of H with Mg surface is strengthened and then the atomic diffusion and molecular dissociation barriers of hydrogen decrease accordingly. Our works will be helpful to understand and to estimate the influence of the lattice deformation on the performance of Mg-containing hydrogen storage materials.

Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds.

Science.gov (United States)

Alkorta, Ibon; Legon, Anthony C

2017-10-23

It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N₂, CO, HC≡CH, CH₂=CH₂, C₃H₆, PH₃, H₂S, HCN, H₂O, H₂CO and NH₃) and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H₂O, F₂, Cl₂, Br₂, ClF, BrCl, H₃SiF, H₃GeF, F₂CO, CO₂, N₂O, NO₂F, PH₂F, AsH₂F, SO₂, SeO₂, SF₂, and SeF₂) can be represented to good approximation by means of the equation D e = c ' N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ' is a constant, conveniently chosen to have the value 1.00 kJ mol -1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1) the hydrogen bond; (2) the halogen bond; (3) the tetrel bond; (4) the pnictogen bond; and (5) the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

Catch bonding in the forced dissociation of a polymer endpoint

Science.gov (United States)

Vrusch, Cyril; Storm, Cornelis

2018-04-01

Applying a force to certain supramolecular bonds may initially stabilize them, manifested by a lower dissociation rate. We show that this behavior, known as catch bonding and by now broadly reported in numerous biophysics bonds, is generically expected when either or both the trapping potential and the force applied to the bond possess some degree of nonlinearity. We enumerate possible scenarios and for each identify the possibility and, if applicable, the criterion for catch bonding to occur. The effect is robustly predicted by Kramers theory and Mean First Passage Time theory and confirmed in direct molecular dynamics simulation. Among the catch scenarios, one plays out essentially any time the force on the bond originates in a polymeric object, implying that some degree of catch bond behavior is to be expected in many settings relevant to polymer network mechanics or optical tweezer experiments.

DFT study of adsorption and dissociation behavior of H2S on Fe-doped graphene

International Nuclear Information System (INIS)

Zhang, Hong-ping; Luo, Xue-gang; Song, Hong-tao; Lin, Xiao-yan; Lu, Xiong; Tang, Youhong

2014-01-01

Highlights: • Fe-doped and Pt-doped graphene can significantly improve the interactions between H 2 S and graphene. • The location of S had an important role in the interactions between H 2 S and Fe-doped graphene. • The influence of Fe-S distance can be very weak in a certain range and H 2 S can be dissociated into S and H 2 . - Abstracts: Understanding the interaction mechanisms of hydrogen sulfide (H 2 S) with graphene is important in developing graphene-based sensors for gas detection and removal. In this study, the effects of doped Fe atom on interaction of H 2 S with graphene were investigated by density functional theory calculations. Analyses of adsorption energy, electron density difference, and density of states indicated that the doped Fe atom can significantly improve the interaction of H 2 S gas molecules with graphene, as well as Pt-doped graphene. The location of the sulfur atom is important in the interactions between H 2 S and Fe-doped graphene. The influence of the Fe-S distance can be very weak within a certain distance, as simulated in this study

Role of dispersion corrected hybrid GGA class in accurately calculating the bond dissociation energy of carbon halogen bond: A benchmark study

Science.gov (United States)

Kosar, Naveen; Mahmood, Tariq; Ayub, Khurshid

2017-12-01

Benchmark study has been carried out to find a cost effective and accurate method for bond dissociation energy (BDE) of carbon halogen (Csbnd X) bond. BDE of C-X bond plays a vital role in chemical reactions, particularly for kinetic barrier and thermochemistry etc. The compounds (1-16, Fig. 1) with Csbnd X bond used for current benchmark study are important reactants in organic, inorganic and bioorganic chemistry. Experimental data of Csbnd X bond dissociation energy is compared with theoretical results. The statistical analysis tools such as root mean square deviation (RMSD), standard deviation (SD), Pearson's correlation (R) and mean absolute error (MAE) are used for comparison. Overall, thirty-one density functionals from eight different classes of density functional theory (DFT) along with Pople and Dunning basis sets are evaluated. Among different classes of DFT, the dispersion corrected range separated hybrid GGA class along with 6-31G(d), 6-311G(d), aug-cc-pVDZ and aug-cc-pVTZ basis sets performed best for bond dissociation energy calculation of C-X bond. ωB97XD show the best performance with less deviations (RMSD, SD), mean absolute error (MAE) and a significant Pearson's correlation (R) when compared to experimental data. ωB97XD along with Pople basis set 6-311g(d) has RMSD, SD, R and MAE of 3.14 kcal mol-1, 3.05 kcal mol-1, 0.97 and -1.07 kcal mol-1, respectively.

Dissociative recombination of molecular ions H2+

International Nuclear Information System (INIS)

Abarenov, A.V.; Marchenko, V.S.

1989-01-01

The total cross sections of dissociation and dissociative recombination of slow electrons and molecular ions H 2 + have been calculated in terms of the quasiclassical and dipole approximations. In the calculations allowance was made for the quantum nature of vibrational motion of heavy particles and presence of autoionization of divergence states of the H 2 (Σ u , nl) molecules. It is shown that the H 2 + ion dissociation cross sections are dominant in increase of the electron energy in the ε >or approx. 2-3 eV region for H 2 + (v) ion distribution over the vibrational levels characteristic for the beam experiments. 15 refs.; 5 figs

Multiple C-H Bond Activations and Ring-Opening C-S Bond Cleavage of Thiophene by Dirhenium Carbonyl Complexes.

Science.gov (United States)

Adams, Richard D; Dhull, Poonam; Tedder, Jonathan D

2018-06-14

The reaction of Re 2 (CO) 8 (μ-C 6 H 5 )(μ-H) (1) with thiophene in CH 2 Cl 2 at 40 °C yielded the new compound Re 2 (CO) 8 (μ-η 2 -SC 4 H 3 )(μ-H) (2), which contains a bridging σ-π-coordinated thienyl ligand formed by the activation of the C-H bond at the 2 position of the thiophene. Compound 2 exhibits dynamical activity on the NMR time scale involving rearrangements of the bridging thienyl ligand. The reaction of compound 2 with a second 1 equiv of 1 at 45 °C yielded the doubly metalated product [Re 2 (CO) 8 (μ-H)] 2 (μ-η 2 -2,3-μ-η 2 -4,5-C 4 H 2 S) (3), formed by the activation of the C-H bond at the 5 position of the thienyl ligand in 2. Heating 3 in a hexane solvent to reflux transformed it into the ring-opened compound Re(CO) 4 [μ-η 5 -η 2 -SCC(H)C(H)C(H)][Re(CO) 3 ][Re 2 (CO) 8 (μ-H)] (4) by the loss of one CO ligand. Compound 4 contains a doubly metalated 1-thiapentadienyl ligand formed by the cleavage of one of the C-S bonds. When heated to reflux (125 °C) in an octane solvent in the presence of H 2 O, the new compound Re(CO) 4 [η 5 -μ-η 2 -SC(H)C(H)C(H)C(H)]Re(CO) 3 (5) was obtained by cleavage of the Re 2 (CO) 8 (μ-H) group from 4 with formation of the known coproduct [Re(CO) 3 (μ 3 -OH)] 4 . All new products were characterized by single-crystal X-ray diffraction analyses.

Search for the H Dibaryon (S = -2) Using Diffraction Dissociation

Energy Technology Data Exchange (ETDEWEB)

Ecklund, K.

2005-04-05

The observed hadrons are understood as bound states of three quarks (baryons) or of quarks and antiquarks (mesons). To date no six quark bound state other than the loosely bound deuteron has been observed. Quantum Chromodynamics permits other color-singlet bound states of quarks, and a number of phenomenological models extended from the baryon (q{sup 3}) and meson (q{bar q}) sectors predict bound six quark states (q{sup 6}). The most probable candidate is the H dibaryon, composed of two each of the lightest three quarks (udsuds), with quantum numbers J{sup P} = 0{sup +}, I = 0 and S = -2. Its mass would likely be between the deuteron mass and twice the {Lambda} (uds) mass. This dissertation describes a search for the H dibaryon conducted in a neutral beam at the Brookhaven National Laboratory's Alternating Gradient Synchrotron. In the experiment a 24.1 GeV/c proton beam struck a 1.35 interaction length platinum target producing a collimated neutral beam (62 {mu}sr at 65 mrad from the incident proton direction) which propagated through a 18 m vacuum decay tank before entering a double arm spectrometer. Approximately 20 m from the production target a 10 cm (0.15 interaction length) long active scintillator dissociator was placed in the beam.

Photo-dissociation of hydrogen passivated dopants in gallium arsenide

International Nuclear Information System (INIS)

Tong, L.; Larsson, J.A.; Nolan, M.; Murtagh, M.; Greer, J.C.; Barbe, M.; Bailly, F.; Chevallier, J.; Silvestre, F.S.; Loridant-Bernard, D.; Constant, E.; Constant, F.M.

2002-01-01

A theoretical and experimental study of the photo-dissociation mechanisms of hydrogen passivated n- and p-type dopants in gallium arsenide is presented. The photo-induced dissociation of the Si Ga -H complex has been observed for relatively low photon energies (3.48 eV), whereas the photo-dissociation of C As -H is not observed for photon energies up to 5.58 eV. This fundamental difference in the photo-dissociation behavior between the two dopants is explained in terms of the localized excitation energies about the Si-H and C-H bonds

Relationship between the Bond dissociation energies and impact sensitivities of some nitro-explosives

Energy Technology Data Exchange (ETDEWEB)

Song, Xiao-Shu [School of Physics and Chemistry, Guizhou Normal University, Guiyang (China); Institute of Atomic and Molecular Physics, Sichuan University, Chengdu (China); Cheng, Xin-Lu; Yang, Xiang-Dong [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu (China); He, Bi [Institute of Chemical Materials, CAEP, Mianyang (China)

2006-08-15

The bond dissociation energy (BDE) for removal of the NO{sub 2} group for eleven CHNO nitro-containing explosive molecules is studied to find its correlation with impact sensitivity. The BDE for removal of the NO{sub 2} group in nitroaromatic molecules with nitro alkyl, and esters with nitro alkyl, is calculated using the B3LYP method of Density Functional Theory with the 6-31G* basis set. The relationship between the impact sensitivities and the weakest C-NO{sub 2} bond dissociation energy values is examined. The results indicate a nearly linear correlation between the impact sensitivity and the ratio of the BDE value to the total molecular energy. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

Enthalpy of formation of anisole: implications for the controversy on the O-H bond dissociation enthalpy in phenol.

Science.gov (United States)

Simões, Ricardo G; Agapito, Filipe; Diogo, Hermínio P; da Piedade, Manuel E Minas

2014-11-20

Significant discrepancies in the literature data for the enthalpy of formation of gaseous anisole, ΔfHmo(PhOCH3, g), have fueled an ongoing controversy regarding the most reliable enthalpy of formation of the phenoxy radical and of the gas phase O-H bond dissociation enthalpy, DHo(PhO-H), in phenol. In the present work ΔfHmo(PhOCH3, g) was reassessed using a combination of calorimetric determinations and high-level (W2-F12) ab initio calculations. Static-bomb combustion calorimetry led to the standard molar enthalpy of formation of liquid anisole at 298.15 K, ΔfHmo(PhOCH3, l) = −(117.1 ± 1.4) kJ·mol(-1). The corresponding enthalpy of vaporization was obtained as, ΔvapHmo(PhOCH3) = 46.41 ± 0.26 kJ·mol(-1), by Calvet-drop microcalorimetry. These results give ΔfHmo(PhOCH3, g) = −(70.7 ± 1.4) kJ·mol(-1), in excellent agreement with ΔfHmo(PhOCH3, g) = −(70.8 ± 3.2) kJ·mol(-1), obtained from the W2-F12 calculations. The ΔfHmo(PhOCH3, g) here recommended leads to ΔfHmo(PhO•, g) = 55.5 ± 2.4 kJ·mol(-)1 and DH°(PhO-H) = 368.1 ± 2.6 kJ·mol(-1).

Bond rearrangement caused by sudden single and multiple ionization of water molecules

International Nuclear Information System (INIS)

Ben-Itzhak, I.; Sayler, A. Max; Leonard, M.; Maseberg, J.W.; Hathiramani, D.; Wells, E.; Smith, M.A.; Xia, Jiangfan; Wang, Pengqian; Carnes, K.D.; Esry, B.D.

2005-01-01

Bond rearrangement, namely the dissociation of water into H 2 + +O q+ following ionization by fast proton and highly charged ion impact, was investigated. Single ionization by fast proton impact exhibits a strong isotopic effect, the dissociation of H 2 O + ->H 2 + +O being about twice as likely as D 2 O + ->D 2 + +O, with HDO + ->HD + +O in between. This suggests that the bond rearrangement does not happen during the slow dissociation, but rather during the very fast ionization, and thus H 2 + should also be produced when the water molecule is multiply ionized. We observed that the H 2 + +O + and H 2 + +O 2+ production in 1MeV/amu F 7+ +H 2 O collisions are 0.209+/-0.006% and 0.0665+/-0.003%, respectively, of the main double-ionization dissociation product, H 2 O 2+ ->H + +OH + . This ratio is similar to the triple to double ionization ratio in similar collisions with atomic targets thus suggesting that the bond-rearrangement fraction out of each ionization level is approximately constant. Similar dissociation channels in the heavier water isotopes, which are expected to be smaller, are under study. Finally, the fragmentation of HDO exhibits very strong isotopic preference for breaking the OH bond over the OD bond

Phenylacetylene and H bond

Indian Academy of Sciences (India)

... all resembling H bonds. Non-linear H bonds due to secondary interactions. C-H stretching frequency shows blue shift. Heavy atom distances are longer than the sum of van der Waals radii. Formed a task group through IUPAC to come up with a modern definition of H bond. 15 international experts including Desiraju.

Nonperfect synchronization of bond-forming and bond-rupturing processes in the reaction H + H2 → H2 + H

International Nuclear Information System (INIS)

Chandra, A.K.; Rao, V.S.

1996-01-01

The simplest prototypical hydrogen transfer reaction, i.e., H + H 2 → H 2 + H, is studied by the quantum-mechanical ab initio methods. Results reveal that during this reaction free valence which almost equals the square of the spin density develops on the migrating hydrogen atom. Bond orders are calculated using Mayer's formalism. Both the variations of bond orders and bond lengths along the reaction path are examined. This analysis reveals that the bond formation and bond cleavage processes in this reaction are not perfectly synchronous. The bond clevage process is slightly more advanced on the reaction path. 38 refs., 6 figs., 2 tabs

Electronic structure of homoleptic transition metal hydrides: TiH4, VH4, CrH4, MnH4, FeH4, CoH4, and NiH4

International Nuclear Information System (INIS)

Hood, D.M.; Pitzer, R.M.; Schaefer III, H.F.

1979-01-01

Ab initio molecular electronic structure theory has been applied to the family of transition metal tetrahydrides TiH 4 through NiH 4 . For the TiH 4 molecule a wide range of contracted Gaussian basis sets has been tested at the self-consistent-field (SCF) level of theory. The largest basis, labeled M(14s 11p 6d/10s 8p 3d), H(5s 1p/3s 1p), was used for all members of the series and should yield wave functions approaching true Hartree-Fock quality. Predicted SCF dissociation energies (relative to M+4H) and M--H bond distances are TiH 4 132 kcal, 1.70 A; VH 4 86 kcal, 1.64 A; CrH 4 65 kcal, 1.59 A; MnH 4 -- 36 kcal, 1.58 A; FeH 4 0 kcal, 1.58 A; CoH 4 27 kcal, 1.61 A; and NiH 4 18 kcal, 1.75 A. It should be noted immediately that each of these SCF dissociation energies will be increased by electron correlation effects by perhaps as much as 90 kcal. For all of these molecules except TiH 4 excited states have also been studied. One of the most interesting trends seen for these excited states is the shortening of the M--H bond as electrons are transferred from the antibonding 4t 2 orbital to the nonbonding 1e orbitals

Dissociation of Methanol and Acetylene by slow Highly Charged Ion Collision

International Nuclear Information System (INIS)

De, Sankar; Rajput, Jyoti; Roy, A; Ahuja, R; Ghosh, P N; Safvan, C P

2007-01-01

We report here the results of dissociation of multiple charged methanol and acetylene molecules in collision with 1.2 MeV Ar 8+ projectiles. We observed a wide range of dissociation products from the TOF spectrum starting from undissociated molecular ions, fragments losing an hydrogen atom due to breakage of C-H and/or O-H bonds, to complete rupture of C-C and C-O skeletons for the respective molecules. From the coincidence map of the fragments, we could separate out the different dissociation channels between carbon and oxygen ionic fragments as well as complete two-body dissociation events. The most striking feature in the breakup of CH 3 OH is the formation of H 2 + and H 3 + due to intramolecular rearrangement of the C-H bonds within the methyl group. In dissociative ionization studies of C 2 H 2 , we observed a diatom-like behaviour of the C-C charged complex as evidenced from the measured slopes of the coincidence islands for carbon atomic charged fragments and theoretical values determined from the charge and momentum distribution of the correlated particles. The shape and orientation of the islands give further information about the momentum balance in the fragmentation process in two-body dissociation

What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os).

Science.gov (United States)

Pandey, Krishna K

2012-03-21

Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of

Dissociative resonance electron capture in methylmercaptane and methylmercaptane-d3

International Nuclear Information System (INIS)

Sugiura, Toshio; Arakawa, Kazuo.

1975-01-01

The formation of negative ions by electron impact of methylmercaptane and methylmercaptane-3 3 has been investigated as a function of the electron energy. Appearance potentials, energies of resonance peaks, full widths of half maxima in resonance peak and relative formation cross sections have been determined about the negative ions of H - , D - , CH 3 S - , CD 3 S - , SH - , S - , CH 2 - , CD 2 - , Ch - and CD - . The dissociation energy of S-H bond and an electron affinity of CH 3 S radical have been determined as 4.7 +- 0.1 and 3.18 +- 0.2 eV, respectively. (auth.)

Dissociation energy of the ground state of NaH

International Nuclear Information System (INIS)

Huang, Hsien-Yu; Lu, Tsai-Lien; Whang, Thou-Jen; Chang, Yung-Yung; Tsai, Chin-Chun

2010-01-01

The dissociation energy of the ground state of NaH was determined by analyzing the observed near dissociation rovibrational levels. These levels were reached by stimulated emission pumping and fluorescence depletion spectroscopy. A total of 114 rovibrational levels in the ranges 9≤v '' ≤21 and 1≤J '' ≤14 were assigned to the X 1 Σ + state of NaH. The highest vibrational level observed was only about 40 cm -1 from the dissociation limit in the ground state. One quasibound state, above the dissociation limit and confined by the centrifugal barrier, was observed. Determining the vibrational quantum number at dissociation v D from the highest four vibrational levels yielded the dissociation energy D e =15 815±5 cm -1 . Based on new observations and available data, a set of Dunham coefficients and the rotationless Rydberg-Klein-Rees curve were constructed. The effective potential curve and the quasibound states were discussed.

Inhibition and Promotion of Pyrolysis by Hydrogen Sulfide (H₂S) and Sulfanyl Radical (SH)

DEFF Research Database (Denmark)

Zeng, Zhe; Altarawneh, Mohammednoor; Oluwoye, Ibukun

2016-01-01

processes. For the three groups of hydrocarbon, Evans–Polanyi plots display linear correlations between the bond dissociation enthalpies of the abstracted hydrogens and the relevant activation energies. In the case of methane, we demonstrated that the reactivity of SH radicals toward abstracting H atoms......This study resolves the interaction of sulfanyl radical (SH) with aliphatic (C1–C4) hydrocarbons, using CBS-QB3 based calculations. We obtained the C–H dissociation enthalpies and located the weakest link in each hydrocarbon. Subsequent computations revealed that, H abstraction by SH from...... the weakest C–H sites in alkenes and alkynes, except for ethylene, appears noticeably exothermic. Furthermore, abstraction of H from propene, 1-butene, and iso-butene displays pronounced spontaneity (i.e., ΔrG° bond. However...

Relationships for the impact sensitivities of energetic C-nitro compounds based on bond dissociation energy.

Science.gov (United States)

Li, Jinshan

2010-02-18

The ZPE-corrected C-NO(2) bond dissociation energies (BDEs(ZPE)) of a series of model C-nitro compounds and 26 energetic C-nitro compounds have been calculated using density functional theory methods. Computed results show that for C-nitro compounds the UB3LYP calculated BDE(ZPE) is less than the UB3P86 using the 6-31G** basis set, and the UB3P86 BDE(ZPE) changes slightly with the basis set varying from 6-31G** to 6-31++G**. For the series of model C-nitro compounds with different chemical skeletons, it is drawn from NBO analysis that the order of BDE(ZPE) is not only in line with that of the NAO bond order but also with that of the energy gap between C-NO(2) bonding and antibonding orbitals. It is found that for the energetic C-nitro compounds whose drop energies (Es(dr)) are below 24.5 J a good linear correlation exists between E(dr) and BDE(ZPE), implying that these compounds ignite through the C-NO(2) dissociation mechanism. After excluding the so-called trinitrotoluene mechanism compounds, a polynomial correlation of ln(E(dr)) with the BDE(ZPE) calculated at density functional theory levels has been established successfully for the 18 C-NO(2) dissociation energetic C-nitro compounds.

A theoretical study of CH4 dissociation on pure and gold-alloyed Ni(111) surfaces

DEFF Research Database (Denmark)

Kratzer, P.; Hammer, Bjørk; Nørskov, Jens Kehlet

1996-01-01

We present a density functional theory study of the first step of CH4 adsorption on the Ni(111) surface, dissociation into adsorbed CH3 and H. The rupture of the C-H bond occurs preferentially on top of a Ni atom, with a dissociation barrier of about 100 kJ/mol (including zero point corrections......). The transition state involves considerable internal excitation of the molecule. The active C-H bond is both stretched to 1.6 Angstrom and tilted relative to the methyl group. A normal mode analysis shows that the reaction coordinate is mainly a C-H stretch, while the orientation of the C-H bond relative...... to the surface is responsible for the highest real mode. Alloying the surface with gold also affects the reactivity of the Ni atoms on adjacent surface sites. The dissociation barrier is increased by 16 and 38 kJ/mol for a Ni atom with one or two gold neighbors, respectively. We attribute these changes...

Microsolvated Model for the Kinetics and Thermodynamics of Glycosidic Bond Dissociative Cleavage of Nucleoside D4G.

Science.gov (United States)

Jiang, Yang; Xue, Ying; Zeng, Yi

2018-02-15

Using the microsolvated model that involves explicit water molecules and implicit solvent in the optimization, two proposed dissociative hydrolysis mechanisms of 2',3'-didehydro-2',3'-dideoxyguanosine (d4G) have been first investigated by means of M06-2X(CPCM, water)/6-31++G(d,p) method. The glycosidic bond dissociation for the generation of the oxacarbenium ion intermediate is the rate-determining step (RDS). The subsequent nucleophilic water attack from different side of the oxacarbenium ion intermediate gives either the α-product [(2S,5S)-5-(hydroxymethyl)-2,5-dihydrofuran-2-ol] or β-product [(2R,5S)-5-(hydroxymethyl)-2,5-dihydrofuran-2-ol] and is thus referred to as α-path (inversion) and β-path (retention). Two to five explicit water molecules (n = 2-5) are considered in the microsolvated model, and n = 3 or 4 is the smallest model capable of minimizing the activation energy for α-path and β-path, respectively. Our theoretical results suggest that α-path (n = 3) is more kinetically favorable with lower free energy barrier (RDS) of 27.7 kcal mol -1 , in contrast to that of 30.7 kcal mol -1 for the β-path (n = 4). The kinetic preference of the α-path is rationalized by NBO analysis. Whereas thte β-path is more thermodynamically favorable over the α-path, where the formation of β-product and α-product are exergonic and endergonic, respectively, providing theoretical support for the experimental observation that the β-cleavage product was the major one after sufficient reaction time. Comparisons of d4G with analogous cyclo-d4G and dG from kinetic free energy barriers and thermodynamic heterolytic dissociation energies were also carried out. Our kinetic and thermodynamic results manifest that the order of glycosidic bond stability should be d4G < cyclo-d4G < dG, which agrees well with the reported experimental stability order of d4G compounds and analogues and gives further understanding on the influence of 6-cyclopropylamino and unsaturated ribose to

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.

Enhancing Protein Disulfide Bond Cleavage by UV Excitation and Electron Capture Dissociation for Top-Down Mass Spectrometry

OpenAIRE

Wongkongkathep, Piriya; Li, Huilin; Zhang, Xing; Loo, Rachel R. Ogorzalek; Julian, Ryan R.; Loo, Joseph A.

2015-01-01

The application of ion pre-activation with 266 nm ultraviolet (UV) laser irradiation combined with electron capture dissociation (ECD) is demonstrated to enhance top-down mass spectrometry sequence coverage of disulfide bond containing proteins. UV-based activation can homolytically cleave a disulfide bond to yield two separated thiol radicals. Activated ECD experiments of insulin and ribonuclease A containing three and four disulfide bonds, respectively, were performed. UV-activation in comb...

Vibrational and cascade dissociation of H{sub 2}{sup +} ions by collision with gas molecules; Dissociation vibrationnelle et dissociation en cascade d'ions H{sub 2}{sup +} par collisions avec les molecules d'un gaz

Energy Technology Data Exchange (ETDEWEB)

Verveer, P [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1966-07-01

Protons produced by collisional dissociation of H{sub 2}{sup +} ions have an energy spectrum with a narrow central peak. For a part the protons in this peak are produced by vibrational dissociation and for another part by a cascade of two collisions. For H{sub 2}{sup +} ions of 50 to 150 keV the cross section for vibrational dissociation is about 4.1 10{sup -19} cm{sup 2}/molecule in hydrogen and 1.1 10{sup -18} cm{sup 2}/molecule in argon. (author) [French] Les protons resultant de la dissociation par collisions d'ions H{sub 2}{sup +} dans un gaz ont un spectre d'energie qui presente un pic central tres etroit. Les protons dans ce pic proviennent, pour une part de la dissociation vibrationnelle et pour l'autre part d'une suite de deux collisions. Dans le domaine d'energie des ions H{sub 2}{sup +} de 50 a 150 keV la section efficace de dissociation vibrationnel vaut 4.1 10{sup -19} cm{sup 2}/molecule pour l'hydrogene et 1,1 10{sup -18} cm{sup 2}/molecule pour l'argon.

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...

G3//BMK and Its Application to Calculation of Bond Dissociation Enthalpies.

Science.gov (United States)

Zheng, Wen-Rui; Fu, Yao; Guo, Qing-Xiang

2008-08-01

On the basis of systematic examinations it was found that the BMK functional significantly outperformed the other popular density functional theory methods including B3LYP, B3P86, KMLYP, MPW1P86, O3LYP, and X3LYP for the calculation of bond dissociation enthalpies (BDEs). However, it was also found that even the BMK functional might dramatically fail in predicting the BDEs of some chemical bonds. To solve this problem, a new composite ab initio method named G3//BMK was developed by combining the strengths of both the G3 theory and BMK. G3//BMK was found to outperform the G3 and G3//B3LYP methods. It could accurately predict the BDEs of diverse types of chemical bonds in various organic molecules within a precision of ca. 1.2 kcal/mol.

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

International Nuclear Information System (INIS)

Blank, D.A.; North, S.W.; Stranges, D.

1997-01-01

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 3 SOCH 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 3 intermediate prior to dissociation to define a stepwise dissociation: (1) CH 3 SOCH 3 → 2CH 3 + SO; (2a) CH 3 SOCH 3 → CH 3 + SOCH 3 ; and (2b) SOCH 3 → SO + CH 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 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 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

Mode Specific Electronic Friction in Dissociative Chemisorption on Metal Surfaces: H2 on Ag(111)

Science.gov (United States)

Maurer, Reinhard J.; Jiang, Bin; Guo, Hua; Tully, John C.

2017-06-01

Electronic friction and the ensuing nonadiabatic energy loss play an important role in chemical reaction dynamics at metal surfaces. Using molecular dynamics with electronic friction evaluated on the fly from density functional theory, we find strong mode dependence and a dominance of nonadiabatic energy loss along the bond stretch coordinate for scattering and dissociative chemisorption of H2 on the Ag(111) surface. Exemplary trajectories with varying initial conditions indicate that this mode specificity translates into modulated energy loss during a dissociative chemisorption event. Despite minor nonadiabatic energy loss of about 5%, the directionality of friction forces induces dynamical steering that affects individual reaction outcomes, specifically for low-incidence energies and vibrationally excited molecules. Mode-specific friction induces enhanced loss of rovibrational rather than translational energy and will be most visible in its effect on final energy distributions in molecular scattering experiments.

Models for calculation of dissociation energies of homonuclear diatomic molecules

International Nuclear Information System (INIS)

Brewer, L.; Winn, J.S.

1979-08-01

The variation of known dissociation energies of the transition metal diatomics across the Periodic Table is rather irregular like the bulk sublimation enthalpy, suggesting that the valence-bond model for bulk metallic systems might be applicable to the gaseous diatomic molecules and the various intermediate clusters. Available dissociation energies were converted to valence-state bonding energies considering various degrees of promotion to optimize the bonding. The degree of promotion of electrons to increase the number of bonding electrons is smaller than for the bulk, but the trends in bonding energy parallel the behavior found for the bulk metals. Thus using the established trends in bonding energies for the bulk elements, it was possible to calculate all unknown dissociation energies to provide a complete table of dissociation energies for all M 2 molecules from H 2 to Lr 2 . For solids such as Mg, Al, Si and most of the transition metals, large promotion energies are offset by strong bonding between the valence state atoms. The main question is whether bonding in the diatomics is adequate to sustain extensive promotion. The most extreme example for which a considerable difference would be expected between the bulk and the diatomics would be that of the Group IIA and IIB metals. The first section of this paper which deals with the alkaline earths Mg and Ca demonstrates a significant influence of the excited valence state even for these elements. The next section then expands the treatment to transition metals

Remote control of the dissociative ionization of H2 based on electron-H2 + entanglement

Science.gov (United States)

Wang, Jun-Ping; He, Feng

2018-04-01

The single ionization of H2 in strong laser fields creates the correlated electron-H2 + pair. Based on such a correlation, we conceive a strategy to control the energy spectra of the freed electron or dissociative fragments by simulating the time-dependent Schrödinger equation. Two attosecond pulses in a train produce the replica of electron-H2 + pairs, which are to be steered by a time-delayed phase-stabilized (mid)infrared laser pulse. By controlling the behavior of the freed electron, the dissociation of H2 + can be controlled even though there is no direct laser-H2 + coupling. On the other hand, the photoelectron energy spectra can be manipulated via laser-H2 + coupling. This study demonstrates the entanglement of molecular quantum wave packets, and affords a route to remotely control molecular dissociative ionization.

Site selective dissociation of ozone upon core excitation

International Nuclear Information System (INIS)

Mocellin, A.; Mundim, M.S.P.; Coutinho, L.H.; Homem, M.G.P.; Naves de Brito, A.

2007-01-01

We present new measurements applied to core excitation of ozone molecule using to analyze the dissociation channels the photo-electron-photo-ion coincidence (PEPICO) and the photo-electron-photo-ion-photo-ion coincidence (PEPIPICO) technique. The new experimental set-up allows measuring O + /O + ion pair coincidences without discrimination. The dissociation channels of several core-excited states have been investigated. The relative yields of dissociation channels were determined from coincidence data. The core excitation from O terminal (O T ) or O central (O C ) induce different fragmentation; preferentially one bond is broken at the O terminal excitation and two bonds when O central is excited, showing site selectivity fragmentation of ozone upon core excitation. The ultra-fast dissociation of the O T 1s -1 7a 1 1 core-excited state is confirmed by the relative yield of dissociation

Bond length effects during the dissociation of O2 on Ni(1 1 1)

International Nuclear Information System (INIS)

Shuttleworth, I.G.

2015-01-01

Graphical abstract: - Highlights: • The dissociation of O 2 on Ni(1 1 1) has been investigated using the Nudged Elastic Band (NEB) technique. • An exceptional correlation has been identified between the O/Ni bond order and the O 2 bond length for a series of sterically different reaction paths. • Direct magnetic phenomena accompany these processes suggesting further mechanisms for experimental control. - Abstract: The interaction between O 2 and Ni(1 1 1) has been investigated using spin-polarised density functional theory. A series of low activation energy (E A = 103–315 meV) reaction pathways corresponding to precursor and non-precursor mediated adsorption have been identified. It has been seen that a predominantly pathway-independent correlation exists between O−Ni bond order and the O 2 bond length. This correlation demonstrates that the O−O interaction predominantly determines the bonding of this system

Carbon disulfide (CS{sub 2}) adsorption and dissociation on the Cu(100) surface: A quantum chemical study

Energy Technology Data Exchange (ETDEWEB)

Wang, Wenju, E-mail: wangwenju1982@163.com; Fan, Lili; Wang, Guoping, E-mail: wgp1976@163.com

2017-08-31

Highlights: • CS{sub 2}, CS, C and S are strongly chemadsorbed on the Cu(100) surface. • C/S/S, S/CS and CS{sub 2} accord to a decreased adsorption strength on the Cu(100). • The asymmetric model CS{sub 2}(II) is easier to dissociate on the Cu(100) surface. - Abstract: Density functional theory (DFT) is used to examine the adsorption and dissociation of CS{sub 2} on the Cu(100) surface. This study evaluates the adsorption energies and geometries of the species (CS{sub 2}, CS, C and S) adsorption on the Cu(100) surface, as well as that coadsorption of CS and a S atom, and that coadsorption of C atom and two S atoms. The results indicate that the species (CS{sub 2}, CS, C and S) are strongly chemadsorbed on the Cu(100) surface through the C−Cu and/or S−Cu bond with an increased adsorption energy (C/S/S > S/CS > CS{sub 2}). Two pathways for CS{sub 2} dissociation on the Cu(100) surface are constructed, and the energy barrier and reaction energy of each step are calculated. It shows that the dissociated energy barrier of the second C−S bond is 0.25 eV higher than that of the first C−S bond in the pathway 1, but in the pathway 2, the dissociated energy barrier of the second C−S bond is 0.11 eV lower than that of the first C−S bond. Comparing the highest dissociated energy barrier of pathway 1 (0.68 eV) and pathway 2 (0.5 eV), the structure of S/C/S(II) is regarded as a preferable product for the dissociation of CS{sub 2} on the Cu(100) surface.

Mo-Mo Quintuple Bond is Highly Reactive in H-H, C-H, and O-H σ-Bond Cleavages Because of the Polarized Electronic Structure in Transition State.

Science.gov (United States)

Chen, Yue; Sakaki, Shigeyoshi

2017-04-03

The recently reported high reactivity of the Mo-Mo quintuple bond of Mo 2 (N ∧ N) 2 (1) {N ∧ N = μ-κ 2 -CH[N(2,6-iPr 2 C 6 H 3 )] 2 } in the H-H σ-bond cleavage was investigated. DFT calculations disclosed that the H-H σ-bond cleavage by 1 occurs with nearly no barrier to afford the cis-dihydride species followed by cis-trans isomerization to form the trans-dihydride product, which is consistent with the experimental result. The O-H and C-H bond cleavages by 1 were computationally predicted to occur with moderate (ΔG° ⧧ = 9.0 kcal/mol) and acceptable activation energies (ΔG° ⧧ = 22.5 kcal/mol), respectively, suggesting that the Mo-Mo quintuple bond can be applied to various σ-bond cleavages. In these σ-bond cleavage reactions, the charge-transfer (CT Mo→XH ) from the Mo-Mo quintuple bond to the X-H (X = H, C, or O) bond and that (CT XH→Mo ) from the X-H bond to the Mo-Mo bond play crucial roles. Though the HOMO (dδ-MO) of 1 is at lower energy and the LUMO + 2 (dδ*-MO) of 1 is at higher energy than those of RhCl(PMe 3 ) 2 (LUMO and LUMO + 1 of 1 are not frontier MO), the H-H σ-bond cleavage by 1 more easily occurs than that by the Rh complex. Hence, the frontier MO energies are not the reason for the high reactivity of 1. The high reactivity of 1 arises from the polarization of dδ-type MOs of the Mo-Mo quintuple bond in the transition state. Such a polarized electronic structure enhances the bonding overlap between the dδ-MO of the Mo-Mo bond and the σ*-antibonding MO of the X-H bond to facilitate the CT Mo→XH and reduce the exchange repulsion between the Mo-Mo bond and the X-H bond. This polarized electronic structure of the transition state is similar to that of a frustrated Lewis pair. The easy polarization of the dδ-type MOs is one of the advantages of the metal-metal multiple bond, because such polarization is impossible in the mononuclear metal complex.

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.

Dissociation of the Phenylarsane Molecular Ion: A Theoretical Study

Energy Technology Data Exchange (ETDEWEB)

Kim, Sun Young; Choe, Joong Chul [Dongguk University, Seoul (Korea, Republic of)

2010-09-15

The potential energy surfaces (PESs) for the primary and secondary dissociations of the phenylarsane molecular ion (1a) were determined from the quantum chemical calculations using the G3(MP2)//B3LYP method. Several pathways for the loss of H· were determined and occurred though rearrangements as well as through direct bond cleavages. The kinetic analysis based on the PES for the primary dissociation showed that the loss of H{sub 2} was more favored than the loss of H·, but the H· loss competed with the H{sub 2} loss at high energies. The bicyclic isomer, 7-arsa-norcaradiene radical cation, was formed through the 1,2 shift of an α-H of 1a and played an important role as an intermediate for the further rearrangements in the loss of H· and the losses of As· and AsH. The reaction pathways for the formation of the major products in the secondary dissociations of [M-H]{sup +} and [M-H{sub 2}]{sup +·} were examined. The theoretical prediction explained the previous experimental results for the dissociation at high energies but not the dissociation at low energies.

A First Principles Study of H2 Adsorption on LaNiO3(001 Surfaces

Directory of Open Access Journals (Sweden)

Changchang Pan

2017-01-01

Full Text Available The adsorption of H2 on LaNiO3 was investigated using density functional theory (DFT calculations. The adsorption sites, adsorption energy, and electronic structure of LaNiO3(001/H2 systems were calculated and indicated through the calculated surface energy that the (001 surface was the most stable surface. By looking at optimized structure, adsorption energy and dissociation energy, we found that there were three types of adsorption on the surface. First, H2 molecules completely dissociate and then tend to bind with the O atoms, forming two –OH bonds. Second, H2 molecules partially dissociate with the H atoms bonding to the same O atom to form one H2O molecule. These two types are chemical adsorption modes; however, the physical adsorption of H2 molecules can also occur. When analyzing the electron structure of the H2O molecule formed by the partial dissociation of the H2 molecule and the surface O atom, we found that the interaction between H2O and the (001 surface was weaker, thus, H2O was easier to separate from the surface to create an O vacancy. On the (001 surface, a supercell was constructed to accurately study the most stable adsorption site. The results from analyses of the charge population; electron localization function; and density of the states indicated that the dissociated H and O atoms form a typical covalent bond and that the interaction between the H2 molecule and surface is mainly due to the overlap-hybridization among the H 1s, O 2s, and O 2p states. Therefore, the conductivity of LaNiO3(001/H2 is stronger after adsorption and furthermore, the conductivity of the LaNiO3 surface is better than that of the LaFeO3 surface.

Site selective dissociation of ozone upon core excitation

Energy Technology Data Exchange (ETDEWEB)

Mocellin, A. [Instituto de Fisica, Universidade de Brasilia-UnB, Box 04455, CEP 70919-970, Brasilia-DF (Brazil)], E-mail: mocellin@fis.unb.br; Mundim, M.S.P. [Instituto de Fisica, Universidade de Brasilia-UnB, Box 04455, CEP 70919-970, Brasilia-DF (Brazil); Coutinho, L.H. [Instituto de Quimica, Universidade Federal do Rio de Janeiro-UFRJ, Box 68563, CEP 21945-970, Rio de Janeiro-RJ (Brazil); Homem, M.G.P. [Laboratorio Nacional de Luz Sincrotron-LNLS, Box 6192, CEP 13084-971, Campinas-SP (Brazil); Naves de Brito, A. [Laboratorio Nacional de Luz Sincrotron-LNLS, Box 6192, CEP 13084-971, Campinas-SP (Brazil); Instituto de Fisica, Universidade de Brasilia-UnB, Box 04455, CEP 70919-970, Brasilia-DF (Brazil)

2007-05-15

We present new measurements applied to core excitation of ozone molecule using to analyze the dissociation channels the photo-electron-photo-ion coincidence (PEPICO) and the photo-electron-photo-ion-photo-ion coincidence (PEPIPICO) technique. The new experimental set-up allows measuring O{sup +}/O{sup +} ion pair coincidences without discrimination. The dissociation channels of several core-excited states have been investigated. The relative yields of dissociation channels were determined from coincidence data. The core excitation from O terminal (O{sub T}) or O central (O{sub C}) induce different fragmentation; preferentially one bond is broken at the O terminal excitation and two bonds when O central is excited, showing site selectivity fragmentation of ozone upon core excitation. The ultra-fast dissociation of the O{sub T} 1s{sup -1}7a{sub 1}{sup 1} core-excited state is confirmed by the relative yield of dissociation.

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...

Anomalous H/D isotope effect in hydrogen bonded systems: H-bonded cyclic structures and transfers of protons

International Nuclear Information System (INIS)

Marechal, Y.

1993-01-01

The systematic H/D substitution is a precious tool to obtain information on the dynamics of H-bonds. It is particularly useful in IR spectroscopy where H-bonds are at the origin of particularly intense and specific bands and where the particularly great value for the m D /m H ratio ensures strongly marked effects. In most H-bonded systems the effects of these substitutions are normal, in the sense that they are at the origin of bands having intensities, centers (of intensity) and widths smaller in D-bonds by a factor close to √2 as compared to H-bonds. In some systems as carboxylic acid dimers, however, anomalous ratios of intensities are found upon such a substitution. Their origin is still obscure. Experimental results suggest that such anomalous ratios have much to do with the cyclic structure of these systems. It leads to stressing an important property of H-bonded cyclic structures which is that they seem necessary for having transfers of protons between molecules through H-bonds in a neutral aqueous medium (p H =7) at room temperature. The mechanism of such transfers of protons is still poorly known, but these transfers are now suspected to play a fundamental role in such widespread reactions as hydrolysis, peptide synthesis, etc... which may make them soon appear as being a crucial basic mechanism for reactivity of aqueous systems, particularly biological systems

Dissociative ionization of methanol in medium intense femtosecond laser field using time-of-flight mass spectrometry

Science.gov (United States)

Elshakre, Mohamed

2015-07-01

800 nm 100 fs laser combined with TOF mass spectrometer was used to investigate the dissociative ionization of methanol, CH3OH in the laser intensity less than 4×1013 W/cm2. The results showed that the dissociation follows a sequential step-wise dissociation pattern, with no sign for Coulomb explosion. At very low intensity 1.4×1013 W/cm2, only the parent ion CH3OH+ appears. At 1.7×1013 W/cm2, the dissociation products are mainly due to hydrogen elimination from the O-H or C-H bonds forming CH3O+ and CH2OH+ primary ions. At 2.0×1013 W/cm2, the C-O bond starts to break forming CH3+, which simultaneously dissociates to CH2+. The primary fragment ions CH3O+ and CH2OH+ start to dissociate into lower secondary fragments as CH2O+ and CHO+ for the former and CHOH+ and COH+ for the latter. At 2.8×1013 W/cm2, secondary dissociation fragments dominate the spectrum including C+, CH+, CH2+, OH+, and O+ and the H+ is detected. At 3.0×1013W/cm2, H2+ is detected. For all ions formed, the ion yield increases with laser intensity till it reaches maximum, after which it drops down manifesting the dissociation of these ions into smaller fragments. Among all ions, only H+ was found to have angular anisotropic distribution.

X-ray Absorption Spectroscopy and Density Functional Theory Studies of [(H3buea)FeIII-X]n1 (X= S2-, O2-,OH-): Comparison of Bonding and Hydrogen Bonding in Oxo and Sulfido Complexes

Energy Technology Data Exchange (ETDEWEB)

Dey, Abhishek; Hocking, Rosalie K.; /Stanford U., Chem. Dept.; Larsen, Peter; Borovik, Andrew S.; /Kansas U.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; /SLAC,

2006-09-27

Iron L-edge, iron K-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [Fe{sup III}H{sub 3}buea(X)]{sup n-} (X = S{sup 2-}, O{sup 2-}, OH{sup -}). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metal-ligand bonding and to evaluate the effects of H-bonding in Fe{sup III}-O vs Fe{sup III-}S complexes. It was found that the Fe{sup III-}O bond, while less covalent, is stronger than the FeIII-S bond. This dominantly reflects the larger ionic contribution to the Fe{sup III-}O bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the Fe-O bond. These results were extended to consider an Fe{sup IV-}O complex with the same ligand environment. It was found that hydrogen bonding to Fe{sup IV-}O is less energetically favorable than that to Fe{sup III-}O, which reflects the highly covalent nature of the Fe{sup IV-}O bond.

Increased Heat Transport in Ultra-hot Jupiter Atmospheres through H2 Dissociation and Recombination

Science.gov (United States)

Bell, Taylor J.; Cowan, Nicolas B.

2018-04-01

A new class of exoplanets is beginning to emerge: planets with dayside atmospheres that resemble stellar atmospheres as most of their molecular constituents dissociate. The effects of the dissociation of these species will be varied and must be carefully accounted for. Here we take the first steps toward understanding the consequences of dissociation and recombination of molecular hydrogen (H2) on atmospheric heat recirculation. Using a simple energy balance model with eastward winds, we demonstrate that H2 dissociation/recombination can significantly increase the day–night heat transport on ultra-hot Jupiters (UHJs): gas giant exoplanets where significant H2 dissociation occurs. The atomic hydrogen from the highly irradiated daysides of UHJs will transport some of the energy deposited on the dayside toward the nightside of the planet where the H atoms recombine into H2; this mechanism bears similarities to latent heat. Given a fixed wind speed, this will act to increase the heat recirculation efficiency; alternatively, a measured heat recirculation efficiency will require slower wind speeds after accounting for H2 dissociation/recombination.

Competition between weak OH···π and CH··O hydrogen bonds: THz spectroscopy of the C₂H₂—H₂O and C₂H₄—H₂O complexes

DEFF Research Database (Denmark)

Andersen, Jonas; Heimdal, Jimmy; Nelander, B.

2017-01-01

-bonded configuration with the H2O subunit acting as the hydrogen bond donor to the π-cloud of C2H4. A (semi)-empirical value for the change of vibrational zero-point energy of 4.0–4.1 kJ mol−1 is proposed and the combination with quantum chemical calculations at the CCSD(T)-F12b/aug-cc-pVQZ level provides a reliable....... The present findings demonstrate that the relative stability of the weak hydrogen bond motifs is not entirely rooted in differences of electronic energy but also to a large extent by differences in the vibrational zero-point energy contributions arising from the class of large-amplitude intermolecular modes....... estimate of 7.1 ± 0.3 kJ mol−1 for the dissociation energy D0 of the C2H4—H2O complex. In addition, tentative assignments for the two strongly infrared active OH librational modes of the ternary C2H4—HOH—C2H4 complex having H2O as a doubly OH⋯π hydrogen bond donor are proposed at 213.6 and 222.3 cm−1...

Shear bond strength of one-step self-etch adhesives: pH influence

Science.gov (United States)

Poggio, Claudio; Beltrami, Riccardo; Scribante, Andrea; Colombo, Marco; Chiesa, Marco

2015-01-01

Background: The aim of this study was to compare the shear bond strength of four one-step self-etch adhesives with different pH values to enamel and dentin. Materials and Methods: In this in vitro study, 200 bovine permanent mandibular incisors were used. Four one-step self-etch adhesives with different pH values were tested both on enamel and on dentin: Adper™ Easy Bond Self-Etch Adhesive (pH = 0.8-1), Futurabond NR (pH=2), G-aenial Bond (pH = 1.5), Clearfil S3 Bond (pH = 2.7). After adhesive systems application, a nanohybrid composite resin was inserted into the bonded surface. The specimens were placed in a universal testing machine. The shear bond strength was performed at a cross-head speed of 1 mm/min until the sample rupture. The shear bond strength values (MPa) of the different groups were compared with analysis of variance after that Kolmogorov and Smirnov tests were applied to assess normality of distributions. P enamel shear bond strength, the highest shear bond strength values were reported with Futurabond NR (P adhesive systems showed lower shear bond strength values with significant differences between them (P 0.05). Conclusion: The pH values of adhesive systems did not influence significantly their shear bond strength to enamel or dentin. PMID:26005459

Solitons on H bonds in proteins

DEFF Research Database (Denmark)

d'Ovidio, F.; Bohr, H.G.; Lindgård, Per-Anker

2003-01-01

system shows that the solitons are spontaneously created and are stable and moving along the helix axis. A perturbation on one of the three H-bond lines forms solitons on the other H bonds as well. The robust solitary wave may explain very long-lived modes in the frequency range of 100 cm(-1) which...... are found in recent x-ray laser experiments. The dynamics parameters of the Toda lattice are in accordance with the usual Lennard-Jones parameters used for realistic H-bond potentials in proteins....

Adsorption of water on O(2x2)/Ru(0001): thermal stability and inhibition of dissociation by H2O-O bonding

Energy Technology Data Exchange (ETDEWEB)

Mugarza, Aitor; Shimizu, Tomoko; Cabrera-Sanfelix, Pepa; Sanchez-Portal, Daniel; Arnau, Andres; Salmeron, Miquel

2008-08-01

The effect of preadsorbed oxygen on the subsequent adsorption and reactions of water on Ru(0001) has been studied using low temperature scanning tunneling microscopy and DFT calculations. Experiments were carried out for O coverages close to 0.25 ML. It was found that no dissociation of water takes place up to the desorption temperature of {approx}180-230 K. DFT calculations show that intact water on O(2x2)/Ru(0001) is {approx} 0.49 eV more stable than the dissociation products, H and OH, at their preferred fcc and top adsorption sites.

Hydrogen dissociation and incorporation on Mg{sub 17}Al{sub 12}(100) surface: A density functional theory study

Energy Technology Data Exchange (ETDEWEB)

Ning, Hua [Guangxi Key Laboratory for Relativistic Astrophysics, Guangxi Colleges and Universities Key Laboratory of Novel Energy Materials and Related Technology, College of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, School of Material Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China); Zhou, Zhiyan; Zhang, Ziyan [Guangxi Key Laboratory for Relativistic Astrophysics, Guangxi Colleges and Universities Key Laboratory of Novel Energy Materials and Related Technology, College of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Zhou, Wenzheng; Li, Guangxu [Guangxi Key Laboratory for Relativistic Astrophysics, Guangxi Colleges and Universities Key Laboratory of Novel Energy Materials and Related Technology, College of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, School of Material Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China); Guo, Jin, E-mail: guojin@gxu.edu.cn [Guangxi Key Laboratory for Relativistic Astrophysics, Guangxi Colleges and Universities Key Laboratory of Novel Energy Materials and Related Technology, College of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials, School of Material Science and Engineering, Guilin University of Electronic Technology, Guilin 541004 (China)

2017-02-28

Highlights: • Hydrogen adsorption, dissociation, and penetration on (in) Mg{sub 17}Al{sub 12} (100) surface are studied. • Hydrogen molecules are dissociated on the surface with barrier of 0.63 eV. • The maximum barrier energy for atomic hydrogen penetration into the subsurface is ∼0.7 eV. • The hybridization between the s orbital of H and the s orbitals of Mg is major. - Abstract: Hydrogen adsorption, dissociation, and penetration on (in) Mg{sub 17}Al{sub 12} (100) surface are studied extensively by DFT total-energy calculations. The adsorption geometries, dissociation barriers, various diffusion pathways, penetrative processes, and electronic structures were investigated. Results show that the atomic and molecular hydrogen forms prefer to be adsorbed on the Mg3-Mg3 bridge sites (C sites). Hydrogen molecules are dissociated on the surface with the minimum barrier energy of 0.63 eV. There are two stages in the process of hydrogen incorporation, which are hydrogen diffusion on the surface and the penetration from the surface into the subsurface. Two possible pathways of atomic hydrogen penetration from surface into subsurface are found. The calculations of electronic structures show that the hybridization between the s orbital of H and the s orbitals of Mg is major. The Mg-Mg bond on the outmost surface is shortened from 4.48 Å to 3.30 Å after the hydrogen adsorption on C sites, showing the strong interaction between Mg and H atoms.

Enhancing Protein Disulfide Bond Cleavage by UV Excitation and Electron Capture Dissociation for Top-Down Mass Spectrometry.

Science.gov (United States)

Wongkongkathep, Piriya; Li, Huilin; Zhang, Xing; Loo, Rachel R Ogorzalek; Julian, Ryan R; Loo, Joseph A

2015-11-15

The application of ion pre-activation with 266 nm ultraviolet (UV) laser irradiation combined with electron capture dissociation (ECD) is demonstrated to enhance top-down mass spectrometry sequence coverage of disulfide bond containing proteins. UV-based activation can homolytically cleave a disulfide bond to yield two separated thiol radicals. Activated ECD experiments of insulin and ribonuclease A containing three and four disulfide bonds, respectively, were performed. UV-activation in combination with ECD allowed the three disulfide bonds of insulin to be cleaved and the overall sequence coverage to be increased. For the larger sized ribonuclease A with four disulfide bonds, irradiation from an infrared laser (10.6 µm) to disrupt non-covalent interactions was combined with UV-activation to facilitate the cleavage of up to three disulfide bonds. Preferences for disulfide bond cleavage are dependent on protein structure and sequence. Disulfide bonds can reform if the generated radicals remain in close proximity. By varying the time delay between the UV-activation and the ECD events, it was determined that disulfide bonds reform within 10-100 msec after their UV-homolytic cleavage.

UV Photofragmentation Dynamics of Protonated Cystine: Disulfide Bond Rupture.

Science.gov (United States)

Soorkia, Satchin; Dehon, Christophe; Kumar, S Sunil; Pedrazzani, Mélanie; Frantzen, Emilie; Lucas, Bruno; Barat, Michel; Fayeton, Jacqueline A; Jouvet, Christophe

2014-04-03

Disulfide bonds (S-S) play a central role in stabilizing the native structure of proteins against denaturation. Experimentally, identification of these linkages in peptide and protein structure characterization remains challenging. UV photodissociation (UVPD) can be a valuable tool in identifying disulfide linkages. Here, the S-S bond acts as a UV chromophore and absorption of one UV photon corresponds to a σ-σ* transition. We have investigated the photodissociation dynamics of protonated cystine, which is a dimer of two cysteines linked by a disulfide bridge, at 263 nm (4.7 eV) using a multicoincidence technique in which fragments coming from the same fragmentation event are detected. Two types of bond cleavages are observed corresponding to the disulfide (S-S) and adjacent C-S bond ruptures. We show that the S-S cleavage leads to three different fragment ions via three different fragmentation mechanisms. The UVPD results are compared to collision-induced dissociation (CID) and electron-induced dissociation (EID) studies.

Application of Berlin's theorem to bond-length changes in isolated molecules and red- and blue-shifting H-bonded clusters

Czech Academy of Sciences Publication Activity Database

Wang, Weizhou; Hobza, Pavel

2008-01-01

Roč. 73, 6/7 (2008), s. 862-872 ISSN 0010-0765 R&D Projects: GA MŠk LC512; GA AV ČR IAA400550510 Institutional research plan: CEZ:AV0Z40550506 Keywords : Berlin's theorem * H-bonding * Blue -shifting H-bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.784, year: 2008

Symmetry Breakdown in Ground State Dissociation of HD+

International Nuclear Information System (INIS)

Ben-Itzhak, I.; Wells, E.; Carnes, K. D.; Krishnamurthi, Vidhya; Weaver, O. L.; Esry, B. D.

2000-01-01

Experimental studies of the dissociation of the electronic ground state of HD + following ionization of HD by fast proton impact indicate that the H + +D 1s dissociation channel is more likely than the H1s+D + dissociation channel by about 7% . This isotopic symmetry breakdown is due to the finite nuclear mass correction to the Born-Oppenheimer approximation which makes the 1sσ state 3.7 meV lower than the 2pσ state at the dissociation limit. The measured fractions of the two dissociation channels are in agreement with coupled-channels calculations of 1sσ to 2pσ transitions. (c) 2000 The American Physical Society

Neutral hydrogen from the foil-induced dissociation of 4HeH+, 3HeH+, and H2+

International Nuclear Information System (INIS)

Cooney, P.J.; Gemmell, D.S.; Kanter, E.P.; Pietsch, W.J.; Zabransky, B.J.

1979-01-01

High resolution energy spectra and angular distributions of H 0 from the dissociation of 4 HeH + , 3 HeH + , and H 2 + in thin carbon foils are presented for incident ion energies ranging from 170 to 1800 keV/amu. For the range of dwell times inside the target foils studied (about 1 to 10 fsec), the dominant mechanism for such dissociation is the Coulomb explosion of the ions inside the target followed by electron capture near the rear surface of the foil. At the shortest of these dwell times, the yield of H 0 for incident ions oriented perpendicular to the beam relative to that for ions aligned with the beam is a factor of two greater than at longer dwell times. These data indicate that, for ion fragments which emerge from the rear surface of the target within a few angstroms of one another, those in the perpendicular orientation have a greater electron capture probability than those emerging in other orientations. 9 references

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)

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(¹A_l) and H (²S) was the only single photon dissociation pathway observed at both wavelengths.

Energy redistribution in the dissociation of low Rydberg states of HeH and 02

International Nuclear Information System (INIS)

Zande, W.J.A. van der.

1988-01-01

In this thesis the dissocation process is studied of the diatomic molecules, heliumhydride and molecular oxygen. In ch.'s 2-4 results on the spectroscopy and dissociative decay of the excited states of heliumhydride (HeH) are explained. The positions and dissociation pathways of the A 2 Σ + and B 2 Π states are determined and a theoretical description of the decay of these states are given. An isotope dependent dissociation behaviour of the C 2 /σ + Rydberg state is reported which explained with this theory. In ch.'s 5-7 observations are presented regarding the first Rydberg states of molecular oxygen. The spectroscopy of the (3sσ)d 1 Π g and C 3 Π g states is treated, and the stability and decay of these Rydberg states is discussed qualitatively. An experimental study is described of the (3sσ)d 1 Π g , v=4-8 states. By isotope studies and resolving rotational lines and the measurements of natural linewidths quantitative estimates have been acquired on coupling strengths, positions of repulsive valence states and perturbations reported in literature from REMPI experiments. The electronic coupling strengths between the C 3 Π g state and the 3 Π g valence state has been established. Observed spin-orbit interactions have been quantified and the dissociation of the multiplet states (C 3 Π g , ω=0-2 has been correlated with the multiplet states of the fragment O 3 P J=0-2 . The spectroscopy of the (3sσ3) Rydberg states which con- verge to and are formed in collisions with the O + 2 , a 4 Π μ ion state, is treated. The (3sσ) 5 /π μ state competition between auto-ionizations and (pre-)dissociation has been observed. 207 refs.; 36 figs.; 18 tabs

The investigation of adsorption and dissociation of H2O on Li2O (111) by ab initio theory

Science.gov (United States)

Kong, Xianggang; Yu, You; Ma, Shenggui; Gao, Tao; Lu, Tiecheng; Xiao, Chengjian; Chen, Xiaojun; Zhang, Chuanyu

2017-06-01

The adsorption and dissociation mechanism of H2O molecule on the Li2O (111) surface have been systematically studied by using the density functional theory calculations. The parallel and vertical configurations of H2O at six different symmetry adsorption sites on the Li2O (111) surface are considered. In our calculations, it is suggested that H2O can dissociate on the perfect Li2O surface, of which the corresponding adsorption energy is 1.118 eV. And the adsorption energy decrease to be 0.241 eV when oxygen atom of H2O bonds to lithium atom of the slab. The final configurations are sensitive to the initial molecular orientation. By Bader charge analysis, the charge transfer from slab to adsorbed H2O/OH can be found due to the downward shift of lowest-unoccupied molecular orbital. We also analyze the vibrational frequencies at the Brillouin Zone centre for H2O molecule adsorbed on the stoichiometric surface. Due to the slightly different structure parameters, the calculated values of the vibrational frequencies of hydroxyl group range from 3824 to 3767 cm-1. Our results agree well with experimental results performed in FT-IR spectrum, which showed that an absorption peak of OH group appeared at 3677 cm-1 at room temperature.

A neural network potential energy surface for the NaH2 system and dynamics studies on the H(2S) + NaH(X1Σ+) → Na(2S) + H2(X1Σg+) reaction.

Science.gov (United States)

Wang, Shufen; Yuan, Jiuchuang; Li, Huixing; Chen, Maodu

2017-08-02

In order to study the dynamics of the reaction H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), a new potential energy surface (PES) for the ground state of the NaH 2 system is constructed based on 35 730 ab initio energy points. Using basis sets of quadruple zeta quality, multireference configuration interaction calculations with Davidson correction were carried out to obtain the ab initio energy points. The neural network method is used to fit the PES, and the root mean square error is very small (0.00639 eV). The bond lengths, dissociation energies, zero-point energies and spectroscopic constants of H 2 (X 1 Σ g + ) and NaH(X 1 Σ + ) obtained on the new NaH 2 PES are in good agreement with the experiment data. On the new PES, the reactant coordinate-based time-dependent wave packet method is applied to study the reaction dynamics of H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), and the reaction probabilities, integral cross-sections (ICSs) and differential cross-sections (DCSs) are obtained. There is no threshold in the reaction due to the absence of an energy barrier on the minimum energy path. When the collision energy increases, the ICSs decrease from a high value at low collision energy. The DCS results show that the angular distribution of the product molecules tends to the forward direction. Compared with the LiH 2 system, the NaH 2 system has a larger mass and the PES has a larger well at the H-NaH configuration, which leads to a higher ICS value in the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction. Because the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction releases more energy, the product molecules can be excited to a higher vibrational state.

Tug-of-war between classical and multicenter bonds in H-(Be)n-H species

Science.gov (United States)

Lundell, Katie A.; Boldyrev, Alexander I.

2018-05-01

Quantum chemical calculations were performed for beryllium homocatenated compounds [H-(Be)n-H]. Global minimum structures were found using machine searches (Coalescence Kick method) with density functional theory. Chemical bonding analysis was performed with the Adaptive Natural Density Partitioning method. It was found that H-(Be)2-H and H-(Be)3-H clusters are linear with classical two-center two-electron bonds, while for n > 3, three-dimensional structures are more stable with multicenter bonding. Thus, at n = 4, multicenter bonding wins the tug-of-war vs. the classical bonding.

H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds

Directory of Open Access Journals (Sweden)

Ibon Alkorta

2016-02-01

Full Text Available A search of the Cambridge Structural Database (CSD was carried out for phosphine-water and arsine-water complexes in which water is either the proton donor in hydrogen-bonded complexes, or the electron-pair donor in pnicogen-bonded complexes. The range of experimental P-O distances in the phosphine complexes is consistent with the results of ab initio MP2/aug’-cc-pVTZ calculations carried out on complexes H2XP:OH2, for X = NC, F, Cl, CN, OH, CCH, H, and CH3. Only hydrogen-bonded complexes are found on the H2(CH3P:HOH and H3P:HOH potential surfaces, while only pnicogen-bonded complexes exist on H2(NCP:OH2, H2FP:OH2, H2(CNP:OH2, and H2(OHP:OH2 surfaces. Both hydrogen-bonded and pnicogen-bonded complexes are found on the H2ClP:OH2 and H2(CCHP:OH2 surfaces, with the pnicogen-bonded complexes more stable than the corresponding hydrogen-bonded complexes. The more electronegative substituents prefer to form pnicogen-bonded complexes, while the more electropositive substituents form hydrogen-bonded complexes. The H2XP:OH2 complexes are characterized in terms of their structures, binding energies, charge-transfer energies, and spin-spin coupling constants 2hJ(O-P, 1hJ(H-P, and 1J(O-H across hydrogen bonds, and 1pJ(P-O across pnicogen bonds.

Dissociative recombination of rare gas hydride ions: II. ArH+

International Nuclear Information System (INIS)

Mitchell, J B A; Novotny, O; LeGarrec, J L; Florescu-Mitchell, A; Rebrion-Rowe, C; Stolyarov, A V; Child, M S; Svendsen, A; Ghazaly, M A El; Andersen, L H

2005-01-01

A storage ring measurement of the rate coefficient for the production of neutral Ar in e + ArH + collisions is described. It is found that the recombination rate is too small to measure at low centre-of-mass energies but the combined rate coefficient for dissociative recombination and dissociative excitation increases above 2.5 eV displaying peaks centred at 7.5 eV, 16 and 26 eV. Calculated potential energy curves for the ground and excited states of ArH + are presented and these aid in the elucidation of the recombination and excitation processes observed at higher energies. The implications for plasma modelling are discussed. (letter to the editor)

A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.

Science.gov (United States)

Scamp, Ryan J; Jirak, James G; Dolan, Nicholas S; Guzei, Ilia A; Schomaker, Jennifer M

2016-06-17

The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.

Heterolytic dissociative adsorption state of dihydrogen favored by interfacial defects

Science.gov (United States)

Song, Zhenjun; Hu, Hanshi; Xu, Hu; Li, Yong; Cheng, Peng; Zhao, Bin

2018-03-01

The atomic-scale insight into dihydrogen on MgO(001) surface deposited on molybdenum substrate with interfacial defects was investigated in detail by employing density functional methods Here we report novel dissociative adsorption behaviors of single hydrogen molecule on the usually inert oxide surfaces, with consideration of two types of dissociation schemes. The heterolytic dissociation state -Mg(H)-O(H)- of dihydrogen is impossible to obtain on neighboring O-Mg sites of perfect bulk MgO(001) terraces. Unusually, the hydrogen molecule can form heterolytic fragmentation states on metal supported MgO(001) films with very low activation barrier (0.398 eV), and the heterolytic dissociation state is much more favorable than homolytic dissociation state both energetically and kinetically in all cases. Electronic properties and bonding attribution of adsorbates and the oxide-metal hybrid structure are revealed by analyzing density of states, differential charge densities, orbital interaction and electron localization function. The characteristic changes to the property and activity of magnesia (001) can have potential application in catalytic reactions.

Adatom Bond Dissociation in the Collision Between an Adsorbed Atom and Incident Diatomic Molecule: A Classical Trajectory Study

International Nuclear Information System (INIS)

Bayhan, U.

2004-01-01

The collisional dissociation of the Atom-Surface bond in the diatomic molecule (gas) / atom (ads) collision taking place on a bcc-structure surface have been studied by classical trajectory methods over the collision energy ranges and the attractive well depth of the diatomic molecule (gas) / atom (ads) interactions

Aromatic C-H bond activation revealed by infrared multiphoton dissociation spectroscopy

Czech Academy of Sciences Publication Activity Database

Jašíková, L.; Hanikýřová, E.; Schröder, Detlef; Roithová, J.

2012-01-01

Roč. 47, č. 4 (2012), s. 460-465 ISSN 1076-5174 Grant - others:GA ČR(CZ) GAP207/11/0338; Seventh Framework Program(XE) 226716 Institutional research plan: CEZ:AV0Z40550506 Keywords : C-H activation * density functional theory calculations * ion spectroscopy * metal oxides * rearrangements Subject RIV: CC - Organic Chemistry Impact factor: 3.214, year: 2012

The adsorption and dissociation of water molecule on goethite (010) surface: A DFT approach

Energy Technology Data Exchange (ETDEWEB)

Zhou, Long, E-mail: shuweixia@ouc.edu.cn [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, College of Chemistry and Chemical Engineering (China); Xiu, Fangyuan [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, College of Chemistry and Chemical Engineering (China); Qiu, Meng [Qingdao Institute of Bioenergy and Bioprocess Technology (China); Xia, Shuwei; Yu, Liangmin [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, College of Chemistry and Chemical Engineering (China)

2017-01-15

Graphical abstract: The optimized structure of hydrated goethite (010) surface with medium water coverage (water density about 6.7 H{sub 2}O/nm{sup 2}). - Highlights: • Stable adsorption and dissociation structure of H{sub 2}O on goethite (010) surface was investigated by DFT. • Reasonable path for water dissociation was proposed by transitional state analysis. • The mechanism of water adsorption on goethite and binding nature were revealed by PDOS. - Abstract: Using density functional theory (DFT) calculation, we investigate the configuration, stability and electronic properties of fresh cleaved (010) goethite surface (Pnma) and this surface exposed to water monolayer at low, medium and high coverage. Water is predicted to be chemisorbed to the surface, together with the surface reconstruction. The interaction energy of the most stable configuration of both low and medium coverage per water molecule is almost the same (−1.17 eV), while that of high coverage is much lower (less than 1.03 eV). It indicates that highly hydrated surface is less stable. PDOS analysis reveals the adsorption of H{sub 2}O is due to the formation of Fe−O bond, caused by overlapping of Fe's 3d and O's 2p orbitals. Dissociation processes at low and medium water coverage are non-spontaneous; while at high coverage, it can undertake spontaneously both thermodynamically and dynamically. The dissociation paths of all three water coverage are the similar. The proton from one adsorbed water is likely to dissociate to bind to the vicinal surface μ{sub 3}−O as an intermediate product; the proton belonged to μ{sub 3}−O transferred to the neighbor surface μ{sub 2}−O as the dissociative configuration.

Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

Energy Technology Data Exchange (ETDEWEB)

Colby, Denise; Bergman, Robert; Ellman, Jonathan

2010-05-13

Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

Probing the Watson-Crick, wobble, and sugar-edge hydrogen bond sites of uracil and thymine.

Science.gov (United States)

Müller, Andreas; Frey, Jann A; Leutwyler, Samuel

2005-06-16

The nucleobases uracil (U) and thymine (T) offer three hydrogen-bonding sites for double H-bond formation via neighboring N-H and C=O groups, giving rise to the Watson-Crick, wobble and sugar-edge hydrogen bond isomers. We probe the hydrogen bond properties of all three sites by forming hydrogen bonded dimers of U, 1-methyluracil (1MU), 3-methyluracil (3MU), and T with 2-pyridone (2PY). The mass- and isomer-specific S1 origins exhibit large spectral blue shifts relative to the 2PY monomer. Ab initio CIS calculations of the spectral shifts of the different hydrogen-bonded dimers show a linear correlation with experiment. This correlation allows us to identify the R2PI spectra of the weakly populated Watson-Crick and wobble isomers of both 2PY.U and 2PY.T. (3) PW91 density functional calculation of the ground-state binding and dissociation energies De and D0 are in agreement with the assignment of the dominant hydrogen bond isomers of 2PY.U, 2PY.3MU and 2PY.T as the sugar-edge form. For 2PY.U, 2PY.T and 2PY.1MU the measured wobble:Watson-Crick:sugar-edge isomer ratios are in good agreement with the calculated ratios, based on the ab initio dissociation energies and gas-phase statistical mechanics. The Watson-Crick and wobble isomers are thereby determined to be several kcal/mol less strongly bound than the sugar-edge isomers. The 36 observed intermolecular frequencies of the nine different H-bonded isomers give detailed insight into the intermolecular force field.

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

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.......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...

Z-H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H2 Evolution.

Science.gov (United States)

Belkova, Natalia V; Filippov, Oleg A; Shubina, Elena S

2018-02-01

The ability of neutral transition-metal hydrides to serve as a source of hydride ion H - or proton H + is well appreciated. The hydride ligands possessing a partly negative charge are proton accepting sites, forming a dihydrogen bond, M-H δ- ⋅⋅⋅ δ+ HX (M=transition metal or metalloid). On the other hand, some metal hydrides are able to serve as a proton source and give hydrogen bond of M-H δ+ ⋅⋅⋅X type (X=organic base). In this paper we analyse recent works on transition-metal and boron hydrides showing i) how formation of an intermolecular complex between the reactants changes the Z-H (M-H and X-H) bond polarity and ii) what is the implication of such activation in the mechanisms of hydrides reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dipole and Coulomb forces in electron capture dissociation and electron transfer dissociation mass spectroscopy.

Science.gov (United States)

Świerszcz, Iwona; Skurski, Piotr; Simons, Jack

2012-02-23

Ab initio electronic structure calculations were performed on a doubly charged polypeptide model H(+)-Lys(Ala)(19)-CO-CH(NH(2))-CH(2)-SS-CH(2)-(NH(2))CH-CO-(Ala)(19)-Lys-H(+) consisting of a C-terminal protonated Lys followed by a 19-Ala α-helix with a 20th Ala-like unit whose side chain is linked by a disulfide bond to a corresponding Ala-like unit connected to a second 19-Ala α-helix terminated by a second C-terminal-protonated Lys. The Coulomb potentials arising from the two charged Lys residues and dipole potentials arising from the two oppositely directed 72 D dipoles of the α-helices act to stabilize the SS bond's σ* orbital. The Coulomb potentials provide stabilization of 1 eV, while the two large dipoles generate an additional 4 eV. Such stabilization allows the SS σ* orbital to attach an electron and thereby generate disulfide bond cleavage products. Although calculations are performed only on SS bond cleavage, discussion of N-C(α) bond cleavage caused by electron attachment to amide π* orbitals is also presented. The magnitudes of the stabilization energies as well as the fact that they arise from Coulomb and dipole potentials are supported by results on a small model system consisting of a H(3)C-SS-CH(3) molecule with positive and negative fractional point charges to its left and right designed to represent (i) two positive charges ca. 32 Å distant (i.e., the two charged Lys sites of the peptide model) and (ii) two 72 D dipoles (i.e., the two α-helices). Earlier workers suggested that internal dipole forces in polypeptides could act to guide incoming free electrons (i.e., in electron capture dissociation (ECD)) toward the positive end of the dipole and thus affect the branching ratios for cleaving various bonds. Those workers argued that, because of the huge mass difference between an anion donor and a free electron, internal dipole forces would have a far smaller influence over the trajectory of a donor (i.e., in electron transfer dissociation

First-principles study of H2 adsorption and dissociation on Zr(0 0 0 1)

International Nuclear Information System (INIS)

Zhang Peng; Wang Shuangxi; Zhao Jian; He Chaohui; Zhang Ping

2011-01-01

Highlights: → The stability of the equilibrium adsorption states is determined after the geometry optimization. → The origin of the stable chemisorbed state is analyzed by the electronic structure and charge redistribution calculation. → The dissociation energetics of H2 are investigated in details by the PES and CINEB calculation. - Abstract: The adsorption and dissociation of H 2 molecules on the Zr(0 0 0 1) surface are systematically investigated by using density functional theory within the generalized gradient approximation and a supercell approach. After geometry optimization, the most stable equilibrium adsorption state is found to be along the top-y entrance. By calculating the adiabatic potential energy surface, the chemisorbed molecular adsorption states are also identified to be along the parallel channel at the top site. The electronic properties of the stable chemisorbed molecular state are analyzed, which show that the interaction between the molecule and substrate is of covalent characteristic with a sizeable charge redistribution. On the other hand, the hcp site is turned out to be the most stable equilibrium adsorption site for hydrogen atom on Zr(0 0 0 1) surface after the dissociation of H 2 . The dissociation energetics of H 2 are studied by calculating the potential energy surface and the minimum energy path of the transition state is determined by using the climb image nudged elastic band method, wherein the fcc-y channel is found to be most stable and favorable for dissociative adsorption of H 2 among the five possible dissociative paths. Remarkably, we find that the adiabatic dissociation process of H 2 is an activated type but with a small energy barrier, which is well consistent with the macroscopic phenomenon that the zirconium metal is easily hydrogenated.

Gene-specific characterization of human histone H2B by electron capture dissociation.

Science.gov (United States)

Siuti, Nertila; Roth, Michael J; Mizzen, Craig A; Kelleher, Neil L; Pesavento, James J

2006-02-01

The basis set of protein forms expressed by human cells from the H2B gene family was determined by Top Down Mass Spectrometry. Using Electron Capture Dissociation for MS/MS of H2B isoforms, direct evidence for the expression of unmodified H2B.Q, H2B.A, H2B.K/T, H2B.J, H2B.E, H2B.B, H2B.F, and monoacetylated H2B.A was obtained from asynchronous HeLa cells. H2B.A was the most abundant form, with the overall expression profile not changing significantly in cells arrested in mitosis by colchicine or during mid-S, mid-G2, G2/M, and mid-G1 phases of the cell cycle. Modest hyperacetylation of H2B family members was observed after sodium butyrate treatment.

Hydrogen bonded C-H···Y (Y = O, S, Hal) molecular complexes: A natural bond orbital analysis

Science.gov (United States)

Isaev, A. N.

2016-03-01

Hydrogen bonded C-H···Y complexes formed by H2O, H2S molecules, hydrogen halides, and halogen-ions with methane, halogen substituted methane as well as with the C2H2 and NCH molecules were studied at the MP2/aug-cc-pVDZ level. The structure of NBOs corresponding to lone pair of acceptor Y, n Y, and vacant anti-σ-bond C-H of proton donor was analyzed and estimates of second order perturbation energy E(2) characterizing donor-acceptor n Y → σ C-H * charge-transfer interaction were obtained. Computational results for complexes of methane and its halogen substituted derivatives show that for each set of analogous structures, the EnY→σ*C-H (2) energy tends to grow with an increase in the s-component percentage in the lone pair NBO of acceptor Y. Calculations for different C···Y distances show that the equilibrium geometries of complexes lie in the region where the E(2) energy is highest and it changes symbatically with the length of the covalent E-H bond when the R(C···Y) distance is varied. The performed analysis allows us to divide the hydrogen bonded complexes into two groups, depending on the pattern of overlapping for NBOs of the hydrogen bridge.

The impact of the self-interaction error on the density functional theory description of dissociating radical cations: ionic and covalent dissociation limits.

Science.gov (United States)

Gräfenstein, Jürgen; Kraka, Elfi; Cremer, Dieter

2004-01-08

Self-interaction corrected density functional theory was used to determine the self-interaction error for dissociating one-electron bonds. The self-interaction error of the unpaired electron mimics nondynamic correlation effects that have no physical basis where these effects increase for increasing separation distance. For short distances the magnitude of the self-interaction error takes a minimum and increases then again for decreasing R. The position of the minimum of the magnitude of the self-interaction error influences the equilibrium properties of the one-electron bond in the radical cations H2+ (1), B2H4+ (2), and C2H6+ (3), which differ significantly. These differences are explained by hyperconjugative interactions in 2 and 3 that are directly reflected by the self-interaction error and its orbital contributions. The density functional theory description of the dissociating radical cations suffers not only from the self-interaction error but also from the simplified description of interelectronic exchange. The calculated differences between ionic and covalent dissociation for 1, 2, and 3 provide an excellent criterion for determining the basic failures of density functional theory, self-interaction corrected density functional theory, and other methods. Pure electronic, orbital relaxation, and geometric relaxation contributions to the self-interaction error are discussed. The relevance of these effects for the description of transition states and charge transfer complexes is shown. Suggestions for the construction of new exchange-correlation functionals are given. In this connection, the disadvantages of recently suggested self-interaction error-free density functional theory methods are emphasized. (c) 2004 American Institute of Physics

Time resolved studies of H2+ dissociation with phase-stabilized laser pulses

International Nuclear Information System (INIS)

Fischer, Bettina

2010-01-01

In the course of this thesis, experimental studies on the dissociation of H 2 + (H 2 + →p+H) in ultrashort laser pulses with a stabilized carrier-envelope phase (CEP) were carried out. In single-pulse measurements, the ability to control the emission direction of low energetic protons, i.e. the localization of the bound electron at one of the nuclei after dissociation, by the CEP was demonstrated. The coincident detection of the emitted protons and electrons and the measurement of their three-dimensional momentum vectors with a reaction microscope allowed to clarify the localization mechanism. Further control was achieved by a pump-control scheme with two timedelayed CEP-stabilized laser pulses. Here the neutral H 2 molecule was ionized in the first pulse and dissociation was induced by the second pulse. Electron localization was shown to depend on the properties of the bound nuclear wave packet in H 2 + at the time the control pulse is applied, demonstrating the ability to use the shape and dynamics of the nuclear wave packet as control parameters. Wave packet simulations were performed reproducing qualitatively the experimental results of the single and the two-pulse measurements. For both control schemes, intuitive models are presented, which qualitatively explain the main features of the obtained results. (orig.)

On the Mechanism of the Copper-Mediated C-S Bond Formation in the Intramolecular Disproportionation of Imine Disulfides

Czech Academy of Sciences Publication Activity Database

Rokob, Tibor András; Rulíšek, Lubomír; Šrogl, Jiří; Révész, Agnes; Zins, Emilie-Laure; Schröder, Detlef

2011-01-01

Roč. 50, č. 20 (2011), s. 9968-9979 ISSN 0020-1669 R&D Projects: GA MŠk LC512 Grant - others:European Research Council(XE) AdG HORIZOMS Institutional research plan: CEZ:AV0Z40550506 Keywords : collision-induced dissociation * DFT calculations * C-S bond formation * Cu(I) catalysis * infrared multiphoton spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.601, year: 2011

Nature of the three-electron bond in H2S∴SH2+

NARCIS (Netherlands)

Bickelhaupt, F. Matthias; Diefenbach, Axel; De Visser, Sam P.; De Koning, Leo J.; Nibbering, Nico M.M.

1998-01-01

We have investigated the model system H2S∴-SH2+, i.e., the sulfur-sulfur bound dimer radical cation of H2S, using both density functional theory (LDA, BP86, PW91) and traditional ab initio theory (up to CCSD-(T)). Our purpose is to better understand the nature of the three-electron bond. The S-S

Cleavage of sp3 C-O bonds via oxidative addition of C-H bonds.

Science.gov (United States)

Choi, Jongwook; Choliy, Yuriy; Zhang, Xiawei; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S

2009-11-04

(PCP)Ir (PCP = kappa(3)-C(6)H(3)-2,6-[CH(2)P(t-Bu)(2)](2)) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, including methoxy-3,5-bis(trifluoromethyl)benzene and methoxypentafluorobenzene, to give the corresponding aryloxide complexes (PCP)Ir(CH(3))(OAr). Although the net reaction is insertion of the Ir center into the C-O bond, density functional theory (DFT) calculations and a significant kinetic isotope effect [k(CH(3))(OAr)/k(CD(3))(OAr) = 4.3(3)] strongly argue against a simple insertion mechanism and in favor of a pathway involving C-H addition and alpha-migration of the OAr group to give a methylene complex followed by hydride-to-methylene migration to give the observed product. Ethoxy aryl ethers, including ethoxybenzene, also undergo C-O bond cleavage by (PCP)Ir, but the net reaction in this case is 1,2-elimination of ArO-H to give (PCP)Ir(H)(OAr) and ethylene. DFT calculations point to a low-barrier pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by beta-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp(3))-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.

An ab initio study of potential energy surfaces of CH 3COCN dissociation on the low-lying states

Science.gov (United States)

Ding, Wan-Jian; Fang, Wei-Hai; Liu, Ruo-Zhuang

2002-01-01

The C-CH 3 and C-CN bond dissociations of CH 3COCN on S 1 and T 1 surfaces are studied at the CAS(8,7)/cc-pVDZ level. The results show that the intersystem crossing from S 1 to T 1 is a favorable pathway of S 1 deactivation. Once on the T 1 surface, the system can dissociate adiabatically to CH3 ( X˜)+ OCCN ( X˜) or CN ( X˜)+ CH3CO ( X˜) , but the former has some preference over the latter. This mechanism is consistent with Cheng's presumption deduced from the experimental facts and theoretical considerations. A comparison with other asymmetrically substituted carbonyl compounds suggests that the selectivity of the α-bond cleavage is mainly dependent on the mechanism of dissociation.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

Science.gov (United States)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-05-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

Science.gov (United States)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-02-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Aggregation-induced chemical reactions: acid dissociation in growing water clusters.

Science.gov (United States)

Forbert, Harald; Masia, Marco; Kaczmarek-Kedziera, Anna; Nair, Nisanth N; Marx, Dominik

2011-03-23

Understanding chemical reactivity at ultracold conditions, thus enabling molecular syntheses via interstellar and atmospheric processes, is a key issue in cryochemistry. In particular, acid dissociation and proton transfer reactions are ubiquitous in aqueous microsolvation environments. Here, the full dissociation of a HCl molecule upon stepwise solvation by a small number of water molecules at low temperatures, as relevant to helium nanodroplet isolation (HENDI) spectroscopy, is analyzed in mechanistic detail. It is found that upon successive aggregation of HCl with H(2)O molecules, a series of cyclic heteromolecular structures, up to and including HCl(H(2)O)(3), are initially obtained before a precursor state for dissociation, HCl(H(2)O)(3)···H(2)O, is observed upon addition of a fourth water molecule. The latter partially aggregated structure can be viewed as an "activated species", which readily leads to dissociation of HCl and to the formation of a solvent-shared ion pair, H(3)O(+)(H(2)O)(3)Cl(-). Overall, the process is mostly downhill in potential energy, and, in addition, small remaining barriers are overcome by using kinetic energy released as a result of forming hydrogen bonds due to aggregation. The associated barrier is not ruled by thermal equilibrium but is generated by athermal non-equilibrium dynamics. These "aggregation-induced chemical reactions" are expected to be of broad relevance to chemistry at ultralow temperature much beyond HENDI spectroscopy.

Molecular treatment of single (dissociative and nondissociative) and double electron capture in He2+ + H2 collisions

International Nuclear Information System (INIS)

Errea, L F; Macias, A; Mendez, L; Pons, B; Riera, A

2003-01-01

We present close-coupling calculations of total cross sections for single and double electron capture in He 2+ + H 2 collisions in the range 0.5- 25 keV amu -1 , and compare them with experimental data. We confirm the experimental finding that the dominant process for E ∼> 3 keV amu -1 is the nondissociative capture He 2+ + H 2 → He + (2l) + H 2 + (1σ g ), while at lower energies it is dissociative capture leading to He + (1s) + H + + H. Our calculations also show that He(1s2l) is the main output of the two electron capture process. (letter to the editor)

The investigation of adsorption and dissociation of H2O on Li2O (111) by ab initio theory

International Nuclear Information System (INIS)

Kong, Xianggang; Yu, You; Ma, Shenggui; Gao, Tao; Lu, Tiecheng; Xiao, Chengjian; Chen, Xiaojun; Zhang, Chuanyu

2017-01-01

Highlights: • The adsorption structures of H 2 O on Li 2 O (111) are obtained by calculations. • By Bader charge analysis, the charge translation from slab to adsorbate is found. • The vibrational frequencies of adsorbate are in line with the experimental values. - Abstract: The adsorption and dissociation mechanism of H 2 O molecule on the Li 2 O (111) surface have been systematically studied by using the density functional theory calculations. The parallel and vertical configurations of H 2 O at six different symmetry adsorption sites on the Li 2 O (111) surface are considered. In our calculations, it is suggested that H 2 O can dissociate on the perfect Li 2 O surface, of which the corresponding adsorption energy is 1.118 eV. And the adsorption energy decrease to be 0.241 eV when oxygen atom of H 2 O bonds to lithium atom of the slab. The final configurations are sensitive to the initial molecular orientation. By Bader charge analysis, the charge transfer from slab to adsorbed H 2 O/OH can be found due to the downward shift of lowest-unoccupied molecular orbital. We also analyze the vibrational frequencies at the Brillouin Zone centre for H 2 O molecule adsorbed on the stoichiometric surface. Due to the slightly different structure parameters, the calculated values of the vibrational frequencies of hydroxyl group range from 3824 to 3767 cm −1 . Our results agree well with experimental results performed in FT-IR spectrum, which showed that an absorption peak of OH group appeared at 3677 cm −1 at room temperature.

A bonding study of c-C5H8 adsorption on Pt(111)

International Nuclear Information System (INIS)

Simonetti, S.; Jasen, P.; Gonzalez, E.; Juan, A.; Brizuela, G.

2006-01-01

The chemisorption of cyclopentane (c-C 5 H 8 ) on Pt(111) has been studied using a qualitative band-structure calculations in the framework of tight-binding implementation with the YAeHMOP package. We modeled the metal surface by a two-dimensional slab of finite thickness with an overlayer of c-C 5 H 8 , in a (3x3) di-σ geometry. The c-C 5 H 8 molecule is attached to the surface with its C?C atoms bonded mainly with two Pt atoms while the opposite CH 2 bends towards the surface. The Pt?Pt bonds in the underlying surface and the C?C bonds of c-C 5 H 8 are weakened upon the chemisorption. A noticeable Pt-H and Pt-C interactions has been observed. We found that of Pt 5d z 2 band plays an important role in the bonding between c-C 5 H 8 and the surface, as do the Pt 6s and 6p z bands. The HOMO-LUMO bands of c-C 5 H 8 are very dispersed, indicative of a strong interaction with the metal surface

Hydrogen spillover in Pt-single-walled carbon nanotube composites: formation of stable C-H bonds.

Science.gov (United States)

Bhowmick, Ranadeep; Rajasekaran, Srivats; Friebel, Daniel; Beasley, Cara; Jiao, Liying; Ogasawara, Hirohito; Dai, Hongjie; Clemens, Bruce; Nilsson, Anders

2011-04-13

Using in situ electrical conductivity and ex situ X-ray photoelectron spectroscopy (XPS) measurements, we have examined how the hydrogen uptake of single-walled carbon nanotubes (SWNTs) is influenced by the addition of Pt nanoparticles. The conductivity of platinum-sputtered single-walled carbon nanotubes (Pt-SWNTs) during molecular hydrogen exposure decreased more rapidly than that of the corresponding pure SWNTs, which supports a hydrogenation mechanism facilitated by "spillover" of dissociated hydrogen from the Pt nanoparticles. C 1s XPS spectra indicate that the Pt-SWNTs store hydrogen by means of chemisorption, that is, covalent C-H bond formation: molecular hydrogen charging at elevated pressure (8.27 bar) and room temperature yielded Pt-SWNTs with up to 16 ± 1.5 at. % sp(3)-hybridized carbon atoms, which corresponds to a hydrogen-storage capacity of 1.2 wt % (excluding the weight of Pt nanoparticles). Pt-SWNTs prepared by the Langmuir-Blodgett (LB) technique exhibited the highest Pt/SWNT ratio and also the best hydrogen uptake. © 2011 American Chemical Society

Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation.

Science.gov (United States)

Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin

2014-09-14

An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

Inter-row Adsorption Configuration and Stability of Threonine Adsorbed on the Ge(100) Surfaces

International Nuclear Information System (INIS)

Lee, Myungjin; Park, Youngchan; Jeong, Hyuk; Lee, Hangil

2013-01-01

The adsorption structures of threonine on the Ge(100) surface were investigated using core-level photoemission spectroscopy (CLPES) in conjunction with density functional theory (DFT) calculations. CLPES measurements were performed to identify the experimentally preferred adsorption structure. The preferred structure indicated the relative reactivities of the carboxyl and hydroxymethyl groups as electron donors to the Ge(100) surface during adsorption. The core-level C 1s, N 1s, and O 1s CLPES spectra indicated that the carboxyl oxygen competed more strongly with the hydroxymethyl oxygen during the adsorption reaction. Three among six possible adsorption structures were identified as energetically favorable using DFT calculation methods that considered the inter- and intra-bonding configurations upon adsorption onto the Ge(100) surface. These structures were O-H dissociated N dative inter bonding, O-H dissociated N dative intra bonding, O-H dissociation bonding. One of the adsorption structures: O-H dissociated N dative inter bonding was predicted to be stable in light of the transition state energies. We thus confirmed that the most favorable adsorption structure is the O-H dissociated N dative-inter bonding structure using CLPES and DFT calculation

UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: Competition between C–Y (Y = halogen) and O–H bond fission

International Nuclear Information System (INIS)

Sage, Alan G.; Oliver, Thomas A. A.; King, Graeme A.; Murdock, Daniel; Harvey, Jeremy N.; Ashfold, Michael N. R.

2013-01-01

The wavelength dependences of C–Y and O–H bond fission following ultraviolet photoexcitation of 4-halophenols (4-YPhOH) have been investigated using a combination of velocity map imaging, H Rydberg atom photofragment translational spectroscopy, and high level spin-orbit resolved electronic structure calculations, revealing a systematic evolution in fragmentation behaviour across the series Y = I, Br, Cl (and F). All undergo O–H bond fission following excitation at wavelengths λ≲ 240 nm, on repulsive ((n/π)σ*) potential energy surfaces (PESs), yielding fast H atoms with mean kinetic energies ∼11 000 cm −1 . For Y = I and Br, this process occurs in competition with prompt C–I and C–Br bond cleavage on another (n/π)σ* PES, but no Cl/Cl* products unambiguously attributable to one photon induced C–Cl bond fission are observed from 4-ClPhOH. Differences in fragmentation behaviour at longer excitation wavelengths are more marked. Prompt C–I bond fission is observed following excitation of 4-IPhOH at all λ≤ 330 nm; the wavelength dependent trends in I/I* product branching ratio, kinetic energy release, and recoil anisotropy suggest that (with regard to C–I bond fission) 4-IPhOH behaves like a mildly perturbed iodobenzene. Br atoms are observed when exciting 4-BrPhOH at long wavelengths also, but their velocity distributions suggest that dissociation occurs after internal conversion to the ground state. O–H bond fission, by tunnelling (as in phenol), is observed only in the cases of 4-FPhOH and, more weakly, 4-ClPhOH. These observed differences in behaviour can be understood given due recognition of (i) the differences in the vertical excitation energies of the C–Y centred (n/π)σ* potentials across the series Y = I < Br < Cl and the concomitant reduction in C–Y bond strength, cf. that of the rival O–H bond, and (ii) the much increased spin-orbit coupling in, particularly, 4-IPhOH. The present results provide (another) reminder of the

UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: competition between C-Y (Y = halogen) and O-H bond fission.

Science.gov (United States)

Sage, Alan G; Oliver, Thomas A A; King, Graeme A; Murdock, Daniel; Harvey, Jeremy N; Ashfold, Michael N R

2013-04-28

The wavelength dependences of C-Y and O-H bond fission following ultraviolet photoexcitation of 4-halophenols (4-YPhOH) have been investigated using a combination of velocity map imaging, H Rydberg atom photofragment translational spectroscopy, and high level spin-orbit resolved electronic structure calculations, revealing a systematic evolution in fragmentation behaviour across the series Y = I, Br, Cl (and F). All undergo O-H bond fission following excitation at wavelengths λ ≲ 240 nm, on repulsive ((n∕π)σ∗) potential energy surfaces (PESs), yielding fast H atoms with mean kinetic energies ∼11,000 cm(-1). For Y = I and Br, this process occurs in competition with prompt C-I and C-Br bond cleavage on another (n∕π)σ∗ PES, but no Cl∕Cl∗ products unambiguously attributable to one photon induced C-Cl bond fission are observed from 4-ClPhOH. Differences in fragmentation behaviour at longer excitation wavelengths are more marked. Prompt C-I bond fission is observed following excitation of 4-IPhOH at all λ ≤ 330 nm; the wavelength dependent trends in I∕I∗ product branching ratio, kinetic energy release, and recoil anisotropy suggest that (with regard to C-I bond fission) 4-IPhOH behaves like a mildly perturbed iodobenzene. Br atoms are observed when exciting 4-BrPhOH at long wavelengths also, but their velocity distributions suggest that dissociation occurs after internal conversion to the ground state. O-H bond fission, by tunnelling (as in phenol), is observed only in the cases of 4-FPhOH and, more weakly, 4-ClPhOH. These observed differences in behaviour can be understood given due recognition of (i) the differences in the vertical excitation energies of the C-Y centred (n∕π)σ∗ potentials across the series Y = I bond strength, cf. that of the rival O-H bond, and (ii) the much increased spin-orbit coupling in, particularly, 4-IPhOH. The present results provide (another) reminder of the risks inherent in extrapolating photochemical

"Vibrational bonding": a new type of chemical bond is discovered.

Science.gov (United States)

Rhodes, Christopher J; Macrae, Roderick M

2015-01-01

A long-sought but elusive new type of chemical bond, occurring on a minimum-free, purely repulsive potential energy surface, has recently been convincingly shown to be possible on the basis of high-level quantum-chemical calculations. This type of bond, termed a vibrational bond, forms because the total energy, including the dynamical energy of the nuclei, is lower than the total energy of the dissociated products, including their vibrational zero-point energy. For this to be the case, the ZPE of the product molecule must be very high, which is ensured by replacing a conventional hydrogen atom with its light isotope muonium (Mu, mass = 1/9 u) in the system Br-H-Br, a natural transition state in the reaction between Br and HBr. A paramagnetic species observed in the reaction Mu +Br2 has been proposed as a first experimental sighting of this species, but definitive identification remains challenging.

Dynamics of dissociative adsorption of hydrogen on Ni(100)

International Nuclear Information System (INIS)

Hamza, A.V.; Madix, R.J.

1985-01-01

Nearly monoenergetic beams of hydrogen and deuterium were used to determine dissociative sticking probabilities for H 2 and D 2 on Ni(100) at various energies. Variation of the surface temperature between 90 and 300 K had no effect on the dissociative sticking probability of H 2 at 3.6 and 5.8 kJ/mol incident beam energy, indicating a direct mechanism of dissociation. A four fold increase in the initial dissociative sticking probability for H 2 from 0.2 to 0.8 was observed by increasing the translational kinetic energy from 0.7 to 7.0 kJ/mol. The initial dissociative sticking probability for D 2 was slightly lower, increasing from 0.15 to 0.75 with increasing translational kinetic energy from 1.3 to 10.5 kJ/mol. The form of the increase with kinetic energy was explained by tunnelling through a low activation barrier, accounting as well for the high dissociation probability at low kinetic energies. The dissociative sticking probability decreased with hydrogen or deuterium adatom coverage at all energies. The decline in sticking probability with hydrogen coverage was fit to a s(theta) = s 0 (1 - a theta)/sup n/ functional form. From this relationship it was deduced that hydrogen adatoms block only single sites and that four vacant sites are needed for dissociation. The dissociative sticking probability for H 2 declined precipitously from 0.77 to 0.16 with oxygen adatom coverage from 0 to 5% of a monolayer at a translational energy of 9.6 kJ.mol. 36 references, 8 figures

Multireference theoretical investigation on selectivity of the bond fissions in photodissociation of acetyl cyanide

Science.gov (United States)

Xiao, Hong-Yan; Liu, Ya-Jun; Fang, Wei-Hai

2007-12-01

The selectivity of the C -CH3 and C-CN bond fissions upon excitation of acetyl cyanide at 193nm has been investigated at the theoretical level of multistate complete active space self-consistent field second order perturbation. The calculated results indicated that the initially excited S3 state relaxes to S2 via ultrafast internal conversion. The S2 state could dissociate via two pathways. One, adiabatically dissociates to CH3CO(X˜)+CN(Ã). The other one internally converts to S1 before S1 intersystem crossing to T1. The T1 state subsequently dissociates to two groups of products: CH3(X˜)+OCCN(X˜) and CH3CO(X˜)+CN(X˜). The experimentally observed preference branching of CN elimination over CH3 one and bond selectivity are the results of the competition between the adiabatic and nonadiabatic dynamics of the S2 state.

Valence bond model potential energy surface for H4

International Nuclear Information System (INIS)

Silver, D.M.; Brown, N.J.

1980-01-01

Potential energy surfaces for the H 4 system are derived using the valence bond procedure. An ab initio evaluation of the valence bond energy expression is described and some of its numerical properties are given. Next, four semiempirical evaluations of the valence bond energy are defined and parametrized to yield reasonable agreement with various ab initio calculations of H 4 energies. Characteristics of these four H 4 surfaces are described by means of tabulated energy minima and equipotential contour maps for selected geometrical arrangements of the four nuclei

UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: Competition between C-Y (Y = halogen) and O-H bond fission

Science.gov (United States)

Sage, Alan G.; Oliver, Thomas A. A.; King, Graeme A.; Murdock, Daniel; Harvey, Jeremy N.; Ashfold, Michael N. R.

2013-04-01

The wavelength dependences of C-Y and O-H bond fission following ultraviolet photoexcitation of 4-halophenols (4-YPhOH) have been investigated using a combination of velocity map imaging, H Rydberg atom photofragment translational spectroscopy, and high level spin-orbit resolved electronic structure calculations, revealing a systematic evolution in fragmentation behaviour across the series Y = I, Br, Cl (and F). All undergo O-H bond fission following excitation at wavelengths λ ≲ 240 nm, on repulsive ((n/π)σ*) potential energy surfaces (PESs), yielding fast H atoms with mean kinetic energies ˜11 000 cm-1. For Y = I and Br, this process occurs in competition with prompt C-I and C-Br bond cleavage on another (n/π)σ* PES, but no Cl/Cl* products unambiguously attributable to one photon induced C-Cl bond fission are observed from 4-ClPhOH. Differences in fragmentation behaviour at longer excitation wavelengths are more marked. Prompt C-I bond fission is observed following excitation of 4-IPhOH at all λ ≤ 330 nm; the wavelength dependent trends in I/I* product branching ratio, kinetic energy release, and recoil anisotropy suggest that (with regard to C-I bond fission) 4-IPhOH behaves like a mildly perturbed iodobenzene. Br atoms are observed when exciting 4-BrPhOH at long wavelengths also, but their velocity distributions suggest that dissociation occurs after internal conversion to the ground state. O-H bond fission, by tunnelling (as in phenol), is observed only in the cases of 4-FPhOH and, more weakly, 4-ClPhOH. These observed differences in behaviour can be understood given due recognition of (i) the differences in the vertical excitation energies of the C-Y centred (n/π)σ* potentials across the series Y = I increased spin-orbit coupling in, particularly, 4-IPhOH. The present results provide (another) reminder of the risks inherent in extrapolating photochemical behaviour measured for one molecule at one wavelength to other (related) molecules and to

Dissociation of fast HeH+ ions in foils and gases

International Nuclear Information System (INIS)

Gemmell, D.S.; Cooney, P.J.; Pietsch, W.J.; Ratkowski, A.J.; Vager, Z.

1978-01-01

To gain understanding of phenomena observed when very simple light diatomic ions are incident at high velocities upon thin foils and gaseous targets, an extensive set of measurements on the dissociation products arising from beams of HeH + was made. Experimental and calculated joint distributions in energy and angle for protons emerging (near the beam direction) from an 85-A carbon foil bombarded by 2.0-MeV HeH + ions are presented

Guided ion beam and theoretical studies of the bond energy of SmS+

Science.gov (United States)

Armentrout, P. B.; Demireva, Maria; Peterson, Kirk A.

2017-12-01

Previous work has shown that atomic samarium cations react with carbonyl sulfide to form SmS+ + CO in an exothermic and barrierless process. To characterize this reaction further, the bond energy of SmS+ is determined in the present study using guided ion beam tandem mass spectrometry. Reactions of SmS+ with Xe, CO, and O2 are examined. Results for collision-induced dissociation processes with all three molecules along with the endothermicity of the SmS+ + CO → Sm+ + COS exchange reaction are combined to yield D0(Sm+-S) = 3.37 ± 0.20 eV. The CO and O2 reactions also yield a SmSO+ product, with measured endothermicities that indicate D0(SSm+-O) = 3.73 ± 0.16 eV and D0(OSm+-S) = 1.38 ± 0.27 eV. The SmS+ bond energy is compared with theoretical values characterized at several levels of theory, including CCSD(T) complete basis set extrapolations using all-electron basis sets. Multireference configuration interaction calculations with explicit spin-orbit calculations along with composite thermochemistry using the Feller-Peterson-Dixon method and all-electron basis sets were also explored for SmS+, and for comparison, SmO, SmO+, and EuO.

AVE bond index in the H-bond of the Watson-Crick pairs

International Nuclear Information System (INIS)

Giambiagi, M.; Giambiagi, M.S. de; Barroso Filho, W.

1981-01-01

The normal Watson-Crick base pairs are treated as super-molecules. The properties of the electronic distribution along the N-H...Y bonds are studied in an all-valence-electrons calculation, through a bond index formula devised for non-orthogonal basis. Eletronic density diagrams of the adenine-uracil base pair are analysed. (Auhor) [pt

Adsorption and dissociation of H2O on Al(1 1 1) surface by density functional theory calculation

International Nuclear Information System (INIS)

Guo, F.Y.; Long, C.G.; Zhang, J.; Zhang, Z.; Liu, C.H.; Yu, K.

2015-01-01

Highlights: • O 2 on Al(1 1 1) surface can spontaneously dissociate, but H 2 O can not. • H 2 O, OH and H on top sites are favorable on Al(1 1 1) surface. • O on the hollow (fcc) site is preferred. • O which plays a key role in the dissociate reaction of H 2 O. - Abstract: Using the first-principles calculations method based on the density functional theory, we systematically study the adsorption behavior of a single molecular H 2 O on a clean and a pre-adsorbed O atom Al(1 1 1) surface, and also its corresponding dissociation reactions. The equilibrium configuration on top, bridge, and hollow (fcc and hcp) site were determined by relaxation of the system relaxation. The adsorptions of H 2 O, OH and H on top sites are favorable on the Al(1 1 1) surface, while that of O on the hollow (fcc) site is preferred. The results show that the hydrogen atom dissociating from H 2 O needs a 248.32 kJ/mol of energy on clean Al(1 1 1) surface, while the dissociating energy decreases to 128.53 kJ/mol with the aid of the O absorption. On the other hand, these phenomena indicate that the dehydrogenated reaction energy barrier of the pre-adsorbed O on metal surface is lower than that of on a clean one, because O can promote the dehydrogenation of H 2 O

Selective bond cleavage in potassium collisions with pyrimidine bases of DNA.

Science.gov (United States)

Almeida, Diogo; Ferreira da Silva, Filipe; García, Gustavo; Limão-Vieira, Paulo

2013-01-11

Electron transfer in alkali-molecule collisions to gas phase thymine and uracil yielding H- formation is selectively controlled in the energy range between 5.3 and 66.1 eV. By tuning the collision energy, electron transfer from the alkali to partly deuterated thymine, methylated thymine at the N1 and methylated uracil at the N3 positions, H- loss proceeds not only through the breaking of the (C-H) against (N-H) bonds but also through N1 against N3 sites. Such selectivity, as far as bond and site are concerned, is here reported for the first time by electron transfer induced dissociation experiments in alkali-molecule collisions.

Interplay of Electronic Cooperativity and Exchange Coupling in Regulating the Reactivity of Diiron(IV)-oxo Complexes towards C-H and O-H Bond Activation.

Science.gov (United States)

Ansari, Azaj; Ansari, Mursaleem; Singha, Asmita; Rajaraman, Gopalan

2017-07-26

Activation of inert C-H bonds such as those of methane are extremely challenging for chemists but in nature, the soluble methane monooxygenase (sMMO) enzyme readily oxidizes methane to methanol by using a diiron(IV) species. This has prompted chemists to look for similar model systems. Recently, a (μ-oxo)bis(μ-carboxamido)diiron(IV) ([Fe IV 2 O(L) 2 ] 2+ L=N,N-bis-(3',5'-dimethyl-4'-methoxypyridyl-2'-methyl)-N'-acetyl-1,2-diaminoethane) complex has been generated by bulk electrolysis and this species activates inert C-H bonds almost 1000 times faster than mononuclear Fe IV =O species and at the same time selectively activates O-H bonds of alcohols. The very high reactivity and selectivity of this species is puzzling and herein we use extensive DFT calculations to shed light on this aspect. We have studied the electronic and spectral features of diiron {Fe III -μ(O)-Fe III } +2 (complex I), {Fe III -μ(O)-Fe IV } +3 (II), and {Fe IV -μ(O)-Fe IV } +4 (III) complexes. Strong antiferromagnetic coupling between the Fe centers leads to spin-coupled S=0, S=3/2, and S=0 ground state for species I-III respectively. The mechanistic study of the C-H and O-H bond activation reveals a multistate reactivity scenario where C-H bond activation is found to occur through the S=4 spin-coupled state corresponding to the high-spin state of individual Fe IV centers. The O-H bond activation on the other hand, occurs through the S=2 spin-coupled state corresponding to an intermediate state of individual Fe IV centers. Molecular orbital analysis reveals σ-π/π-π channels for the reactivity. The nature of the magnetic exchange interaction is found to be switched during the course of the reaction and this offers lower energy pathways. Significant electronic cooperativity between two metal centers during the course of the reaction has been witnessed and this uncovers the reason behind the efficiency and selectivity observed. The catalyst is found to prudently choose the desired spin

H2S adsorption and decomposition on the gradually reduced α-Fe2O3(001) surface: A DFT study

Science.gov (United States)

Lin, Changfeng; Qin, Wu; Dong, Changqing

2016-11-01

Reduction of iron based desulfurizer occurs during hot gas desulfurization process, which will affect the interaction between H2S and the desulfurizer surface. In this work, a detailed adsorption behavior and dissociation mechanism of H2S on the perfect and reduced α-Fe2O3(001) surfaces, as well as the correlation between the interaction characteristic and reduction degree of iron oxide, have been studied by using periodic density functional theory (DFT) calculations. Results demonstrate that H2S firstly chemisorbs on surface at relatively higher oxidation state (reduction degree χ 33%. Reduction of iron oxide benefits the H2S adsorption. Further, dissociation processes of H2S via molecular and dissociative adsorption were investigated. Results show that after reduction of Fe2O3 into the oxidation state around FeO and Fe, the reduced surface exhibits very strong catalytic capacity for H2S decomposition into S species. Meanwhile, the overall dissociation process on all surfaces is exothermic. These results provide a fundamental understanding of reduction effect of iron oxide on the interaction mechanism between H2S and desulfurizer surface, and indicate that rational control of reduction degree of desulfurizer is essential for optimizing the hot gas desulfurization process.

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

Science.gov (United States)

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of bond strength of self-etching adhesives having different pH on primary and permanent teeth dentin.

Science.gov (United States)

Ozmen, Bilal; Koyuturk, Alp Erdin; Tokay, Ugur; Cortcu, Murat; Sari, Mustafa Erhan

2015-10-16

The purpose of this in vitro study was to evaluate the dentin shear bond strength of 4 self-etching adhesives having a different pH on primary and permanent teeth dentin. The occlusal enamel was removed from 60 freshly extracted third molar and 60 primary second molar human teeth, which were randomly separated into 4 groups (n = 15). Four adhesive systems were applied: G-Bond (GC Corporation, Tokyo, Japan, pH: 1.5), Futura Bond M (Voco, Cuxhaver, Germany, pH: 1.4), Adper Prompt L-Pop (3M/ESPE, St Paul, MN, USA, pH: 0.8), and Clearfil S(3) Bond (Kuraray Medical, Tokyo, Japan, pH: 2.7) according to the manufacturer's instructions. After the application of dentin bonding agents, a composite resin material (Z250 Restorative A2, 3M ESPE, St. Paul, MN, USA) for permanent teeth and a compomer resin material (Dyract Extra A2, Dentsply, Konstanz, Germany) for primary teeth was applied onto the prepared dentin surfaces. The data were obtained by using a universal test machine at a crosshead speed of 1 mm/min. The mean values were compared using Tukey's multiple comparison test. Although there was no difference between adhesives on the permanent teeth, Clearfil S3 adhesive showed higher bond (18.07 ± 0.58 MPa) (P>0.05). Lower bond strength values were obtained from primary teeth and especially G-Bond adhesive (9.36 ± 0.48 MPa) (Padhesives with different pH and solvent types can be used successfully for permanent teeth dentin but adhesives with low pH did not provide greater shear bond strength values.

Theoretical characterizations of novel C2H5O+ reactions

Science.gov (United States)

Hudson, Charles E.; McAdoo, David J.

2004-03-01

Assorted reactions of C2H5O+ isomers are characterized by theory, including tracing their courses by means of intrinsic reaction coordinate computations. We establish that CH3CH=OH+ eliminates methane by transferring H from oxygen to a methyl hydrogen and then to the CC bond to produce CHO++CH4. This adds to the limited knowledge of the involvement of hypervalent structures in the reactions of cations in the gas phase. Second, we characterized the course of CH3CH=OH+-->H3O++HC[triple bond; length as m-dash]CH. In this dissociation, H first migrates from the methyl to the oxygen to give O-protonated vinyl alcohol, a stable intermediate. Then the H2O swings outward to over the middle of the CC bond while one of the two hydrogens on the non-O-bearing carbon revolves to between the oxygen and the two carbons, leading to formation of a [H3O+ HC[triple bond; length as m-dash]CH] complex. This complex contains sufficient energy to dissociate its partners because a high barrier is crossed in its formation. Third, we found that methane elimination from CH3O+=CH2 involves stretching of the CH3---O bond and then rotation of the methyl so that a methyl hydrogen is pointed directly toward the oxygen. This reaction is completed by further rotation of the methyl to abstract a methylene hydrogen to the opposite side of the methyl from that initially bonded to oxygen. This clearly establishes that this dissociation takes place through an ion-neutral complex. Each of the reaction coordinates for the three preceding reactions traverses a novel bonding stage involving H, evidence that such are not unusual in gas phase ion chemistry. Finally, we showed that in the rearrangement CH3O+=CH2-->CH2=O+CH3, before Ht is transferred CH2 rotates around the C=C bond from being in the skeletal plane to being perpendicular to it, and Ht remains in the skeletal plane throughout its transfer. This pathway appears to balance avoiding an orbital symmetry-forbidden suprafacial transition state with

Discovering H-bonding rules in crystals with inductive logic programming.

Science.gov (United States)

Ando, Howard Y; Dehaspe, Luc; Luyten, Walter; Van Craenenbroeck, Elke; Vandecasteele, Henk; Van Meervelt, Luc

2006-01-01

In the domain of crystal engineering, various schemes have been proposed for the classification of hydrogen bonding (H-bonding) patterns observed in 3D crystal structures. In this study, the aim is to complement these schemes with rules that predict H-bonding in crystals from 2D structural information only. Modern computational power and the advances in inductive logic programming (ILP) can now provide computational chemistry with the opportunity for extracting structure-specific rules from large databases that can be incorporated into expert systems. ILP technology is here applied to H-bonding in crystals to develop a self-extracting expert system utilizing data in the Cambridge Structural Database of small molecule crystal structures. A clear increase in performance was observed when the ILP system DMax was allowed to refer to the local structural environment of the possible H-bond donor/acceptor pairs. This ability distinguishes ILP from more traditional approaches that build rules on the basis of global molecular properties.

Dissociative ionization of H2 and D2 by electron impact near threshold

NARCIS (Netherlands)

Boesten, L.G.J.; Heideman, H.G.M.

We have studied the dissciative ionization of H2 and D2 by electron impact. It is found that in the vicinity of the 2Σ+g dissociation threshold of H+2 (18.08 eV) a significant fraction of the produced protons originates from the process e + H2 → H− + H+ + e (threshold at 17.34 eV). Similar results

Quantification of the selective activation of C--H bonds in short chain alkanes: The reactivity of ethane, propane, isobutane, n-butane, and neopentane on Ir(111)

International Nuclear Information System (INIS)

Johnson, D.F.; Weinberg, W.H.

1995-01-01

The initial probabilities of precursor-mediated, dissociative chemisorption of the saturated hydrocarbons 13 C-labeled ethane, propane, isobutane, n-butane, and neopentane on the close-packed Ir(111) surface have been measured. The selective activation of primary (1 degree), secondary (2 degree), and tertiary (3 degree) C--H bonds has been quantified by examining the reactivities of the selectively deuterated isotopomers of propane, C 3 H 8 , CH 3 CD 2 CH 3 , and C 3 D 8 , and of isobutane, (CH 3 ) 3 CH, (CH 3 ) 3 CD, and (CD 3 ) 3 CH. With respect to the bottom of the physically adsorbed well for each hydrocarbon, the apparent C--H bond activation energies have been found to be 10.4±0.3 kcal/mol (ethane), 11.4±0.3 kcal/mol (propane), 11.5±0.3 kcal/mol (n-butane), 11.3±0.3 kcal/mol (i-butane), and 11.3±0.3 kcal/mol (neopentane). For all the alkanes examined, the ratios of the preexponential factors of the rate coefficients of reaction and desorption are 1x10 -2 . The C--D bond activation energies are higher than the corresponding C--H bond activation energies by 480 cal/mol (ethane), 630 cal/mol (propane), and 660 cal/mol (i-butane). By analyzing the primary kinetic isotope effects for the selectively deuterated isotopomers of propane and isobutane, the 2 degree C--H bond activation energy is found to be 310±160 cal/mol less than the 1 degree C--H bond activation energy on this surface, and similarly, 3 degree C--H bond cleavage is less by 80±70 cal/mol. The quantification of the branching ratios within the C--H bond activation channel for propane and isobutane on this surface shows that the formation of 1 degree-alkyl intermediates is, in general, favored over the formation of either 2 degree- or 3 degree-alkyl intermediates. (Abstract Truncated)

Noncollinear Spin States for Density Functional Calculations of Open-Shell and Multi-Configurational Systems: Dissociation of MnO and NiO and Barrier Heights of O3, BeH2, and H4.

Science.gov (United States)

Luo, Sijie; Truhlar, Donald G

2013-12-10

When the spins of molecular orbitals are allowed to be aligned with different directions in space rather than being aligned collinearly, the resulting noncollinear spin orbitals add extra flexibility to variational optimization of the orbitals, and solutions obtained with collinear spin orbitals may be unstable with respect to becoming noncollinear in the expanded variational space. The goal of the present work is to explore whether and in what way the molecular orbitals of the Kohn-Sham density functional theory become noncollinear when fully optimized for multi-reference molecules, transition states, and reaction paths. (We note that a noncollinear determinant has intermediate flexibility between a collinear determinant and a linear combination of many collinear determinants with completely independent coefficients. However, the Kohn-Sham method is defined to involve the variational optimization of a single determinant, and a noncollinear determinant represents the limit of complete optimization in the Kohn-Sham scheme.) We compare the results obtained with the noncollinear Kohn-Sham (NKS) scheme to those obtained with the widely used unrestricted Kohn-Sham (UKS) scheme for two types of multi-reference systems. For the dissociation of the MnO and NiO transition metal oxides, we find UKS fails to dissociate to the ground states of neutral atoms, while NKS dissociates to the correct limit and predicts potential energy curves that vary smoothly at intermediate bond lengths. This is due to the instability of UKS solutions at large bond distances. For barrier heights of O3, BeH2, and H4, NKS is shown to stabilize the multi-reference transition states by expanding the variational space. Although the errors vary because they are closely coupled with the capability of the employed exchange-correlation functionals in treating the multi-configurational states, these findings demonstrate that results with collinear spin orbitals should be further scrutinized, and future

Cocrystals of 6-propyl-2-thiouracil: N-H···O versus N-H···S hydrogen bonds.

Science.gov (United States)

Tutughamiarso, Maya; Egert, Ernst

2011-11-01

In order to investigate the relative stability of N-H···O and N-H···S hydrogen bonds, we cocrystallized the antithyroid drug 6-propyl-2-thiouracil with two complementary heterocycles. In the cocrystal pyrimidin-2-amine-6-propyl-2-thiouracil (1/2), C(4)H(5)N(3)·2C(7)H(10)N(2)OS, (I), the `base pair' is connected by one N-H···S and one N-H···N hydrogen bond. Homodimers of 6-propyl-2-thiouracil linked by two N-H···S hydrogen bonds are observed in the cocrystal N-(6-acetamidopyridin-2-yl)acetamide-6-propyl-2-thiouracil (1/2), C(9)H(11)N(3)O(2)·2C(7)H(10)N(2)OS, (II). The crystal structure of 6-propyl-2-thiouracil itself, C(7)H(10)N(2)OS, (III), is stabilized by pairwise N-H···O and N-H···S hydrogen bonds. In all three structures, N-H···S hydrogen bonds occur only within R(2)(2)(8) patterns, whereas N-H···O hydrogen bonds tend to connect the homo- and heterodimers into extended networks. In agreement with related structures, the hydrogen-bonding capability of C=O and C=S groups seems to be comparable.

Time resolved studies of H{sub 2}{sup +} dissociation with phase-stabilized laser pulses

Energy Technology Data Exchange (ETDEWEB)

Fischer, Bettina

2010-06-23

In the course of this thesis, experimental studies on the dissociation of H{sub 2}{sup +}(H{sub 2}{sup +}{yields}p+H) in ultrashort laser pulses with a stabilized carrier-envelope phase (CEP) were carried out. In single-pulse measurements, the ability to control the emission direction of low energetic protons, i.e. the localization of the bound electron at one of the nuclei after dissociation, by the CEP was demonstrated. The coincident detection of the emitted protons and electrons and the measurement of their three-dimensional momentum vectors with a reaction microscope allowed to clarify the localization mechanism. Further control was achieved by a pump-control scheme with two timedelayed CEP-stabilized laser pulses. Here the neutral H{sub 2} molecule was ionized in the first pulse and dissociation was induced by the second pulse. Electron localization was shown to depend on the properties of the bound nuclear wave packet in H{sub 2}{sup +} at the time the control pulse is applied, demonstrating the ability to use the shape and dynamics of the nuclear wave packet as control parameters. Wave packet simulations were performed reproducing qualitatively the experimental results of the single and the two-pulse measurements. For both control schemes, intuitive models are presented, which qualitatively explain the main features of the obtained results. (orig.)

Fixed-Node Diffusion Quantum Monte Carlo Method on Dissociation Energies and Their Trends for R-X Bonds (R = Me, Et, i-Pr, t-Bu).

Science.gov (United States)

Hou, Aiqiang; Zhou, Xiaojun; Wang, Ting; Wang, Fan

2018-05-15

Achieving both bond dissociation energies (BDEs) and their trends for the R-X bonds with R = Me, Et, i-Pr, and t-Bu reliably is nontrivial. Density functional theory (DFT) methods with traditional exchange-correlation functionals usually have large error on both the BDEs and their trends. The M06-2X functional gives rise to reliable BDEs, but the relative BDEs are determined not as accurately. More demanding approaches such as some double-hybrid functionals, for example, G4 and CCSD(T), are generally required to achieve the BDEs and their trends reliably. The fixed-node diffusion quantum Monte Carlo method (FN-DMC) is employed to calculated BDEs of these R-X bonds with X = H, CH 3 , OCH 3 , OH, and F in this work. The single Slater-Jastrow wave function is adopted as trial wave function, and pseudopotentials (PPs) developed for quantum Monte Carlo calculations are chosen. Error of these PPs is modest in wave function methods, while it is more pronounced in DFT calculations. Our results show that accuracy of BDEs with FN-DMC is similar to that of M06-2X and G4, and trends in BDEs are calculated more reliably than M06-2X. Both BDEs and trends in BDEs of these bonds are reproduced reasonably with FN-DMC. FN-DMC using PPs can thus be applied to BDEs and their trends of similar chemical bonds in larger molecules reliably and provide valuable information on properties of these molecules.

Study on the dissociative recombination of HeH+ by multi-channel quantum defect theory

Directory of Open Access Journals (Sweden)

Takagi Hidekazu

2015-01-01

Full Text Available The dissociative recombination of HeH+ is studied using multi-channel quantum defect theory. We investigated how the partial waves of incident electrons affect the DR cross section. The DR cross section depends on the position of the center of partial wave expansion for the adiabatic S-matrix of electron scattering. When the Rydberg states correlate with the Rydberg states of the hydrogen atom at large internuclear distances, the center should be on the hydrogen atom for a better convergence of the expansion.

The effect of the two tailored femtosecond laser pulses in the enhancement of methane dissociation

International Nuclear Information System (INIS)

Sadighi-Bonabi, R.; Dehghani, Z.; Irani, E.

2010-01-01

Complete text of publication follows. Based on the gradient optimization method a useful approach for dissociation of the methane molecule is introduced. This analytical model produces an optimized two tailored rectangular laser pulses which dissociates the molecular ion CH 4 + with maximum probability of 1. In this approach the field assisted dissociation is used by a semi-classical view. It is assumed that only the selective dissociative bond is in direction of the laser electric field are effective. Saturation is found for dissociation of the mentioned molecular bond, where the first pulse should have higher intensity than the second pulse. In addition to that, the sensitivity of the dissociation probability to the initial bond length and the control of the desired product channel by variation of the laser intensity and its duration of laser field is presented.

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

International Nuclear Information System (INIS)

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

2014-01-01

Time dependent density matrix functional theory in its adiabatic linear response formulation delivers exact excitation energies ω α and oscillator strengths f 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 α (R) curves along the bond dissociation coordinate R for the molecules LiH, Li 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

Water growth on metals and oxides: binding, dissociation and role of hydroxyl groups

Energy Technology Data Exchange (ETDEWEB)

Salmeron, M.; Bluhm, H.; Tatarkhanov, M.; Ketteler, G.; Shimizu, T.K.; Mugarza, A.; Deng, Xingyi; Herranz, T.; Yamamoto, S.; Nilsson, A.

2008-09-01

The authors discuss the role of the presence of dangling H bonds from water or from surface hydroxyl species on the wetting behavior of surfaces. Using Scanning Tunneling and Atomic Force Microscopies, and Photoelectron Spectroscopy, they have examined a variety of surfaces, including mica, oxides, and pure metals. They find that in all cases, the availability of free, dangling H-bonds at the surface is crucial for the subsequent growth of wetting water films. In the case of mica electrostatic forces and H-bonding to surface O atoms determine the water orientation in the first layer and also in subsequent layers with a strong influence in its wetting characteristics. In the case of oxides like TiO{sub 2}, Cu{sub 2}O, SiO{sub 2} and Al{sub 2}O{sub 3}, surface hydroxyls form readily on defects upon exposure to water vapor and help nucleate the subsequent growth of molecular water films. On pure metals, such as Pt, Pd, and Ru, the structure of the first water layer and whether or not it exhibits dangling H bonds is again crucial. Dangling H-bonds are provided by molecules with their plane oriented vertically, or by OH groups formed by the partial dissociation of water. By tying the two II atoms of the water molecules into strong H-bonds with pre-adsorbed O on Ru can also quench the wettability of the surface.

The investigation of adsorption and dissociation of H{sub 2}O on Li{sub 2}O (111) by ab initio theory

Energy Technology Data Exchange (ETDEWEB)

Kong, Xianggang [Institute of Atom and Molecular physics, Sichuan University, Chengdu, 610065 (China); Yu, You [College of Optoelectronic Technology, Chengdu University of Information Technology, Chengdu, 610225 (China); Ma, Shenggui [Institute of Atom and Molecular physics, Sichuan University, Chengdu, 610065 (China); Gao, Tao, E-mail: gaotao@scu.edu.cn [Institute of Atom and Molecular physics, Sichuan University, Chengdu, 610065 (China); Lu, Tiecheng [Department of Physics and Key Laboratory for Radiation Physics & Technology of Ministry of Education, Sichuan University, Chengdu, 610065 (China); Xiao, Chengjian; Chen, Xiaojun [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900 (China); Zhang, Chuanyu [College of Geophysics, Chengdu University of Technology, Chengdu, 610059 (China)

2017-06-15

Highlights: • The adsorption structures of H{sub 2}O on Li{sub 2}O (111) are obtained by calculations. • By Bader charge analysis, the charge translation from slab to adsorbate is found. • The vibrational frequencies of adsorbate are in line with the experimental values. - Abstract: The adsorption and dissociation mechanism of H{sub 2}O molecule on the Li{sub 2}O (111) surface have been systematically studied by using the density functional theory calculations. The parallel and vertical configurations of H{sub 2}O at six different symmetry adsorption sites on the Li{sub 2}O (111) surface are considered. In our calculations, it is suggested that H{sub 2}O can dissociate on the perfect Li{sub 2}O surface, of which the corresponding adsorption energy is 1.118 eV. And the adsorption energy decrease to be 0.241 eV when oxygen atom of H{sub 2}O bonds to lithium atom of the slab. The final configurations are sensitive to the initial molecular orientation. By Bader charge analysis, the charge transfer from slab to adsorbed H{sub 2}O/OH can be found due to the downward shift of lowest-unoccupied molecular orbital. We also analyze the vibrational frequencies at the Brillouin Zone centre for H{sub 2}O molecule adsorbed on the stoichiometric surface. Due to the slightly different structure parameters, the calculated values of the vibrational frequencies of hydroxyl group range from 3824 to 3767 cm{sup −1}. Our results agree well with experimental results performed in FT-IR spectrum, which showed that an absorption peak of OH group appeared at 3677 cm{sup −1} at room temperature.

Observation of H-bond mediated 3hJH2H3coupling constants across Watson-Crick AU base pairs in RNA

International Nuclear Information System (INIS)

Luy, Burkhard; Richter, Uwe; DeJong, Eric S.; Sorensen, Ole W.; Marino, John P.

2002-01-01

3h J H2H3 trans-hydrogen bond scalar coupling constants have been observed for the first time in Watson-Crick AU base pairs in uniformly 15 N-labeled RNA oligonucleotides using a new 2h J NN -HNN-E. COSY experiment. The experiment utilizes adenosine H2 (AH2) for original polarization and detection, while employing 2h J NN couplings for coherence transfer across the hydrogen bonds (H-bonds). The H3 protons of uracil bases are unperturbed throughout the experiment so that these protons appear as passive spins in E. COSY patterns. 3h J H2H3 coupling constants can therefore be accurately measured in the acquisition dimension from the displacement of the E. COSY multiplet components, which are separated by the relatively large 1 J H3N3 coupling constants in the indirect dimension of the two-dimensional experiment. The 3h J H2H3 scalar coupling constants determined for AU base pairs in the two RNA hairpins examined here have been found to be positive and range in magnitude up to 1.8 Hz. Using a molecular fragment representation of an AU base pair, density functional theory/finite field perturbation theory (DFT/FPT) methods have been applied to attempt to predict the relative contributions of H-bond length and angular geometry to the magnitude of 3h J H2H3 coupling constants. Although the DFT/FPT calculations did not reproduce the full range of magnitude observed experimentally for the 3h J H2H3 coupling constants, the calculations do predict the correct sign and general trends in variation in size of these coupling constants. The calculations suggest that the magnitude of the coupling constants depends largely on H-bond length, but can also vary with differences in base pair geometry. The dependency of the 3h J H2H3 coupling constant on H-bond strength and geometry makes it a new probe for defining base pairs in NMR studies of nucleic acids

H/D Isotope Effects in Hydrogen Bonded Systems

Directory of Open Access Journals (Sweden)

Aleksander Filarowski

2013-04-01

Full Text Available An extremely strong H/D isotope effect observed in hydrogen bonded A-H…B systems is connected with a reach diversity of the potential shape for the proton/deuteron motion. It is connected with the anharmonicity of the proton/deuteron vibrations and of the tunneling effect, particularly in cases of short bridges with low barrier for protonic and deuteronic jumping. Six extreme shapes of the proton motion are presented starting from the state without possibility of the proton transfer up to the state with a full ionization. The manifestations of the H/D isotope effect are best reflected in the infra-red absorption spectra. A most characteristic is the run of the relationship between the isotopic ratio nH/nD and position of the absorption band shown by using the example of NHN hydrogen bonds. One can distinguish a critical range of correlation when the isotopic ratio reaches the value of ca. 1 and then increases up to unusual values higher than . The critical range of the isotope effect is also visible in NQR and NMR spectra. In the critical region one observes a stepwise change of the NQR frequency reaching 1.1 MHz. In the case of NMR, the maximal isotope effect is reflected on the curve presenting the dependence of Δd (1H,2H on d (1H. This effect corresponds to the range of maximum on the correlation curve between dH and ΔpKa that is observed in various systems. There is a lack in the literature of quantitative information about the influence of isotopic substitution on the dielectric properties of hydrogen bond except the isotope effect on the ferroelectric phase transition in some hydrogen bonded crystals.

Fast MAS ¹H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

Energy Technology Data Exchange (ETDEWEB)

Gill, Lance [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Beste, Ariana [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Institute for Computational Sciences (JIBS); Univ. of Tennessee, Knoxville, TN (United States); Chen, Banghao [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Li, Meijun [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Mann, Amanda K. P. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Overbury, Steven H. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Hagaman, Edward W. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

2017-03-22

¹H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO₂ that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution ¹H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T₁) and spin–spin (T₂) relaxation, and DFT calculations. In air, the (100) surface exists as a fully hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce³⁺ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D₂O does not occur under mild or forcing conditions. Despite large differences in the T₁ of surface hydroxyls and physisorbed water, surface hydroxyl T₁ values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na⁺ remaining in incompletely washed ceria nanocubes

A multivariate relationship for the impact sensitivities of energetic N-nitrocompounds based on bond dissociation energy.

Science.gov (United States)

Li, Jinshan

2010-02-15

The ZPE-corrected N-NO(2) bond dissociation energies (BDEs(ZPE)) of a series of model N-nitrocompounds and typical energetic N-nitrocompounds have been calculated using density functional theory methods. Computed results show that using the 6-31G** basis set the UB3LYP calculated BDE(ZPE) is similar to the B3PW91 but is less than the UB3P86 and that for both UB3P86 and UB3PW91 methods the 6-31G(**) calculated BDE(ZPE) is close to the 6-31++G(**). For the series of model N-nitrocompounds it is drawn from the NBO analysis that at the UB3LYP/6-31G(**) level the order of BDE(ZPE) is not only in line with that of bond order but also with that of the energy gap between N-NO(2) bond and antibond orbitals. For the typical energetic N-nitrocompounds the impact sensitivity is strongly related to the BDE(ZPE) indeed, and based on the BDEs(ZPE) calculated at different density functional theory levels this work has established a good multivariate correlation of impact sensitivity with molecular parameters, which provides a method to address the sensitivity problem.

Does GaH5 exist?

Science.gov (United States)

Speakman, Lucas D.; Turney, Justin M.; Schaefer, Henry F.

2005-11-01

The existence or nonexistence of GaH5 has been widely discussed [N. M. Mitzel, Angew. Chem. Int. Ed. 42, 3856 (2003)]. Seven possible structures for gallium pentahydride have been systematically investigated using ab initio electronic structure theory. Structures and vibrational frequencies have been determined employing self-consistent field, coupled cluster including all single and double excitations (CCSD), and CCSD with perturbative triples levels of theory, with at least three correlation-consistent polarized-valence-(cc-pVXZ and aug-cc-pVXZ) type basis sets. The X˜A'1 state for GaH5 is predicted to be weakly bound complex 1 between gallane and molecular hydrogen, with Cs symmetry. The dissociation energy corresponding to GaH5→GaH3+H2 is predicted to be De=2.05kcalmol-1. The H-H stretching fundamental is predicted to be v =4060cm-1, compared to the tentatively assigned experimental feature of Wang and Andrews [J. Phys. Chem. A 107, 11371 (2003)] at 4087cm-1. A second Cs structure 2 with nearly equal energy is predicted to be a transition state, corresponding to a 90° rotation of the H2 bond. Thus the rotation of the hydrogen molecule is essentially free. However, hydrogen scrambling through the C2v structure 3 seems unlikely, as the activation barrier for scrambling is at least 30kcalmol-1 higher in energy than that for the dissociation of GaH5 to GaH3 and H2. Two additional structures consisting of GaH3 with a dihydrogen bond perpendicular to gallane (C3v structure 4) and an in-plane dihydrogen bond [Cs(III) structure 5] were also examined. A C3v symmetry second-order saddle point has nearly the same energy as the GaH3+H2 dissociation limit, while the Cs(III) structure 5 is a transition structure to the C3v structure. The C4v structure 6 and the D3h structure 7 are much higher in energy than GaH3+H2 by 88 and 103kcalmol-1, respectively.

Recombination and dissociative recombination of H2+ and H3+ ions on surfaces with application to hydrogen negative ion sources

International Nuclear Information System (INIS)

Hiskes, J.R.; Karo, A.M.

1988-12-01

A four-step model for recombination and dissociative recombination of H 2 + and H 3 + ions on metal surfaces is discussed. Vibrationally excited molecules, H 2 (v''), from H 3 + recombination are produced in a broad spectrum that enhances the excited level distribution. The application of this latter process to hydrogen negative ion discharges is discussed. 5 refs., 3 figs., 1 tab

High-order above-threshold dissociation of molecules

Science.gov (United States)

Lu, Peifen; Wang, Junping; Li, Hui; Lin, Kang; Gong, Xiaochun; Song, Qiying; Ji, Qinying; Zhang, Wenbin; Ma, Junyang; Li, Hanxiao; Zeng, Heping; He, Feng; Wu, Jian

2018-03-01

Electrons bound to atoms or molecules can simultaneously absorb multiple photons via the above-threshold ionization featured with discrete peaks in the photoelectron spectrum on account of the quantized nature of the light energy. Analogously, the above-threshold dissociation of molecules has been proposed to address the multiple-photon energy deposition in the nuclei of molecules. In this case, nuclear energy spectra consisting of photon-energy spaced peaks exceeding the binding energy of the molecular bond are predicted. Although the observation of such phenomena is difficult, this scenario is nevertheless logical and is based on the fundamental laws. Here, we report conclusive experimental observation of high-order above-threshold dissociation of H2 in strong laser fields where the tunneling-ionized electron transfers the absorbed multiphoton energy, which is above the ionization threshold to the nuclei via the field-driven inelastic rescattering. Our results provide an unambiguous evidence that the electron and nuclei of a molecule as a whole absorb multiple photons, and thus above-threshold ionization and above-threshold dissociation must appear simultaneously, which is the cornerstone of the nowadays strong-field molecular physics.

Hydropersulfides: H-Atom Transfer Agents Par Excellence.

Science.gov (United States)

Chauvin, Jean-Philippe R; Griesser, Markus; Pratt, Derek A

2017-05-10

Hydropersulfides (RSSH) are formed endogenously via the reaction of the gaseous biotransmitter hydrogen sulfide (H 2 S) and disulfides (RSSR) and/or sulfenic acids (RSOH). RSSH have been investigated for their ability to store H 2 S in vivo and as a line of defense against oxidative stress, from which it is clear that RSSH are much more reactive to two-electron oxidants than thiols. Herein we describe the results of our investigations into the H-atom transfer chemistry of RSSH, contrasting it with the well-known H-atom transfer chemistry of thiols. In fact, RSSH are excellent H-atom donors to alkyl (k ∼ 5 × 10 8 M -1 s -1 ), alkoxyl (k ∼ 1 × 10 9 M -1 s -1 ), peroxyl (k ∼ 2 × 10 6 M -1 s -1 ), and thiyl (k > 1 × 10 10 M -1 s -1 ) radicals, besting thiols by as little as 1 order and as much as 4 orders of magnitude. The inherently high reactivity of RSSH to H-atom transfer is based largely on thermodynamic factors; the weak RSS-H bond dissociation enthalpy (∼70 kcal/mol) and the associated high stability of the perthiyl radical make the foregoing reactions exothermic by 15-34 kcal/mol. Of particular relevance in the context of oxidative stress is the reactivity of RSSH to peroxyl radicals, where favorable thermodynamics are bolstered by a secondary orbital interaction in the transition state of the formal H-atom transfer that drives the inherent reactivity of RSSH to match that of α-tocopherol (α-TOH), nature's premier radical-trapping antioxidant. Significantly, the reactivity of RSSH eclipses that of α-TOH in H-bond-accepting media because of their low H-bond acidity (α 2 H ∼ 0.1). This affords RSSH a unique versatility compared to other highly reactive radical-trapping antioxidants (e.g., phenols, diarylamines, hydroxylamines, sulfenic acids), which tend to have high H-bond acidities. Moreover, the perthiyl radicals that result are highly persistent under autoxidation conditions and undergo very rapid dimerization (k = 5 × 10 9 M -1 s -1 ) in

Relation between frequency and H bond length in heavy water: Towards the understanding of the unusual properties of H bond dynamics in nanoporous media

International Nuclear Information System (INIS)

Pommeret, Stanislas; Leicknam, Jean-Claude; Bratos, Savo; Musat, Raluca; Renault, Jean Philippe

2009-01-01

The published work on H bond dynamics mainly refers to diluted solutions HDO/D 2 O rather than to normal water. The reasons for this choice are both theoretical and experimental. Mechanical isolation of the OH vibrator eliminating the resonant energy transfer makes it a better probe of the local H bond network, while the dilution in heavy water reduces the infrared absorption, which permits the use of thicker experimental cells. The isotopic substitution does not alter crucially the nature of the problem. The length r of an OH . . . O group is statistically distributed over a large interval comprised between 2.7 and 3.2 A with a mean value r 0 = 2.86 A. Liquid water may thus be viewed as a mixture of hydrogen bonds of different length. Two important characteristics of hydrogen bonding must be mentioned. (i) The OH stretching vibrations are strongly affected by this interaction. The shorter the length r of the hydrogen bond, the strongest the H bond link and the lower is its frequency ω: the covalent OH bond energy is lent to the OH. . .O bond and reinforces the latter. A number of useful relationships between ω and r were published to express this correlation. The one adopted in our previous work is the relationship due to Mikenda. (ii) Not only the OH vibrations, but also the HDO rotations are influenced noticeably by hydrogen bonding. This is due to steric forces that hinder the HDO rotations. As they are stronger in short than in long hydrogen bonds, rotations are slower in the first case than in the second. This effect was only recently discovered, but its existence is hardly to be contested. In the present contribution, we want to revisit the relationship between the frequency of the OH vibrator and the distance OH. . .O.

Ionization and dissociation dynamics of vinyl bromide probed by femtosecond extreme ultraviolet transient absorption spectroscopy

International Nuclear Information System (INIS)

Lin, Ming-Fu; Neumark, Daniel M.; Gessner, Oliver; Leone, Stephen R.

2014-01-01

Strong-field induced ionization and dissociation dynamics of vinyl bromide, CH 2 =CHBr, are probed using femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy. Strong-field ionization is initiated with an intense femtosecond, near infrared (NIR, 775 nm) laser field. Femtosecond XUV pulses covering the photon energy range of 50-72 eV probe the subsequent dynamics by measuring the time-dependent spectroscopic features associated with transitions of the Br (3d) inner-shell electrons to vacancies in molecular and atomic valence orbitals. Spectral signatures are observed for the depletion of neutral C 2 H 3 Br, the formation of C 2 H 3 Br + ions in their ground (X ~ ) and first excited (A ~ ) states, the production of C 2 H 3 Br ++ ions, and the appearance of neutral Br ( 2 P 3/2 ) atoms by dissociative ionization. The formation of free Br ( 2 P 3/2 ) atoms occurs on a timescale of 330 ± 150 fs. The ionic A ~ state exhibits a time-dependent XUV absorption energy shift of ∼0.4 eV within the time window of the atomic Br formation. The yield of Br atoms correlates with the yield of parent ions in the A ~ state as a function of NIR peak intensity. The observations suggest that a fraction of vibrationally excited C 2 H 3 Br + (A ~ ) ions undergoes intramolecular vibrational energy redistribution followed by the C–Br bond dissociation. The C 2 H 3 Br + (X ~ ) products and the majority of the C 2 H 3 Br ++ ions are relatively stable due to a deeper potential well and a high dissociation barrier, respectively. The results offer powerful new insights about orbital-specific electronic processes in high field ionization, coupled vibrational relaxation and dissociation dynamics, and the correlation of valence hole-state location and dissociation in polyatomic molecules, all probed simultaneously by ultrafast table-top XUV spectroscopy

Dissociative electron attachment studies on acetone

International Nuclear Information System (INIS)

Prabhudesai, Vaibhav S.; Tadsare, Vishvesh; Ghosh, Sanat; Gope, Krishnendu; Davis, Daly; Krishnakumar, E.

2014-01-01

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 − is found to be the most dominant fragment followed by O − and OH − 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 − and O − 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

Reduced step edges on rutile TiO (110) as competing defects to oxygen vacancies on the terraces and reactive sites for ethanol dissociation

DEFF Research Database (Denmark)

Martinez, U.; Hansen, Jonas Ørbæk; Salazar, Estephania Lira

2012-01-01

microscopy studies, we here present experimental evidence for the existence of O vacancies along the ⟨11̅ 1⟩R step edges (OS vac.’s) on rutile TiO2(110). Both the distribution of bridging O vacancies on the terraces and temperature-programed reaction experiments of ethanol-covered TiO2(110) point...... to the existence of the OS vac.’s. Based on experiments and density functional theory calculations, we show that OS vac.’s are reactive sites for ethanol dissociation via O-H bond scission. Implications of these findings are discussed...

Deuterium enrichment by selective photo-induced dissociation of an organic carbonyl compound

International Nuclear Information System (INIS)

Marling, J.B.

1981-01-01

A deuterium-enriched material is produced by selective photoinduced dissociation of a gas phase organic carbonyl compound containing at least one hydrogen atom bonded to an atom adjacent to a carbonyl group. Alkyl carbonyl compounds such as acetone, acetaldehyde, trifluoroacetic acid, cyclobutanone, cyclopentanone, methyl acetate, 3,3-dimethyl-2-butanone, 2,4-pentanedione, and 4-methyl-2-pentanone are preferred. The carbonyl compound is subjected to intense infrared radiation from one laser, or two lasers operating at different frequencies, to selectively dissociate the deuterated molecules into stable products. The undissociated compound may be redeuterated by direct aqueous liquid phase H/D exchange, or by indirect liquid phase exchange using an alkanol in an intermediate step

Ionisation and dissociation of water induced by swift multicharged ions

International Nuclear Information System (INIS)

Legendre, S.

2006-02-01

Ionization and dissociation of water molecules and water clusters induced by 11.7 MeV/A Ni 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 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 2 O 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)

At least 10% shorter C–H bonds in cryogenic protein crystal structures than in current AMBER forcefields

Energy Technology Data Exchange (ETDEWEB)

Pang, Yuan-Ping, E-mail: pang@mayo.edu

2015-03-06

High resolution protein crystal structures resolved with X-ray diffraction data at cryogenic temperature are commonly used as experimental data to refine forcefields and evaluate protein folding simulations. However, it has been unclear hitherto whether the C–H bond lengths in cryogenic protein structures are significantly different from those defined in forcefields to affect protein folding simulations. This article reports the finding that the C–H bonds in high resolution cryogenic protein structures are 10–14% shorter than those defined in current AMBER forcefields, according to 3709 C–H bonds in the cryogenic protein structures with resolutions of 0.62–0.79 Å. Also, 20 all-atom, isothermal–isobaric, 0.5-μs molecular dynamics simulations showed that chignolin folded from a fully-extended backbone formation to the native β-hairpin conformation in the simulations using AMBER forcefield FF12SB at 300 K with an aggregated native state population including standard error of 10 ± 4%. However, the aggregated native state population with standard error reduced to 3 ± 2% in the same simulations except that C–H bonds were shortened by 10–14%. Furthermore, the aggregated native state populations with standard errors increased to 35 ± 3% and 26 ± 3% when using FF12MC, which is based on AMBER forcefield FF99, with and without the shortened C–H bonds, respectively. These results show that the 10–14% bond length differences can significantly affect protein folding simulations and suggest that re-parameterization of C–H bonds according to the cryogenic structures could improve the ability of a forcefield to fold proteins in molecular dynamics simulations. - Highlights: • Cryogenic crystal structures are commonly used in computational studies of proteins. • C–H bonds in the cryogenic structures are shorter than those defined in forcefields. • A survey of 3709 C–H bonds shows that the cryogenic bonds are 10–14% shorter. • The

Photoelectron Diffraction Imaging for C2H2 and C2H4 Chemisorbed on Si(100) Reveals a New Bonding Configuration

International Nuclear Information System (INIS)

Xu, S. H.; Keeffe, M.; Yang, Y.; Chen, C.; Yu, M.; Lapeyre, G. J.; Rotenberg, E.; Denlinger, J.; Yates, J. T. Jr.

2000-01-01

A new adsorption site for adsorbed acetylene on Si(100) is observed by photoelectron imaging based on the holographic principle. The diffraction effects in the carbon 1s angle-resolved photoemission are inverted (including the small-cone method) to obtain an image of the atom's neighboring carbon. The chemisorbed acetylene molecule is bonded to four silicon surface atoms. In contrast to the C 2 H 2 case, the image for adsorbed C 2 H 4 shows it bonded to two Si surface atoms. (c) 2000 The American Physical Society

Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions

Science.gov (United States)

Zhou, Tian

Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the

Channel-coupling theory of covalent bonding in H2: A further application of arrangement-channel quantum mechanics

International Nuclear Information System (INIS)

Levin, F.S.; Krueger, H.

1977-01-01

The dissociation energy D/sub e/ and the equilibrium proton-proton separation R/sub eq/ of H 2 are calculated using the methods of arrangement-channel quantum mechanics. This theory is the channel component version of the channel-coupling array approach to many-body scattering, applied to bound-state problems. In the approximation used herein, the wave function is identical to that of the classic Heitler-London-Sugiura valence-bond calculation, which gave D/sub e/ = 3.14 eV and R/sub eq/ = 1.65a 0 , values accurate to 34% and 17.8%, respectively. The present method yields D/sub e/ = 4.437 eV and R/sub eq/ approx. = 1.42a 0 , accurate to 6.5% and 1%, respectively. Some implications of these results are discussed

A genetically-encoded chloride and pH sensor for dissociating ion dynamics in the nervous system

Directory of Open Access Journals (Sweden)

Joseph Valentino Raimondo

2013-11-01

Full Text Available Within the nervous system, intracellular Cl- and pH regulate fundamental processes including cell proliferation, metabolism, synaptic transmission and network excitability. Cl- and pH are often co-regulated, and network activity results in the movement of both Cl- and H+. Tools to accurately measure these ions are crucial for understanding their role under physiological and pathological conditions. Although genetically-encoded Cl- and pH sensors have been described previously, these either lack ion specificity or are unsuitable for neuronal use. Here we present ClopHensorN - a new genetically-encoded ratiometric Cl- and pH sensor that is optimized for the nervous system. We demonstrate the ability of ClopHensorN to dissociate and simultaneously quantify Cl- and H+ concentrations under a variety of conditions. In addition, we establish the sensor’s utility by characterizing activity-dependent ion dynamics in hippocampal neurons.

First-principles analysis of C2H2 molecule diffusion and its dissociation process on the ferromagnetic bcc-Fe(110) surface

International Nuclear Information System (INIS)

Ikeda, Minoru; Yamasaki, Takahiro; Kaneta, Chioko

2010-01-01

Using the projector-augmented plane wave method, we study diffusion and dissociation processes of C 2 H 2 molecules on the ferromagnetic bcc-Fe(110) surface and investigate the formation process of graphene created by C 2 H 2 molecules. The most stable site for C 2 H 2 on the Fe surface is a hollow site and its adsorption energy is - 3.5 eV. In order to study the diffusion process of the C 2 H 2 molecule, the barrier height energies for the C atom, C 2 -dimer and CH as well as the C 2 H 2 molecule are estimated using the nudged elastic band method. The barrier height energy for C 2 H 2 is 0.71 eV and this indicates that the C 2 H 2 diffuses easily on this FM bcc-Fe(110) surface. We further investigate the two step dissociation process of C 2 H 2 on Fe. The first step is the dissociation of C 2 H 2 into C 2 H and H, and the second step is that of C 2 H into C 2 and H. Their dissociation energies are 0.9 and 1.2 eV, respectively. These energies are relatively small compared to the dissociation energy 7.5 eV of C 2 H 2 into C 2 H and H in the vacuum. Thus, the Fe surface shows catalytic effects. We further investigate the initial formation process of graphene by increasing the coverage of C 2 H 2 . The formation process of the benzene molecule on the FM bcc(110) surface is also discussed. We find that there exists a critical coverage of C 2 H 2 which characterizes the beginning of the formation of the graphene.

First-principles analysis of C2H2 molecule diffusion and its dissociation process on the ferromagnetic bcc-Fe110 surface.

Science.gov (United States)

Ikeda, Minoru; Yamasaki, Takahiro; Kaneta, Chioko

2010-09-29

Using the projector-augmented plane wave method, we study diffusion and dissociation processes of C(2)H(2) molecules on the ferromagnetic bcc-Fe(110) surface and investigate the formation process of graphene created by C(2)H(2) molecules. The most stable site for C(2)H(2) on the Fe surface is a hollow site and its adsorption energy is - 3.5 eV. In order to study the diffusion process of the C(2)H(2) molecule, the barrier height energies for the C atom, C(2)-dimer and CH as well as the C(2)H(2) molecule are estimated using the nudged elastic band method. The barrier height energy for C(2)H(2) is 0.71 eV and this indicates that the C(2)H(2) diffuses easily on this FM bcc-Fe(110) surface. We further investigate the two step dissociation process of C(2)H(2) on Fe. The first step is the dissociation of C(2)H(2) into C(2)H and H, and the second step is that of C(2)H into C(2) and H. Their dissociation energies are 0.9 and 1.2 eV, respectively. These energies are relatively small compared to the dissociation energy 7.5 eV of C(2)H(2) into C(2)H and H in the vacuum. Thus, the Fe surface shows catalytic effects. We further investigate the initial formation process of graphene by increasing the coverage of C(2)H(2). The formation process of the benzene molecule on the FM bcc(110) surface is also discussed. We find that there exists a critical coverage of C(2)H(2) which characterizes the beginning of the formation of the graphene.

Dissociative subtype of DSM-5 posttraumatic stress disorder in U.S. veterans.

Science.gov (United States)

Tsai, Jack; Armour, Cherie; Southwick, Steven M; Pietrzak, Robert H

2015-01-01

The Diagnostic and Statistical Manual of Mental Disorders, 5th edition (DSM-5) formally introduced a dissociative subtype of posttraumatic stress disorder (PTSD). This study examined the proportion of U.S. veterans with DSM-5 PTSD that report dissociative symptoms; and compared veterans with PTSD with and without the dissociative subtype and trauma-exposed controls on sociodemographics, clinical characteristics, and quality of life. Multivariable analyses were conducted on a nationally representative sample of 1484 veterans from the National Health and Resilience in Veterans Study (second baseline survey conducted September-October, 2013). Of the 12.0% and 5.2% of veterans who screened positive for lifetime and past-month DSM-5 PTSD, 19.2% and 16.1% screened positive for the dissociative subtype, respectively. Among veterans with PTSD, those with the dissociative subtype reported more severe PTSD symptoms, comorbid depressive and anxiety symptoms, alcohol use problems, and hostility than those without the dissociative subtype. Adjusting for PTSD symptom severity, those with the dissociative subtype continued to report more depression and alcohol use problems. These results underscore the importance of assessing, monitoring, and treating the considerable proportion of veterans with PTSD and dissociative symptoms. Published by Elsevier Ltd.

Raman spectrum of predissociating H/sub 2/S

International Nuclear Information System (INIS)

Kleinermanns, K.; Suntz, R.; Schneider, R.

1986-01-01

Emission spectroscopy of photodissociating molecules provides interesting insights into the short-time dynamics of bond raptures. The authors report here a resolved H/sub 2/S photoemission spectrum after excitation at 193 nm, although its electronic spectrum in this wavelength region is diffuse. The electronic spectrum of H/sub 2/S between 250 and 170 nm is nearly continuous probably due to predissociation

Using block diagonalization to determine dissociating autoionizing states: Application to N2H, and the outlook for SH

Directory of Open Access Journals (Sweden)

Kashinski D.O.

2015-01-01

Full Text Available We describe our implementation of the block diagonalization method for calculating the potential surfaces necessary to treat dissociative recombination (DR of electrons with N2H+. Using the methodology we have developed over the past few years, we performed multi-reference, configuration interaction calculations for N2H+ and N2H with a large active space using the GAMESS electronic structure code. We treated both linear and bent geometries of the molecules, with N2 fixed at its equilibrium separation. Because of the strong Rydberg-valence coupling in N2H, it is essential to isolate the appropriate dissociating, autoionizing states. Our procedure requires only modest additional effort beyond the standard methodology. The results indicate that the crossing between the dissociating neutral curve and the initial ion potential is not favorably located for DR, even if the molecule bends. The present calculations thereby confirm our earlier results for linear N2H and reinforce the conclusion that the direct mechanism for DR is likely to be inefficient. We also describe interesting features of our preliminary calculations on SH.

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.

SOFT X-RAY IRRADIATION OF H{sub 2}S ICE AND THE PRESENCE OF S{sub 2} IN COMETS

Energy Technology Data Exchange (ETDEWEB)

Jimenez-Escobar, A.; Munoz Caro, G. M. [Centro de Astrobiologia (CSIC-INTA), Carretera de Ajalvir, km 4, Torrejon de Ardoz, 28850 Madrid (Spain); Ciaravella, A.; Candia, R.; Micela, G. [INAF-Osservatorio Astronomico di Palermo, P.za Parlamento 1, 90134 Palermo (Italy); Cecchi-Pestellini, C., E-mail: munozcg@cab.inta-csic.es [INAF-Osservatorio Astronomico di Cagliari, Strada n.54, Loc. Poggio dei Pini, I-09012 Capoterra (Canada) (Italy)

2012-06-01

Little is known about the effects of X-rays in interstellar ices. To understand the sulfur depletion in dense clouds and the presence of S{sub 2} in comets, we simulated experimentally the soft X-ray processing (0.3 keV) of H{sub 2}S ice for the first time. Experiments were performed under ultrahigh vacuum conditions at 8 K using infrared and quadrupole mass spectrometry to monitor the solid and gas phases, respectively. A UV irradiation experiment using a similar dose was made for comparison. After X-ray irradiation, an infrared absorption appears near 4.0 {mu}m which is attributed to H{sub 2}S{sub 2} formation in the ice. This identification is also supported by the desorption at 133 K of m/z 66, 65, 64, corresponding to the mass fragments of H{sub 2}S{sub 2}. The H{sub 2}S{sub 2} species is expected to be present in interstellar and cometary ices that were processed by X-rays. Further irradiation leads to dissociation of this molecule forming S{sub 2} and larger S-molecules up to S{sub 8}, which may explain the depletion of sulfur in dense clouds. CS{sub 2} was so far the parent molecule proposed for S{sub 2} formation in comets. But the abundance of H{sub 2}S{sub 2}, formed by irradiation of pure H{sub 2}S or H{sub 2}S in an H{sub 2}O-ice matrix, should be larger than that of CS{sub 2} in the ice, the latter requiring a carbon source for its formation. Based on our experimental results, we propose that S{sub 2} in comets could be formed by dissociation of H{sub 2}S{sub 2} in the ice.

H{sub 2} dissociation on γ-Al{sub 2}O{sub 3} supported Cu/Pd atoms: A DFT investigation

Energy Technology Data Exchange (ETDEWEB)

Wang, Hongtao [College of Environmental Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Key Laboratory of Coal Science and Technology of Shanxi Province and Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Chen, Lijuan [Key Laboratory of Coal Science and Technology of Shanxi Province and Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Lv, Yongkang, E-mail: lykang@tyut.edu.cn [Key Laboratory of Coal Science and Technology of Shanxi Province and Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Ren, Ruipeng, E-mail: s2003wht@126.com [Key Laboratory of Coal Science and Technology of Shanxi Province and Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China)

2014-01-30

The density functional theory (DFT) was applied to investigate the promotion effects of single Cu and Pd atoms deposition on γ-Al{sub 2}O{sub 3} surface for the adsorption and dissociation of H{sub 2} molecule, which is of importance for many catalysis reactions. Due to its strong Lewis acidity, the tri-coordinated surface Al site was identified to be the most preferable site for both Cu and Pd location. The inner surface electrons rearrangement from O to Al of alumina was found to be a key factor to stabilize the Cu/Pd adsorption configurations, rather than the total electrons transfer between Cu/Pd and the surface. It was found that the supported Cu and Pd atoms are more active for H{sub 2} dissociation than the clean γ-Al{sub 2}O{sub 3} surface. The supported Pd is more active than Cu for H{sub 2} dissociation. In addition, the metal–support interaction of the γ-Al{sub 2}O{sub 3} supported Cu/Pd atoms are more favored than the metal–metal interaction of the metal clusters for the H{sub 2} dissociated adsorption.

Dissociation of water and Acetic acid on PbS from first principles

Science.gov (United States)

Satta, Alessandra; Ruggerone, Paolo; de Giudici, Giovanni

2008-03-01

The adsorption of complex molecules at mineral surfaces are crucial ingredients for understanding the mechanisms that rule the interaction between minerals and the biosphere and for predicting both the stability and the reactivity of minerals. The present work focuses mainly on the early stages of different adsorption reactions occurring at both the cleavage surface and a high-index vicinal surface of galena (PbS). We have studied the dissociation mechanism of water and acetic acid on the galena surfaces by means of ab initio calculations within the framework of the density functional theory in the generalized gradient approximation and of pseudopotential approach. The calculated adsorption energies of the molecules indicate the stepped surface as the most reactive, as expected. The free energy surface during the reaction process has been explored via metadynamics[1]. The optimized configurations of both reactants and products obtained, were then used to accurately calculate the dissociation energy via the Nudge Elastic Band method[2]. [1] A. Laio and M. Parrinello, PNAS 99, 12562 (2002). [2] G. Mills and H. Jonsson, Phys. Rev. Lett. 72, 1124 (1994).

Cell membrane antigen-antibody complex dissociation by the widely used glycine-HCL method: an unreliable procedure for studying antibody internalization.

Science.gov (United States)

Tsaltas, G; Ford, C H

1993-02-01

Methods following the process of binding and internalization of antibodies to cell surface antigens have often employed low pH isoosmolar buffers in order to dissociate surface antigen-antibody complexes. One of the most widely used buffers is a 0.05 M glycine-HCL buffer pH 2.8. Since the efficacy of action of this buffer was critical to a series of internalization experiments employing monoclonal antibodies (Mabs) to carcinoembryonic antigen (CEA) expressing cancer cell lines in this laboratory, we tested its performance in a number of different assays. Our results indicate that this buffer only partially dissociates antigen-antibody bonds and therefore can introduce major inaccuracies in internalization experiments.

Theoretical resonant electron-impact vibrational excitation, dissociative recombination and dissociative excitation cross sections of ro-vibrationally excited BeH"+ ion

International Nuclear Information System (INIS)

Laporta, V.; Chakrabarti, K.; Celiberto, R.; Janev, R. K.; Mezei, J. Zs.; Niyonzima, S.; Tennyson, J.; Schneider, I.F.

2017-01-01

A theoretical study of resonant vibrational excitation, dissociative recombination and dissociative excitation processes of the beryllium monohydride cation, BeH"+ , induced by electron impact, is reported. Full sets of ro-vibrationally-resolved cross sections and of the corresponding Maxwellian rate coefficients are presented for the three processes. Particular emphasis is given to the high-energy behaviour. Potential curves of "2σ"+, "2σ and "2δ symmetries and the corresponding resonance widths, obtained from R-matrix calculations, provide the input for calculations which use a local complex-potential model for resonant collisions in each of the three symmetries. Rotational motion of nuclei and isotopic effects are also discussed. The relevant results are compared with those obtained using a multichannel quantum defect theory method. Full results are available from the Phys4Entry database.

Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

Science.gov (United States)

Sharma, Ankit; Hartwig, John F

2013-11-27

We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

B-H Bond Activation by an Amidinate-Stabilized Amidosilylene: Non-Innocent Amidinate Ligand.

Science.gov (United States)

Khoo, Sabrina; Shan, Yu-Liang; Yang, Ming-Chung; Li, Yongxin; Su, Ming-Der; So, Cheuk-Wai

2018-05-21

The activation of B-H and B-Cl bonds in boranes by base-stabilized low-valent silicon compounds is described. The reaction of the amidinato amidosilylene-borane adduct [L{Ar(Me 3 Si)N}SiBH 3 ] [1; L = PhC(N tBu) 2 , and Ar = 2,6- iPr 2 C 6 H 3 ] with MeOTf in toluene at room temperature formed [L{Ar(Me 3 Si)N}SiBH 2 OTf] (2). [LSiN(SiMe 3 )Ar] in compound 2 then underwent a B-H bond activation with BH 2 OTf in refluxing toluene to afford the B-H bond activation product [LB(H)Si(H)(OTf){N(SiMe 3 )Ar}] (3). On the other hand, when compound 2 was reacted with 4-dimethylaminopyridine in refluxing toluene, another B-H bond activation product [(μ-κ1:κ1-L)B(H)(DMAP)Si(H){N(Ar)SiMe 3 }]OTf (4) was afforded. Mechanistic studies show that "(μ-κ1:κ1-L)B(H)(OTf)Si(H){N(Ar)SiMe 3 }" (2A) is the key intermediate in the reactions mentioned above. The formation of 2A is further evidenced by the activation of the B-Cl bond in PhBCl 2 by the amidinato silicon(I) dimer [LSi:] 2 to form the B-Cl bond activation product [(μ-κ1:κ1-L)B(Cl)(Ph)Si(Cl)] 2 (6). Compounds 2-4 and 6 were characterized by nuclear magnetic resonance spectroscopy and X-ray crystallography.

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.

Zn Coordination Chemistry:  Development of Benchmark Suites for Geometries, Dipole Moments, and Bond Dissociation Energies and Their Use To Test and Validate Density Functionals and Molecular Orbital Theory.

Science.gov (United States)

Amin, Elizabeth A; Truhlar, Donald G

2008-01-01

We present nonrelativistic and relativistic benchmark databases (obtained by coupled cluster calculations) of 10 Zn-ligand bond distances, 8 dipole moments, and 12 bond dissociation energies in Zn coordination compounds with O, S, NH3, H2O, OH, SCH3, and H ligands. These are used to test the predictions of 39 density functionals, Hartree-Fock theory, and seven more approximate molecular orbital theories. In the nonrelativisitic case, the M05-2X, B97-2, and mPW1PW functionals emerge as the most accurate ones for this test data, with unitless balanced mean unsigned errors (BMUEs) of 0.33, 0.38, and 0.43, respectively. The best local functionals (i.e., functionals with no Hartree-Fock exchange) are M06-L and τ-HCTH with BMUEs of 0.54 and 0.60, respectively. The popular B3LYP functional has a BMUE of 0.51, only slightly better than the value of 0.54 for the best local functional, which is less expensive. Hartree-Fock theory itself has a BMUE of 1.22. The M05-2X functional has a mean unsigned error of 0.008 Å for bond lengths, 0.19 D for dipole moments, and 4.30 kcal/mol for bond energies. The X3LYP functional has a smaller mean unsigned error (0.007 Å) for bond lengths but has mean unsigned errors of 0.43 D for dipole moments and 5.6 kcal/mol for bond energies. The M06-2X functional has a smaller mean unsigned error (3.3 kcal/mol) for bond energies but has mean unsigned errors of 0.017 Å for bond lengths and 0.37 D for dipole moments. The best of the semiempirical molecular orbital theories are PM3 and PM6, with BMUEs of 1.96 and 2.02, respectively. The ten most accurate functionals from the nonrelativistic benchmark analysis are then tested in relativistic calculations against new benchmarks obtained with coupled-cluster calculations and a relativistic effective core potential, resulting in M05-2X (BMUE = 0.895), PW6B95 (BMUE = 0.90), and B97-2 (BMUE = 0.93) as the top three functionals. We find significant relativistic effects (∼0.01 Å in bond lengths, ∼0

Reversible Heterolytic Cleavage of the H-H Bond by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and Hydride

Energy Technology Data Exchange (ETDEWEB)

Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris

2017-05-18

Controlling the heterolytic cleavage of the H-H bond of dihydrogen is critically important in catalytic hydrogenations and in the catalytic oxidation of H2. We show how the rate of reversible heterolytic cleavage of H2 can be controlled over nearly four orders of magnitude at 25 °C, from 2.1 × 103 s-1 to ≥107 s-1. Bifunctional Mo complexes, [CpMo(CO)(κ3-P2N2)]+ (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane with alkyl/aryl groups on N and P), have been developed for heterolytic cleavage of H2 into a proton and a hydride, akin to Frustrated Lewis Pairs. The H-H bond cleavage is enabled by the basic amine in the second coordination sphere. The products of heterolytic cleavage of H2, Mo hydride complexes bearing protonated amines, [CpMo(H)(CO)(P2N2H)]+, were characterized by spectroscopic studies and by X-ray crystallography. Variable temperature 1H, 15N and 2-D 1H-1H ROESY NMR spectra indicated rapid exchange of the proton and hydride. The exchange rates are in the order [CpMo(H)(CO)(PPh2NPh2H)]+ > [CpMo(H)(CO)(PtBu2NPh2H)]+ > [CpMo(H)(CO)(PPh2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NtBu2H)]+. The pKa values determined in acetonitrile range from 9.3 to 17.7, and show a linear correlation with the logarithm of the exchange rates. Thus the exchange dynamics are controlled through the relative acidity of the [CpMo(H)(CO)(P2N2H)]+ and [CpMo(H2)(CO)(P2N2)]+ isomers, providing a design principle for controlling heterolytic cleavage of H2.

The hydrogen bond between N-H or O-H and organic fluorine: favourable yes, competitive no.

Science.gov (United States)

Taylor, Robin

2017-06-01

A study was made of X-H...F-C interactions (X = N or O) in small-molecule crystal structures. It was primarily based on 6728 structures containing X-H and C-F and no atom heavier than chlorine. Of the 28 451 C-F moieties in these structures, 1051 interact with X-H groups. However, over three-quarters of these interactions are either the weaker components of bifurcated hydrogen bonds (so likely to be incidental contacts) or occur in structures where there is a clear insufficiency of good hydrogen-bond acceptors such as oxygen, nitrogen or halide. In structures where good acceptors are entirely absent, there is about a 2 in 3 chance that a given X-H group will donate to fluorine. Viable alternatives are X-H...π hydrogen bonds (especially to electron-rich aromatics) and dihydrogen bonds. The average H...F distances of X-H...F-C interactions are significantly shorter for CR 3 F (R = C or H) and Csp 2 -F acceptors than for CRF 3 . The X-H...F angle distribution is consistent with a weak energetic preference for linearity, but that of H...F-C suggests a flat energy profile in the range 100-180°. X-H...F-C interactions are more likely when the acceptor is Csp 2 -F or CR 3 F, and when the donor is C-NH 2 . They also occur significantly more often in structures containing tertiary alcohols or solvent molecules, or with Z' > 1, i.e. when there may be unusual packing problems. It is extremely rare to find X-H...F-C interactions in structures where there are several unused good acceptors. When it does happen, there is often a clear reason, e.g. awkwardly shaped molecules whose packing isolates a donor group from the good acceptors.

Infrared matrix isolation study of hydrogen bonds involving C-H bonds: Substituent effects

International Nuclear Information System (INIS)

Jeng, M.L.H.; Ault, B.S.

1989-01-01

The matrix isolation technique combined with infrared spectroscopy has been employed to isolate and characterize hydrogen-bonded complexes between a series of substituted alkynes and several oxygen and nitrogen bases. Distinct evidence for hydrogen bond formation was observed in each case, with a characteristic red shift of the hydrogen stretching motion ν r . Shifts between 100 and 300 cm -1 were observed, the largest being for the complex of CF 3 CCH with (CH 3 ) 3 N. The perturbed carbon-carbon triple bond stretching vibration was observed for most complexes, as was the alkynic hydrogen bending motion. Attempts were made to correlate the magnitude of the red shift of ν s with substituent constants for the different substituted alkynes; a roughly linear correlation was found with the Hammett σ parameter. Lack of correlation Δν s with either σ 1 or σ R alone suggests that both inductive and resonance contributions to the strength of the hydrogen-bonding interaction are important

Dissociative attachment reactions of electrons with gas phase superacids

International Nuclear Information System (INIS)

Liu, X.

1992-01-01

Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients β for reactions of electrons with gas phase superacids HCo(PF 3 ) 4 , HRh(PF 3 ) 4 and carbonyl hydride complexes HMn(CO) 5 , HRe(CO) 5 have been determined under thermal conditions over the approximate temperature range 300∼550 K. The superacids react relatively slowly ( max ) with free electrons in a thermal plasma, and the values of β obtained this far do not show a correlation between acidity and β. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; it was found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF 3 ) 4 was found to be independent of temperature even though the β[HCo(PF 3 ) 4 ] increases with temperature. This proposes that the electron attachment process occurs well before the excited complex dissociates. In addition, the activation energy of HCo(PF 3 ) 4 for electron attachment has been derived from the Arrhenius plots. The carbonyl hydride complexes, HMn(CO) 5 and HRe(CO) 5 , react relatively rapidly (>1/4 of β max ) with free electrons in thermal plasma. This indicates that these reactions cannot be significantly endothermic. Observation of rapid attachment for these non-superacids shows that the Mn-CO and Re-CO bonds are weaker than the Mn-H and Re-H bonds, respectively. Comparisons between the carbonyl and trifluorophosphine cases implies that fast electron capture is related more to the CO ligand than to the transition-metal species

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

The highest frequency hydrogen bond fundamental of formic acid dimer, ν24 (Bu), is experimentally located at 264 cm−1. FTIR spectra of this in-plane bending mode of (HCOOH)2 and band centers of its symmetric D isotopologues (isotopomers) recorded in a supersonic slit jet expansion are presented...... thermodynamics treatment of the dimerization process up to room temperature. We obtain D0 = 59.5(5) kJ/mol as the best experimental estimate for the dimer dissociation energy at 0 K. Further improvements have to wait for a more consistent determination of the room temperature equilibrium constant....

Effects of chirping on the dissociation dynamics of H2 in a two-frequency laser field

International Nuclear Information System (INIS)

Datta, Avijit; Bhattacharyya, S.S.; Kim, Bongsoo

2002-01-01

We present the effects of frequency chirping of laser pulses on (1+1)-photon resonance-enhanced dissociation dynamics of H 2 . The dissociation occurs via two closely spaced nonadiabatically coupled intermediate levels which are in one-photon resonance or near resonance with the initial level. Predissociating levels embedded into continua are considered. When the first laser field is sufficiently intense and suitably chirped, the dissociation probability is enhanced by adiabatic rapid passage through the avoided crossing arising from the frequency swept radiative interaction. The whole population of the ground level can be effectively transferred to the intermediate levels by this technique facilitating the dissociation process by the second field. We also report the effect of frequency detuning and chirp width on the dissociation probability. Widths of the two peaks of the dissociation line shape increase with an increase in chirp width, resulting in the possibility of control in the dissociation yield. When the first field is a laser pulse of low intensity and constant frequency and the second laser frequency is chirped, predissociating levels take important parts in the dissociation dynamics and we obtain a signature of the nonadiabatic effect of the first step on the second step of photodissociation dynamics. This feature is due to the presence of the predissociating levels and the nonadiabatic mixing of two intermediate levels. All these results can be explained in terms of the adiabatic dressed levels

Dissociation Energies of Diatomic Molecules

International Nuclear Information System (INIS)

Qun-Chao, Fan; Wei-Guo, Sun

2008-01-01

Molecular dissociation energies of 10 electronic states of alkali molecules of KH, 7 LiD, 7 LiH, 6 LiH, 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 D e theory , which are in excellent agreement with the experimental dissociation energies D e expt . (atomic and molecular physics)

Transition probabilities and dissociation energies of MnH and MnD molecules

International Nuclear Information System (INIS)

Nagarajan, K.; Rajamanickam, N.

1997-01-01

The Frank-Condon factors (vibrational transition probabilities) and r-centroids have been evaluated by the more reliable numerical integration procedure for the bands of A-X system of MnH and MnD molecules, using a suitable potential. By fitting the Hulburt- Hirschfelder function to the experimental potential curve using correlation coefficient, the dissociation energy for the electronic ground states of MnH and MnD molecules, respectively have been estimated as D 0 0 =251±5 KJ.mol -1 and D 0 0 =312±6 KJ.mol -1 . (authors)

Optimal control of bond selectivity in unimolecular reactions

International Nuclear Information System (INIS)

Shi Shenghua; Rabitz, H.

1991-01-01

The optimal control theory approach to designing optimal fields for bond-selective unimolecular reactions is presented. A set of equations for determining the optimal fields, which will lead to the achievement of the objective of bond-selective dissociation is developed. The numerical procedure given for solving these equations requires the repeated calculation of the time propagator for the system with the time-dependent Hamiltonian. The splitting approximation combined with the fast Fourier transform algorithm is used for computing the short time propagator. As an illustrative example, a model linear triatomic molecule is treated. The model system consists of two Morse oscillators coupled via kinetic coupling. The magnitude of the dipoles of the two Morse oscillators are the same, the fundamental frequencies are almost the same, but the dissociation energies are different. The rather demanding objective under these conditions is to break the stronger bond while leaving the weaker one intact. It is encouraging that the present computational method efficiently gives rise to the optimal field, which leads to the excellent achievement of the objective of bond selective dissociation. (orig.)

Theoretical study of the mechanism of formation of a chemical bond between two ions: A+ and B+. Application to CO++. Interpretation of N2O++ photo-dissociation mechanisms

International Nuclear Information System (INIS)

Levasseur, Nathalie

1989-01-01

This research thesis reports the theoretical study of the mechanism of formation of a chemical bond between two positively charged species, within the frame of the valence-bond theory and in the CO model case. The analysis in terms of orthogonal and non orthogonal orbitals leads to two very different interpretations, and allows potential curves of doubly charged diatomic ions to be simply explained, the generally evoked model to be put into question again, and a predictive model to be developed. The theoretical determination of N 2 O potential energy surfaces and of the first states of N 2 O ++ ( 3 Σ - , 1 Δ, 1 Σ + et 3 Π) allowed experimental results of N 2 O ++ photo-dissociation to be at least qualitatively understood and interpreted. Moreover, the study of electronic configurations involved in dissociation, showed that the model elaborated for a diatomic molecule is also valid for a triatomic system [fr

Bonding character and s-p hybridization of orbitals of hydride molecules according to photoelectron spectroscopy data

International Nuclear Information System (INIS)

Vovna, V.I.

1988-01-01

In consideration of the electron structure of the molecules in terms of canonical many-centered orbitals by s-p hybridization we mean mixture of the ns and np orbitals of an atom into one molecular orbital. The PE spectra of the valence levels of the molecules give direct information on the influence of s-p hybridization on the bonding character and energies of the levels [1, 3]. In this article we discuss the influence of hybridization on the bonding character of the MO of the isoelectronic series A 7 H - A 6 H 2 - A 5 H 2 - A 4 H 4 according to the results of PE spectroscopy. To simplify the discussion we adopt the approximation of Kupmans theorem IP i = -var epsilon i

Hydrogen bonding as the origin of the switching behavior in dithiolated phenylene-vinylene oligomers

KAUST Repository

Obodo, Tobechukwu Joshua

2013-08-29

We investigate theoretically the switching behavior of a dithiolated phenylene-vinylene oligomer sandwiched between Au(111) electrodes using self-interaction corrected density-functional theory combined with the nonequilibrium Green\\'s-function method for quantum transport. The molecule presents a configurational bistability, which can be exploited in constructing molecular memories, switches, and sensors. We find that protonation of the terminating thiol groups is at the origin of the change in conductance. H bonding at the thiol group weakens the S-Au bond and reduces by about one order of magnitude the transmission coefficient at the Fermi level, and thus the linear response conductance. Furthermore, protonation downshifts in energy the position of the highest occupied molecular orbital, so that the current of the protonated species is lower than that of the unprotonated one along the entire bias range investigated, from −1.5 to 1.5 V. A second protonation at the opposite thiol group has only minor effects and no further drastic reduction in transmission takes place. Our results allow us to re-interpret the experimental data originally attributing the conductance reduction to H dissociation.

When Langmuir is too simple: H-2 dissociation on Pd(111) at high coverage

DEFF Research Database (Denmark)

Lopez, Nuria; Lodziana, Zbigniew; Illas, F.

2004-01-01

Recent experiments of H-2 adsorption on Pd(111) [T. Mitsui et al., Nature (London) 422, 705 (2003)] have questioned the classical Langmuir picture of second order adsorption kinetics at high surface coverage requiring pairs of empty sites for the dissociative chemisorption. Experiments find that ...

Vibrational excitation and dissociative recombination of the LiH+ ion

Czech Academy of Sciences Publication Activity Database

Čurík, Roman; Greene, C. H.

2007-01-01

Roč. 105, 11-12 (2007), s. 1565-1574 ISSN 0026-8976 R&D Projects: GA AV ČR IAA100400501; GA AV ČR 1ET400400413 Institutional research plan: CEZ:AV0Z40400503 Keywords : dissociative recombination * vibrational excitation * lithium hydride * quantum defect the ory Subject RIV: CF - Physical ; The oretical Chemistry Impact factor: 1.568, year: 2007

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.

Dissociation kinetics of Fe(III)- and Al(III)-natural organic matter complexes at pH 6.0 and 8.0 and 25 °C

Science.gov (United States)

Jones, Adele M.; Pham, A. Ninh; Collins, Richard N.; Waite, T. David

2009-05-01

The rate at which iron- and aluminium-natural organic matter (NOM) complexes dissociate plays a critical role in the transport of these elements given the readiness with which they hydrolyse and precipitate. Despite this, there have only been a few reliable studies on the dissociation kinetics of these complexes suggesting half-times of some hours for the dissociation of Fe(III) and Al(III) from a strongly binding component of NOM. First-order dissociation rate constants are re-evaluated here at pH 6.0 and 8.0 and 25 °C using both cation exchange resin and competing ligand methods for Fe(III) and a cation exchange resin method only for Al(III) complexes. Both methods provide similar results at a particular pH with a two-ligand model accounting satisfactorily for the dissociation kinetics results obtained. For Fe(III), half-times on the order of 6-7 h were obtained for dissociation of the strong component and 4-5 min for dissociation of the weak component. For aluminium, the half-times were on the order of 1.5 h and 1-2 min for the strong and weak components, respectively. Overall, Fe(III) complexes with NOM are more stable than analogous complexes with Al(III), implying Fe(III) may be transported further from its source upon dilution and dispersion.

Backbone conformation affects duplex initiation and duplex propagation in hybridisation of synthetic H-bonding oligomers.

Science.gov (United States)

Iadevaia, Giulia; Núñez-Villanueva, Diego; Stross, Alexander E; Hunter, Christopher A

2018-06-06

Synthetic oligomers equipped with complementary H-bond donor and acceptor side chains form multiply H-bonded duplexes in organic solvents. Comparison of the duplex forming properties of four families of oligomers with different backbones shows that formation of an extended duplex with three or four inter-strand H-bonds is more challenging than formation of complexes that make only two H-bonds. The stabilities of 1 : 1 complexes formed between length complementary homo-oligomers equipped with either phosphine oxide or phenol recognition modules were measured in toluene. When the backbone is very flexible (pentane-1,5-diyl thioether), the stability increases uniformly by an order of magnitude for each additional base-pair added to the duplex: the effective molarities for formation of the first intramolecular H-bond (duplex initiation) and subsequent intramolecular H-bonds (duplex propagation) are similar. This flexible system is compared with three more rigid backbones that are isomeric combinations of an aromatic ring and methylene groups. One of the rigid systems behaves in exactly the same way as the flexible backbone, but the other two do not. For these systems, the effective molarity for formation of the first intramolecular H-bond is the same as that found for the other two backbones, but additional H-bonds are not formed between the longer oligomers. The effective molarities are too low for duplex propagation in these systems, because the oligomer backbones cannot adopt conformations compatible with formation of an extended duplex.

Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate.

Science.gov (United States)

Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B

2015-01-28

(1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

Energy-sensitive imaging detector applied to the dissociative recombination of D2H+

International Nuclear Information System (INIS)

Buhr, H.; Schwalm, D.; Mendes, M. B.; Novotny, O.; Berg, M. H.; Bing, D.; Krantz, C.; Orlov, D. A.; Sorg, T.; Stuetzel, J.; Varju, J.; Wolf, A.; Heber, O.; Rappaport, M. L.; Zajfman, D.

2010-01-01

We report on an energy-sensitive imaging detector for studying the fragmentation of polyatomic molecules in the dissociative recombination of fast molecular ions with electrons. The system is based on a large area (10x10 cm 2 ) position-sensitive, double-sided Si-strip detector with 128 horizontal and 128 vertical strips, whose pulse height information is read out individually. The setup allows us to uniquely identify fragment masses and is thus capable of measuring branching ratios between different fragmentation channels, kinetic energy releases, and breakup geometries as a function of the relative ion-electron energy. The properties of the detection system, which has been installed at the Test Storage Ring (TSR) facility of the Max-Planck Institute for Nuclear Physics in Heidelberg, is illustrated by an investigation of the dissociative recombination of the deuterated triatomic hydrogen cation D 2 H + . A huge isotope effect is observed when comparing the relative branching ratio between the D 2 + H and the HD + D channel; the ratio 2B(D 2 + H)/B(HD + D), which is measured to be 1.27±0.05 at relative electron-ion energies around 0 eV, is found to increase to 3.7±0.5 at ∼5 eV.

Energy-sensitive imaging detector applied to the dissociative recombination of D2H+

Science.gov (United States)

Buhr, H.; Mendes, M. B.; Novotný, O.; Schwalm, D.; Berg, M. H.; Bing, D.; Heber, O.; Krantz, C.; Orlov, D. A.; Rappaport, M. L.; Sorg, T.; Stützel, J.; Varju, J.; Wolf, A.; Zajfman, D.

2010-06-01

We report on an energy-sensitive imaging detector for studying the fragmentation of polyatomic molecules in the dissociative recombination of fast molecular ions with electrons. The system is based on a large area (10×10 cm2) position-sensitive, double-sided Si-strip detector with 128 horizontal and 128 vertical strips, whose pulse height information is read out individually. The setup allows us to uniquely identify fragment masses and is thus capable of measuring branching ratios between different fragmentation channels, kinetic energy releases, and breakup geometries as a function of the relative ion-electron energy. The properties of the detection system, which has been installed at the Test Storage Ring (TSR) facility of the Max-Planck Institute for Nuclear Physics in Heidelberg, is illustrated by an investigation of the dissociative recombination of the deuterated triatomic hydrogen cation D2H+. A huge isotope effect is observed when comparing the relative branching ratio between the D2 + H and the HD + D channel; the ratio 2B(D2 + H)/B(HD + D), which is measured to be 1.27±0.05 at relative electron-ion energies around 0 eV, is found to increase to 3.7±0.5 at ~5 eV.

Experimental investigation of dissociation pathways of cooled HeH+ following valence electron excitation at 32 nm by intense free-electron-laser radiation

International Nuclear Information System (INIS)

Pedersen, H. B.; Lammich, L.; Domesle, C.; Jordon-Thaden, B.; Ullrich, J.; Wolf, A.; Heber, O.; Treusch, R.; Guerassimova, N.

2010-01-01

The dissociation pathways of HeH + have been investigated below the first ionization continuum by photoabsorption at 32 nm, using fragment momentum imaging in a crossed-beams experiment at the free-electron laser in Hamburg (FLASH). Investigations were done both for ions with several vibrational levels excited in the ion source and for ions vibrationally cooled in an electrostatic ion trap prior to the irradiation. The product channels He + (1s)+H(nl) and He(1snl)+H + were separated and the He(1snl)+H + channel was particularly studied by coincidence detection of the He and H + fragments on two separate fragment detectors. At 32 nm excitation, the branching ratio between the product channels was found to be σ He + +H /σ He+H + =0.96±0.11 for vibrationally hot and 1.70±0.48 for vibrationally cold ions. The spectra of kinetic energy releases for both channels revealed that photodissociation at 32 nm leads to high Rydberg states (n > or approx. 3-4) of the emerging atomic fragments irrespective of the initial vibrational excitation of HeH + . The fragment angular distributions showed that dissociation into the He+H + channel mostly (∼70%) proceeds through 1 Π states, while for the He + +H channel 1 Σ and 1 Π states are of about equal importance.

Development of HIP bonding procedure and mechanical properties of HIP bonded joints for reduced activation ferritic steel F-82H

International Nuclear Information System (INIS)

Oda, Masahiro; Kurasawa, Toshimasa; Kuroda, Toshimasa; Hatano, Toshihisa; Takatsu, Hideyuki

1997-03-01

Structural materials of blanket components in fusion DEMO reactors will receive a neutron wall load more than 3-5MW/m 2 as well as exposed by surface heat flux more than 0.5MW/m 2 . A reduced activation ferritic steel F-82H has been developed by JAERI in collaboration with NKK from viewpoints of resistance for high temperature and neutron loads and lower radioactivity. This study intends to obtain basic performance of F-82H to establish the fabrication procedure of the first wall and blanket box by using Hot Isostatic Pressing (HIP) bonding. Before HIP bonding tests, effects of heat treatment temperature and surface roughness on mechanical properties of joints were investigated in the heat treatment tests and diffusion bonding tests, respectively. From these results, the optimum HIP bonding conditions and the post heat treatment were selected. Using these conditions, the HIP bonding tests were carried out to evaluate HIP bondability and to obtain mechanical properties of the joints. Sufficient HIP bonding performance was obtained under the temperature of 1040degC, the compressive stress of 150MPa, the holding time of 2h, and the surface roughness ∼μ m. Mechanical properties of HIP bonded joints with these conditions were similar to those of as-received base metal. An oxide formation on the surface to be bonded would need to be avoided for sufficient bonding. The bonding ratio, Charpy impact value and fatigue performance of the joints strongly depended on the HIP conditions, especially temperature, while micro-structure, Vickers hardness and tensile properties had little dependence on the HIP temperature. The surface roughness strongly affected the bonding ratio and would be required to be in the level of a few μ m. In the HIP bonding test of the welded material, the once-melted surface could be jointed by the HIP bonding under the above-mentioned procedure. (J.P.N.)

The effect of carbon-chain oxygenation in the carbon-carbon dissociation.

Science.gov (United States)

Dos Santos, Lisandra Paulino; Baptista, Leonardo

2018-06-01

Currently, there is a trend of moving away from the use of fossil fuels to the use of biofuels. This modification changes the molecular structure of gasoline and diesel constituents, which should impact pollutant emissions and engine efficiency. An important property of automotive fuels is the resistance to autoignition. The goal of the present work is to evaluate thermochemical and kinetic parameters that govern the carbon-carbon bond dissociation and relate these parameters, in conjunction with molecular properties, to autoignition resistance. Three model reactions were investigated in the present work: dissociation of ethane, ethanol, and ethanal. All studies were conducted at the multiconfigurational level of theory, and the rate coefficients were evaluated from 300 to 2000 K. The comparison of dissociation energies and Arrhenius expressions indicates that autoignition resistance is related to the kinetic control of dissociation reactions and it is possible to relate the higher octane number of ethanol based fuels to the kinetics parameters of carbon-carbon bond fission. Graphical abstract Effect of the functional group in the Arrhenius parameters of the C-C dissociation. Arrhenius curves calculated at NEVPT2(6,6)/6-311G(2df,2pd).

Recent advances in C(sp3–H bond functionalization via metal–carbene insertions

Directory of Open Access Journals (Sweden)

Bo Wang

2016-04-01

Full Text Available The recent development of intermolecular C–H insertion in the application of C(sp3–H bond functionalizations, especially for light alkanes, is reviewed. The challenging problem of regioselectivity in C–H bond insertions has been tackled by the use of sterically bulky metal catalysts, such as metal porphyrins and silver(I complexes. In some cases, high regioselectivity and enantioselectivity have been achieved in the C–H bond insertion of small alkanes. This review highlights the most recent accomplishments in this field.

Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water

Science.gov (United States)

Zhovtobriukh, Iurii; Besley, Nicholas A.; Fransson, Thomas; Nilsson, Anders; Pettersson, Lars G. M.

2018-04-01

The connection between specific features in the water X-ray absorption spectrum and X-ray emission spectrum (XES) and the local H-bond coordination is studied based on structures obtained from path-integral molecular dynamics simulations using either the opt-PBE-vdW density functional or the MB-pol force field. Computing the XES spectrum using all molecules in a snapshot results in only one peak in the lone-pair (1b1) region, while the experiment shows two peaks separated by 0.8-0.9 eV. Different H-bond configurations were classified based on the local structure index (LSI) and a geometrical H-bond cone criterion. We find that tetrahedrally coordinated molecules characterized by high LSI values and two strong donated and two strong accepted H-bonds contribute to the low energy 1b1 emission peak and to the post-edge region in absorption. Molecules with the asymmetric H-bond environment with one strong accepted H-bond and one strong donated H-bond and low LSI values give rise to the high energy 1b1 peak in the emission spectrum and mainly contribute to the pre-edge and main-edge in the absorption spectrum. The 1b1 peak splitting can be increased to 0.62 eV by imposing constraints on the H-bond length, i.e., for very tetrahedral structures short H-bonds (less than 2.68 Å) and for very asymmetric structures elongated H-bonds (longer than 2.8 Å). Such structures are present, but underrepresented, in the simulations which give more of an average of the two extremes.

Relationship between x-ray emission and absorption spectroscopy and the local H-bond environment in water.

Science.gov (United States)

Zhovtobriukh, Iurii; Besley, Nicholas A; Fransson, Thomas; Nilsson, Anders; Pettersson, Lars G M

2018-04-14

The connection between specific features in the water X-ray absorption spectrum and X-ray emission spectrum (XES) and the local H-bond coordination is studied based on structures obtained from path-integral molecular dynamics simulations using either the opt-PBE-vdW density functional or the MB-pol force field. Computing the XES spectrum using all molecules in a snapshot results in only one peak in the lone-pair (1b 1 ) region, while the experiment shows two peaks separated by 0.8-0.9 eV. Different H-bond configurations were classified based on the local structure index (LSI) and a geometrical H-bond cone criterion. We find that tetrahedrally coordinated molecules characterized by high LSI values and two strong donated and two strong accepted H-bonds contribute to the low energy 1b 1 emission peak and to the post-edge region in absorption. Molecules with the asymmetric H-bond environment with one strong accepted H-bond and one strong donated H-bond and low LSI values give rise to the high energy 1b 1 peak in the emission spectrum and mainly contribute to the pre-edge and main-edge in the absorption spectrum. The 1b 1 peak splitting can be increased to 0.62 eV by imposing constraints on the H-bond length, i.e., for very tetrahedral structures short H-bonds (less than 2.68 Å) and for very asymmetric structures elongated H-bonds (longer than 2.8 Å). Such structures are present, but underrepresented, in the simulations which give more of an average of the two extremes.

CO dissociation on magnetic Fen clusters

KAUST Repository

Jedidi, Abdesslem; Markovits, Alexis; Minot, Christian; Abderrabba, Manef Ben; Van Hove, Michel A.

2014-01-01

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

Diffusion bonding of reduced activation ferritic steel F82H for demo blanket application

International Nuclear Information System (INIS)

Kurasawa, T.; Tamura, M.

1996-01-01

A reduced activation ferritic steel, a grade F82H developed by JAERI, is a promising candidate structural material for the blanket and the first wall of DEMO reactors. In the present study, diffusion bonding of F82H has been investigated to develop the fabrication procedures of the blanket box and the first wall panel with cooling channels embedded by F82H. The parameters examined are the bonding temperature (810-1050 C), bonding pressure (2-10 MPa) and roughness of the bonding surface (0.5-12.8 μR max ), and metallurgical examination and mechanical tests of the diffusion bonded joints have been conducted. From the tests, sufficient bonding was obtained under the temperatures of 840-1 050 C (compressive stress of 3-12 MPa), and it was found that heat treatment following diffusion bonding is essential to obtain the mechanical properties similar to that of the base metal. (orig.)

CO dissociation and CO hydrogenation on smooth and ion-bombarded Pd(1 1 1): SFG and XPS spectroscopy at mbar pressures

Science.gov (United States)

Rupprechter, G.; Kaichev, V. V.; Unterhalt, H.; Morkel, M.; Bukhtiyarov, V. I.

2004-07-01

The CO dissociation probability on transition metals is often invoked to explain the product distribution (selectivity) of catalytic CO hydrogenation. Along these lines, we have investigated CO adsorption and dissociation on smooth and ion-bombarded Pd(1 1 1) at pressures up to 1 mbar using vibrational sum frequency generation (SFG) and X-ray photoelectron spectroscopy (XPS). Under high pressure, CO adsorbate structures were observed that were identical to high-coverage structures in UHV. On ion-bombarded surfaces an additional species was detected which was attributed to CO bridge bonded to defect (low-coordinated) sites. On both surfaces, no indications of CO dissociation were found even after hours of 0.1 mbar CO exposure. However, exposing CO/H 2 mixtures to ion-bombarded Pd(1 1 1) produced carbonaceous deposits suggesting CH xO species as precursors for CO bond cleavage and that the formation of CH xO is facilitated by surface defects. The relevance of the observations for CO hydrogenation on Pd catalysts is discussed.

CO dissociation and CO hydrogenation on smooth and ion-bombarded Pd(1 1 1): SFG and XPS spectroscopy at mbar pressures

Energy Technology Data Exchange (ETDEWEB)

Rupprechter, G.; Kaichev, V.V.; Unterhalt, H.; Morkel, M.; Bukhtiyarov, V.I

2004-07-31

The CO dissociation probability on transition metals is often invoked to explain the product distribution (selectivity) of catalytic CO hydrogenation. Along these lines, we have investigated CO adsorption and dissociation on smooth and ion-bombarded Pd(1 1 1) at pressures up to 1 mbar using vibrational sum frequency generation (SFG) and X-ray photoelectron spectroscopy (XPS). Under high pressure, CO adsorbate structures were observed that were identical to high-coverage structures in UHV. On ion-bombarded surfaces an additional species was detected which was attributed to CO bridge bonded to defect (low-coordinated) sites. On both surfaces, no indications of CO dissociation were found even after hours of 0.1 mbar CO exposure. However, exposing CO/H{sub 2} mixtures to ion-bombarded Pd(1 1 1) produced carbonaceous deposits suggesting CH{sub x}O species as precursors for C---O bond cleavage and that the formation of CH{sub x}O is facilitated by surface defects. The relevance of the observations for CO hydrogenation on Pd catalysts is discussed.

Excited-State N2 Dissociation Pathway on Fe-Functionalized Au.

Science.gov (United States)

Martirez, John Mark P; Carter, Emily A

2017-03-29

Localized surface plasmon resonances (LSPRs) offer the possibility of light-activated chemical catalysis on surfaces of strongly plasmonic metal nanoparticles. This technology relies on lower-barrier bond formation and/or dissociation routes made available through energy transfer following the eventual decay of LSPRs. The coupling between these decay processes and a chemical trajectory (nuclear motion, charge-transfer, intersystem crossing, etc.) dictates the availability of these alternative (possibly lower barrier) excited-state channels. The Haber-Bosch method of NH 3 synthesis from N 2 and H 2 is notoriously energy intensive. This is due to the difficulty of N 2 dissociation despite the overall reaction being thermodynamically favorable at ambient temperatures and pressures. LSPRs may provide means to improve the kinetics of N 2 dissociation via induced resonance electronic excitation. In this work, we calculate, via embedded n-electron valence second-order perturbation theory within the density functional embedding theory, the excited-state potential energy surfaces for dissociation of N 2 on an Fe-doped Au(111) surface. This metal alloy may take advantage simultaneously of the strong LSPR of Au and the catalytic activity of Fe toward N 2 dissociation. We find the ground-state dissociation activation energy to be 4.74 eV/N 2 , with Fe as the active site on the surface. Consecutive resonance energy transfers (RETs) may be accessed due to the availability of many electronically excited states with intermediate energies arising from the metal surface that may couple to states induced by the Fe-dopant and the adsorbate molecule, and crossing between excited states may effectively lower the dissociation barrier to 1.33 eV. Our work illustrates that large energetic barriers, prohibitive toward chemical reaction, may be overcome through multiple RETs facilitating an otherwise difficult chemical process.

Fragmentation of C2H4 by charge-changing collisions of O2+ ions

International Nuclear Information System (INIS)

Sato, S.; Mizuno, T.; Yamada, T.; Imai, M.; Shibata, H.; Itoh, A.; Tsuchida, H.

2009-01-01

We investigated molecular fragmentation of C 2 H 4 in charge-changing collisions of 1.14MeV O 2+ ions. Branching ratios associated with decaying from temporary produced (C 2 H 4 ) r+ ions into various fragment channels were obtained. Dissociation via a C-C bond breaking is preferential in 1-electron loss collisions in comparison with 1-electron capture collisions. We confirmed that multiple ionization and dissociation rarely occur in electron capture collisions, while they occur rather strongly in electron loss collisions. (author)

Dissociative Photoionization of 1-Halogenated Silacyclohexanes: Silicon Traps the Halogen.

Science.gov (United States)

Bodi, Andras; Sigurdardottir, Katrin Lilja; Kvaran, Ágúst; Bjornsson, Ragnar; Arnason, Ingvar

2016-11-23

The threshold photoelectron spectra and threshold photoionization mass spectra of 1-halogenated-1-silacyclohexanes, for the halogens X = F, Cl, Br, and I, have been obtained using synchrotron vacuum ultraviolet radiation and photoelectron photoion coincidence spectroscopy. As confirmed by a similar ionization onset and density functional theory molecular orbitals, the ionization to the ground state is dominated by electron removal from the silacyclohexane ring for X = F, Cl, and Br, and from the halogen lone pair for X = I. The breakdown diagrams show that the dissociative photoionization mechanism is also different for X = I. Whereas the parent ions decay by ethylene loss for X = F to Br in the low-energy regime, the iodine atom is lost for X = I. The first step is followed by a sequential ethylene loss at higher internal energies in each of the compounds. It is argued that the tendency of silicon to lower bond angles stabilizes the complex cation in which C 2 H 4 is η 2 -coordinated to it, and which precedes ethylene loss. Together with the relatively strong silicon-halogen bonds and the increased inductive effect of the silacyclohexane ring in stabilizing the cation, this explains the main differences observed in the fragmentation of the halogenated silacyclohexane and halogenated cyclohexane ions. The breakdown diagrams have been modeled taking into account slow dissociations at threshold and the resulting kinetic shift. The 0 K appearance energies have been obtained to within 0.08 eV for the ethylene loss for X = F to Br (10.56, 10.51, and 10.51 eV, respectively), the iodine atom loss for X = I (10.11 eV), the sequential ethylene loss for X = F to I (12.29, 12.01, 11.94, and 11.86 eV, respectively), and the minor channels of H loss for X = F (10.56 eV) and propylene loss in X = Cl (also at 10.56 eV). The appearance energies for the major channels likely correspond to the dissociative photoionization reaction energy.

GABA, depressants and chloride ions affect the rate of dissociation of 35S-t-butylbicyclophosphorothionate binding

International Nuclear Information System (INIS)

Maksay, G.; Ticku, M.K.

1985-01-01

The dissociation of 35 S-TBPS was studied from binding sites of rat cerebral cortex. Monophasic dissociation plots became polyphasic and accelerated in the presence of micromolar concentrations of GABA suggesting the involvement of low (or super-low) affinity GABA receptors. The presence of the depressants etazolate, R(-)MPPB and ethanol resulted in similarly accelerated dissociation patterns. In contrast, the convulsants S(+)MPPB and pentamethylenetetrazol did not significantly affect the dissociation of TBPS. Dissociation initiated by dilution was not affected either by an excess of picrotoxin or by varying the equilibrium occupancy of the TBPS sites. These findings rule out the possibility of a kinetic cooperativity for the binding of convulsants. The removal of chloride ions also enhanced the rate of TBPS dissociation. Kinetic heterogeneity of the TBPS binding sites can be interpreted with allosteric interactions mediated by various sites at the GABA receptor complex coupled to different states of the chloride ionophore. 15 references, 3 figures, 1 table

Real space in situ bond energies: toward a consistent energetic definition of bond strength.

Science.gov (United States)

Menéndez-Crespo, Daniel; Costales, Aurora; Francisco, Evelio; Martin Pendas, Angel

2018-04-14

A rigorous definition of intrinsic bond strength based on the partitioning of a molecule into real space fragments is presented. Using the domains provided by the quantum theory of atoms in molecules (QTAIM) together with the interacting quantum atoms (IQA) energetic decomposition, we show how an in situ bond strength, matching all the requirements of an intrinsic bond energy, can be defined between each pair of fragments. Total atomization or fragmentation energies are shown to be equal to the sum of these in situ bond energies (ISBEs) if the energies of the fragments are measured with respect to their in-the-molecule state. These energies usually lie above the ground state of the isolated fragments by quantities identified with the standard fragment relaxation or deformation energies, which are also provided by the protocol. Deformation energies bridge dissociation energies with ISBEs, and can be dissected using well-known tools of real space theories of chemical bonding. Similarly, ISBEs can be partitioned into ionic and covalent contributions, and this feature adds to the chemical appeal of the procedure. All the energetic quantities examined are observable and amenable, in principle, to experimental determination. Several systems, exemplifying the role of each energetic term herein presented are used to show the power of the approach. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

1H-1H correlations across N-H···N hydrogen bonds in nucleic acids

International Nuclear Information System (INIS)

Majumdar, Ananya; Gosser, Yuying; Patel, Dinshaw J.

2001-01-01

In 2H J NN -COSY experiments, which correlate protons with donor/acceptor nitrogens across N d ···HN a bonds, the receptor nitrogen needs to be assigned in order to unambiguously identify the hydrogen bond. For many situations this is a non-trivial task which is further complicated by poor dispersion of (N a ,N d ) resonances. To address these problems, we present pulse sequences to obtain direct, internucleotide correlations between protons in uniformly 13 C/ 15 N labeled nucleic acids containing N d ···HN a hydrogen bonds. Specifically, the pulse sequence H2(N1N3)H3 correlates H2(A,ω 1 ):H3(U,ω 2 ) protons across Watson-Crick A-U and mismatched G·A base pairs, the sequences H5(N3N1)H1/H6(N3N1)H1 correlate H5(C,ω 1 )/H6(C,ω 1 ):H1(G,ω 2 ) protons across Watson-Crick G-C base pairs, and the H 2 (N2N7)H8 sequence correlates NH 2 (G,A,C;ω 1 ):H8(G,A;ω 2 ) protons across G·G, A·A, sheared G·A and other mismatch pairs. These 1 H- 1 H connectivities circumvent the need for independent assignment of the donor/acceptor nitrogen and related degeneracy issues associated with poorly dispersed nitrogen resonances. The methodology is demonstrated on uniformly 13 C/ 15 N labeled samples of (a) an RNA regulatory element involving the HIV-1 TAR RNA fragment, (b) a multi-stranded DNA architecture involving a G·(C-A) triad-containing G-quadruplex and (c) a peptide-RNA complex involving an evolved peptide bound to the HIV-1 Rev response element (RRE) RNA fragment

Modification of Purine and Pyrimidine Nucleosides by Direct C-H Bond Activation

Directory of Open Access Journals (Sweden)

Yong Liang

2015-03-01

Full Text Available Transition metal-catalyzed modifications of the activated heterocyclic bases of nucleosides as well as DNA or RNA fragments employing traditional cross-coupling methods have been well-established in nucleic acid chemistry. This review covers advances in the area of cross-coupling reactions in which nucleosides are functionalized via direct activation of the C8-H bond in purine and the C5-H or C6-H bond in uracil bases. The review focuses on Pd/Cu-catalyzed couplings between unactivated nucleoside bases with aryl halides. It also discusses cross-dehydrogenative arylations and alkenylations as well as other reactions used for modification of nucleoside bases that avoid the use of organometallic precursors and involve direct C-H bond activation in at least one substrate. The scope and efficiency of these coupling reactions along with some mechanistic considerations are discussed.

Energy localization and molecular dissociation

International Nuclear Information System (INIS)

Takeno, S.; Tsironis, G.P.

2005-01-01

We study analytically as well as numerically the role that large-amplitude vibrations play during the process of molecular dissociation. Our model consists of a linear three-atom molecule composed of identical atoms interacting with their nearest neighbors by Morse potentials. We find a close relation between energy localization and bond breaking and evaluate numerically the corresponding reaction paths

Three methods to measure RH bond energies

International Nuclear Information System (INIS)

Berkowitz, J.; Ellison, G.B.; Gutman, D.

1993-01-01

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

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....

N-(N-[2-(3,5-Difluorophenyl)acetyl]-(S)-alanyl)-(S)-phenylglycine tert-butyl ester (DAPT): an inhibitor of γ-secretase, revealing fine electronic and hydrogen-bonding features

Energy Technology Data Exchange (ETDEWEB)

Czerwinski, Andrzej; Valenzuela, Francisco [Peptides International Inc., 11621 Electron Drive, Louisville, KY 40299 (United States); Afonine, Pavel [Lawrence Berkeley National Laboratory, One Cyclotron Road, Building 64R0121, Berkeley, CA 94720 (United States); Dauter, Miroslawa, E-mail: dauter@anl.gov [Basic Research Program, SAIC-Frederick Inc., Synchrotron Radiation Research Section, MCL, NCI, Argonne National Laboratory, Biosciences Division, Building 202, Argonne, IL 60439 (United States); Dauter, Zbigniew [Synchrotron Radiation Research Section, MCL, NCI, Argonne National Laboratory, Biosciences Division, Building 202, Argonne, IL 60439 (United States); Peptides International Inc., 11621 Electron Drive, Louisville, KY 40299 (United States)

2010-12-01

The title compound, C{sub 23}H{sub 26}F{sub 2}N{sub 2}O{sub 4}, is a dipeptidic inhibitor of γ-secretase, one of the enzymes involved in Alzheimer’s dis@@ease. The mol@@ecule adopts a compact conformation, without intra@@molecular hydrogen bonds. In the crystal structure, one of the amide N atoms forms the only inter@@molecular N—H⋯O hydrogen bond; the second amide N atom does not form hydrogen bonds. High-resolution synchrotron diffraction data permitted the unequivocal location and refinement without restraints of all H atoms, and the identification of the characteristic shift of the amide H atom engaged in the hydrogen bond from its ideal position, resulting in a more linear hydrogen bond. Significant residual densities for bonding electrons were revealed after the usual SHELXL refinement, and modeling of these features as additional inter@@atomic scatterers (IAS) using the program PHENIX led to a significant decrease in the R factor from 0.0411 to 0.0325 and diminished the r.m.s. deviation level of noise in the final difference Fourier map from 0.063 to 0.037 e Å{sup −3}.

Observation of double-well potential of NaH C 1Σ+ state: Deriving the dissociation energy of its ground state.

Science.gov (United States)

Chu, Chia-Ching; Huang, Hsien-Yu; Whang, Thou-Jen; Tsai, Chin-Chun

2018-03-21

Vibrational levels (v = 6-42) of the NaH C 1 Σ + state including the inner and outer wells and the near-dissociation region were observed by pulsed optical-optical double resonance fluorescence depletion spectroscopy. The absolute vibrational quantum number is identified by comparing the vibrational energy difference of this experiment with the ab initio calculations. The outer well with v up to 34 is analyzed using the Dunham expansion and a Rydberg-Klein-Rees (RKR) potential energy curve is constructed. A hybrid double-well potential combined with the RKR potential, the ab initio calculation, and a long-range potential is able to describe the whole NaH C 1 Σ + state including the higher vibrational levels (v = 35-42). The dissociation energy of the NaH C 1 Σ + state is determined to be D e (C) = 6595.10 ± 5 cm -1 and then the dissociation energy of the NaH ground state D e (X) = 15 807.87 ± 5 cm -1 can be derived.

Multicomponent DFT study of geometrical H/D isotope effect on hydrogen-bonded organic conductor, κ-H3(Cat EDT-ST)2

Science.gov (United States)

Yamamoto, Kaichi; Kanematsu, Yusuke; Nagashima, Umpei; Ueda, Akira; Mori, Hatsumi; Tachikawa, Masanori

2017-04-01

We theoretically investigated a significant contraction of the hydrogen-bonding O⋯O distance upon H/D substitution in our recently developed purely organic crystals, κ-H3(Cat-EDT-ST)2 (H-ST) and its isotopologue κ-D3(Cat-EDT-ST)2 (D-ST), having π-electron systems coupled with hydrogen-bonding fluctuation. The origin of this geometrical H/D isotope effect was elucidated by using the multicomponent DFT method, which takes the H/D nuclear quantum effect into account. The optimized O⋯O distance in H-ST was found to be longer than that in D-ST due to the anharmonicity of the potential energy curve along the Osbnd H bond direction, which was in reasonable agreement with the experimental trend.

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

KAUST Repository

Falivene, Laura; Poater, Albert; Cazin, Catherine S J; Slugovc, Christian; Cavallo, Luigi

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.

c-C5H5 on a Ni(1 1 1) surface: Theoretical study of the adsorption, electronic structure and bonding

International Nuclear Information System (INIS)

German, E.; Simonetti, S.; Pronsato, E.; Juan, A.; Brizuela, G.

2008-01-01

In the present work the ASED-MO method is applied to study the adsorption of cyclopentadienyl anion on a Ni(1 1 1) surface. The adsorption with the centre of the aromatic ring placed above the hollow position has been identified to be energetically the most favourable. The aromatic ring remains almost flat, the H atoms are tilted 17 deg. away from the metal surface. We modelled the metal surface by a two-dimensional slab of finite thickness, with an overlayer of c-C 5 H 5 - , one c-C 5 H 5 - per nine surface Ni atoms. The c-C 5 H 5 - molecule is attached to the surface with its five C atoms bonding mainly with three Ni atoms. The Ni-Ni bond in the underlying surface and the C-C bonds of c-C 5 H 5 - are weakened upon adsorption. We found that the band of Ni 5d z 2 orbitals plays an important role in the bonding between c-C 5 H 5 - and the surface, as do the Ni 6s and 6p z bands

Strong-Field Modulated Diffraction Effects in the Correlated Electron-Nuclear Motion in Dissociating H2+

International Nuclear Information System (INIS)

He Feng; Becker, Andreas; Thumm, Uwe

2008-01-01

We show that the electronic dynamics in a molecule driven by a strong field is complex and potentially even counterintuitive. As a prototype example, we simulate the interaction of a dissociating H 2 + molecule with an intense infrared laser pulse. Depending on the laser intensity, the direction of the electron's motion between the two nuclei is found to follow or oppose the classical laser-electric force. We explain the sensitive dependence of the correlated electronic-nuclear motion in terms of the diffracting electronic momentum distribution of the dissociating two-center system. The distribution is dynamically modulated by the nuclear motion and periodically shifted in the oscillating infrared electric field

New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

Directory of Open Access Journals (Sweden)

Pavel Nagorny

2016-12-01

Full Text Available Hydrogen bond donor catalysis represents a rapidly growing subfield of organocatalysis. While traditional hydrogen bond donors containing N–H and O–H moieties have been effectively used for electrophile activation, activation based on other types of non-covalent interactions is less common. This mini review highlights recent progress in developing and exploring new organic catalysts for electrophile activation through the formation of C–H hydrogen bonds and C–X halogen bonds.

Bond breaking and bond formation: how electron correlation is captured in many-body perturbation theory and density-functional theory.

Science.gov (United States)

Caruso, Fabio; Rohr, Daniel R; Hellgren, Maria; Ren, Xinguo; Rinke, Patrick; Rubio, Angel; Scheffler, Matthias

2013-04-05

For the paradigmatic case of H(2) dissociation, we compare state-of-the-art many-body perturbation theory in the GW approximation and density-functional theory in the exact-exchange plus random-phase approximation (RPA) for the correlation energy. For an unbiased comparison and to prevent spurious starting point effects, both approaches are iterated to full self-consistency (i.e., sc-RPA and sc-GW). The exchange-correlation diagrams in both approaches are topologically identical, but in sc-RPA they are evaluated with noninteracting and in sc-GW with interacting Green functions. This has a profound consequence for the dissociation region, where sc-RPA is superior to sc-GW. We argue that for a given diagrammatic expansion, sc-RPA outperforms sc-GW when it comes to bond breaking. We attribute this to the difference in the correlation energy rather than the treatment of the kinetic energy.

Note: Recombination of H+ and OH− ions along water wires

International Nuclear Information System (INIS)

Lee, Song Hi; Rasaiah, Jayendran C.

2013-01-01

Transport and recombination of hydrogen and hydroxide ions along a hydrogen-bonded water wire are studied by molecular dynamics simulation using a dissociating model for water. The results are compared with a recent CP-MD study of neutralization in bulk water [A. Hassanali, M. K. Prakrash, H. Eshet, and M. Parrinello, Proc. Natl. Acad. Sci. U.S.A. 108, 20410 (2011)]. The translocation of H + and OH − along the wire is faster than in the bulk water, followed by compression of the water wire when two water molecules separate the transported ions. Neutralization occurs with the concerted transfer of three protons as in the bulk water, followed by energy dissipation along the water chain

H2+ embedded in a Debye plasma: Electronic and vibrational properties

International Nuclear Information System (INIS)

Angel, M.L.; Montgomery, H.E.

2011-01-01

The effect of plasma screening on the electronic and vibrational properties of the H 2 + molecular ion was analyzed within the Born-Oppenheimer approximation. When a molecule is embedded in a plasma, the plasma screens the electrostatic interactions. This screening is accounted in the Schroedinger equation by replacing the Coulomb potentials with Yukawa potentials that incorporate the Debye length as a screening parameter. Variational expansions in confocal elliptical coordinates were used to calculate energies of the 1sσ g and 2pσ u states over a range of Debye lengths and bond distances. When the Debye length is comparable to the equilibrium bond distance, the dissociation energy is reduced while the equilibrium internuclear separation is increased. Expectation values, static dipole polarizabilities and spectroscopic constants were calculated for the 1sσ g state. - Highlights: → Effect of plasma screening on the properties of the H 2 + molecular ion. → Used a variational wavefunction in confocal elliptical coordinates. → Potential energy curves for the ground and first excited state are presented. → Decreasing Debye length increases polarizability of the electron distribution.

The electronic structure and bonding of a H-H pair in the vicinity of a BCC Fe bulk vacancy

Energy Technology Data Exchange (ETDEWEB)

Juan, A.; Pistonesi, C.; Brizuela, G. [Universidad Nacional del Sur, Bahia Blanca (Argentina). Departamento de Fisica; Garcia, A.J. [Universidad Nacional del Sur, Bahia Blanca (Argentina). Departamento de Ciencias de la Computacion

2003-09-01

The H-Fe interaction near a bcc Fe vacancy is analysed using a semi-empirical theoretical method. Calculations were performed using a Fe{sub 86} cluster with a vacancy. Hydrogen atoms are positioned in their local energy minima configurations. Changes in the electronic structure of Fe atoms near a vacancy were analysed for the system without H, with one H and with two H atoms. Fe atoms surrounding the vacancy weaken their bond when hydrogen is present. This is due to the formation of H-Fe bonds. Hydrogen influences only its nearest-neighbour Fe atoms. The H-H interaction was also analysed. For H-H distance of 0.82 Angstrom an H-H association is formed, while H-Fe interaction and Fe-Fe weakening is markedly reduced, when compared with other H-H interactions. (author)

Photophysics of Curcumin excited state in toluene-polar solvent mixtures: Role of H-bonding properties of the polar solvent

Energy Technology Data Exchange (ETDEWEB)

Saini, R.K.; Das, K., E-mail: kaustuv@rrcat.gov.in

2014-01-15

Excited state dynamics of Curcumin in binary solvent mixtures of toluene and polar H-bonding solvents were compared by using an instrument endowed with 40 ps time resolution. The solvation time constant of Curcumin increases significantly (and can therefore be measured) in polar solvents which have, either, both H-bond donating and accepting ability, or, only H-bond donating ability. These results suggest that the rate limiting step in the excited state dynamics of the pigment might be the formation and reorganization of the intermolecular H-bonding between the keto group of the pigment and the H-bond donating moieties of the polar solvent. -- Highlights: • Excited state dynamics of Curcumin in a binary solvent mixture of toluene and three polar H-bonding solvents were compared. • The solvation time constant increases significantly with polar solvents having, H-bond donating and accepting, or, H-bond donating ability. • Observed results suggest that H-bonding property of polar solvent plays an important role in the excited state dynamics. • Intermolecular H-bonding between the keto group of the pigment and polar solvent may be the rate limiting step.

Photophysics of Curcumin excited state in toluene-polar solvent mixtures: Role of H-bonding properties of the polar solvent

International Nuclear Information System (INIS)

Saini, R.K.; Das, K.

2014-01-01

Excited state dynamics of Curcumin in binary solvent mixtures of toluene and polar H-bonding solvents were compared by using an instrument endowed with 40 ps time resolution. The solvation time constant of Curcumin increases significantly (and can therefore be measured) in polar solvents which have, either, both H-bond donating and accepting ability, or, only H-bond donating ability. These results suggest that the rate limiting step in the excited state dynamics of the pigment might be the formation and reorganization of the intermolecular H-bonding between the keto group of the pigment and the H-bond donating moieties of the polar solvent. -- Highlights: • Excited state dynamics of Curcumin in a binary solvent mixture of toluene and three polar H-bonding solvents were compared. • The solvation time constant increases significantly with polar solvents having, H-bond donating and accepting, or, H-bond donating ability. • Observed results suggest that H-bonding property of polar solvent plays an important role in the excited state dynamics. • Intermolecular H-bonding between the keto group of the pigment and polar solvent may be the rate limiting step

Corrosion of glass-bonded sodalite as a function of pH and temperature

International Nuclear Information System (INIS)

Morss, L. R.; Stanley, M.; Tatko, C.; Ebert, W. L.

1999-01-01

This paper reports the results of corrosion tests with monoliths of sodalite, binder glass, and glass-bonded sodalite, a ceramic waste form (CWF) that is being developed to immobilize radioactive electrorefiner salt used to condition spent sodium-bonded nuclear fuel. These tests were performed with dilute pH-buffered solutions in the pH range of 5-10 at temperatures of 70 and 90 C. The pH dependence of the forward dissolution rates of the CWF and its components have been determined. The pH dependence of the dissolution rates of sodalite, binder glass, and glass-bonded sodalite are similar to the pH dependence of dissolution rate of borosilicate nuclear waste glasses, with a negative pH dependence in the acidic region and a positive pH dependence in the basic region. Our results on the forward dissolution rates and their temperature and pH dependence will be used as components of a waste form degradation model to predict the long-term behavior of the CWF in a nuclear waste repository

A Comprehensive Study on the Electronic State of Hydrogen in α-Phase PdH(D)x-Does a Chemical Bond Between Pd and H(D) Exist?

Science.gov (United States)

Dekura, Shun; Kobayashi, Hirokazu; Ikeda, Ryuichi; Maesato, Mitsuhiko; Yoshino, Haruka; Ohba, Masaaki; Ishimoto, Takayoshi; Kawaguchi, Shogo; Kubota, Yoshiki; Yoshioka, Satoru; Matsumura, Syo; Sugiyama, Takeharu; Kitagawa, Hiroshi

2018-06-12

The palladium(Pd)-hydrogen(H) system is one of the most famous hydrogen storage systems. Although there has been much research on β-phase PdH(D)x, we comprehensively investigated the nature of the interaction between Pd and H(D) in α-phase PdH(D)x (x H(D) chemical bond for the first time, by various in situ experimental techniques and first-principles theoretical calculations. The lattice expansion by H(D) dissolution in the α-phase lattice suggests the existence of interaction between Pd and H(D). The decrease of magnetic susceptibility and the increase of electrical resistivity indicate that the electronic states are changed by the H(D) dissolution in the α phase. In situ solid-state 1H and 2H NMR results and first-principles theoretical calculations revealed that a Pd-H(D) chemical bond exists in the α phase, but the bonding character of the Pd-H(D) chemical bond in the α phase is quite different from that in the β phase; the nature of the Pd-H(D) chemical bond in the α phase is a localized covalent bond whereas that in the β phase is a metallic bond. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidative addition of C--H bonds in organic molecules to transition metal centers

International Nuclear Information System (INIS)

Bergman, R.G.

1989-04-01

Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs

Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

Science.gov (United States)

Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

2018-01-16

Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

Science.gov (United States)

Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

2018-01-01

Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

Science.gov (United States)

Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R

2016-11-10

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using

Structure, bonding and energetics of N-heterocyclic carbene (NHC ...

Indian Academy of Sciences (India)

... of Science Education and Research (NISER), Bhubaneswar, 751 005 India .... out with Gaussian software with the default conver- .... with Multiwfn software.67 The FBO bond order has ... free energy ( G) of bond dissociation are given in.

Role of the H bond network in the radiation chemistry of hydrated systems

International Nuclear Information System (INIS)

Pommeret, S.; Renault, J.P.; Caeer, S.Le; Vigneron, G.; Vuilleumier, R.; Bratos, S.; Leicknam, J.Cl.

2006-01-01

In the present contribution a review of the recent work on the H bond dynamics, in absence of any reactant and a new theory that unambiguously establishes a new link between spectroscopic observation and geometric properties is presented, along with results on the radiation chemistry of nanoporous media and its influence on the H bond network of an interface

The electronic donation and frequency shifts on the YCCH⋯BH₄⁻ boron-bonded complexes (Y=H, CH₃, CF₃ and CCl₃).

Science.gov (United States)

Pordeus, Renato Q; Rego, Danilo G; Oliveira, Boaz G

2015-06-15

In this theoretical work, the tetrahydroborate ion (BH4(-)) was used as proton acceptor in the formation of the YCC-H⋯BH4(-) complexes (Y=H, CH3, CCl3 and CF3). Using B3LYP/6-311++G(d,p) level of theory, the results of structure corroborate with the analyses of infrared spectra showing that the changes in the bond lengths are in good agreement with the frequency shifts of the HCC-H, H3CCC-H, Cl3CCC-H and F3CCC-H proton donors. Based on the calculations carried out by the Quantum Theory of Atoms in Molecules (QTAIM), the reductions of electronic density corroborate with the red shifts in the frequencies of the C-H bonds. In addition to that, the C-H bonds are polarized because the contributions of s orbital diminish whereas of p increase. In line with this, the variations on the atomic radii computed via QTAIM calculations show that carbon outweigh hydrogen as follows (ΔrC>ΔrH). This scenario is indirectly supported by the Bent's rule of the chemical bonding. Although the interaction energies (corrected with BSSE and ZPE) vary between -19 and -67 kJ mol(-1), these complexes interact without covalent character. Copyright © 2015 Elsevier B.V. All rights reserved.

N-H···S Interaction Continues To Be an Enigma: Experimental and Computational Investigations of Hydrogen-Bonded Complexes of Benzimidazole with Thioethers.

Science.gov (United States)

Wategaonkar, Sanjay; Bhattacherjee, Aditi

2018-05-03

The N-H···S hydrogen bond, even though classified as an unconventional hydrogen bond, is found to bear important structural implications on protein structure and folding. In this article, we report a gas-phase study of the N-H···S hydrogen bond between the model compounds of histidine (benzimidazole, denoted BIM) and methionine (dimethyl sulfide, diethyl sulfide, and tetrahydrothiophene, denoted Me 2 S, Et 2 S, and THT, respectively). A combination of laser spectroscopic methods such as laser-induced fluorescence (LIF), two-color resonant two-photon ionization (2cR2PI), and fluorescence depletion by infrared spectroscopy (FDIR) is used in conjunction with DFT and ab initio calculations to characterize the nature of this prevalent H-bonding interaction in simple bimolecular complexes. A single conformer was found to exist for the BIM-Me 2 S complex, whereas the BIM-Et 2 S and BIM-THT complexes showed the presence of three and two conformers, respectively. These conformers were characterized on the basis of IR spectroscopic results and electronic structure calculations. Quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO), and energy decomposition (NEDA) analyses were performed to investigate the nature of the N-H···S H-bond. Comparison of the results with the N-H···O type of interactions in BIM and indole revealed that the strength of the N-H···S H-bond is similar to N-H···O in these binary gas-phase complexes.

Effects of expanding compact H II regions upon molecular clouds: Molecular dissociation waves, shock waves, and carbon ionization

International Nuclear Information System (INIS)

Hill, J.K.; Hollenbach, D.J.

1978-01-01

The effect of young expanding compact H II regions upon their molecular environments are studied, emphasizing the simultaneous evolution of the molecular hydrogen dissociation front and the shocked shell of gas surrounding the nebula. For H II regions powered by 05 stars embedded in molecular clouds of ambient density 10 3 -10 4 cm -3 the dissociation wave initially travels outward much more rapidly than the shock, but later decelerates and is swept up by the shock about 10 5 yr after the expansion begins. The 21 cm line of atomic hydrogen will be optically thick in both the preshock and postshock gas for most of this period. The most important coolant transitions are the [O I] 63 μm line and, for t> or approx. =10 5 yr, the rotational transitions of H 2 and/or the rotational transitions of CO. The vibrational transitions of H 2 are excited predominantly by ultraviolet pumping. We estimate the preshock and postshock carbon recombination-line emission measures

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.

Magnetic feature and near-infrared absorption of a [Pt(mnt)2]-based H-bond supramolecular crystal

International Nuclear Information System (INIS)

Li, Cui-Ping; Nie, Li; Pei, Wen-Bo; Li, Li; Tian, Zheng-Fang; Liu, Jian-Lan; Gao, Xu-Sheng; Ren, Xiao-Ming

2016-01-01

A new salt [H 2 DABCO][Pt(mnt) 2 ] 2 (1) (mnt 2- =maleonitriledithiolate and H 2 DABCO 2+ is diprotonated 1,4-diazabicyclo[2.2.2]octane) has been synthesized; its crystal structure, magnetic and near-IR absorption properties have been investigated. Two different [Pt(mnt) 2 ] - anions form the strong π-dimers, labeled as Pt(1)-dimer and Pt(2)-dimer, with quite shorter Pt…Pt and S…S distances and molecular plane-to-plane distance (<3.5 Å) within a dimer. The [Pt(mnt) 2 ] 2 2- π-dimers are connected through the cations in the strong H-bond manner to form three-dimensional H-bond supramolecular crystal. The salt shows weak paramagnetism in 1.99–300 K and this is due to the existence of strong antiferromagnetic coupling within a π-dimer. In addition, a small thermal hysteresis loop is observed at ca. 120 K, indicating that a phase transition probably occurs that is further confirmed by variable-temperature IR spectra. Another fascinating functionality of 1 is the intense near-IR absorption in the region of 750–2500 nm, and this near-IR absorption feature makes it to be a promising optical material. - Graphical abstract: A H-bond supramolecular crystal of [H 2 DABCO][Pt(mnt) 2 ] 2 shows a magnetic phase transition at ca. 120 K with sizable thermal hysteresis loop and intense near-IR absorption in the region of 750–2500 nm.

Population of the 3s state in hydrogen due to H+, H2+ and H3+ impact on ethylene, 1-butene and cis-2-butene

International Nuclear Information System (INIS)

Loyd, D.H.; Dawson, H.R.

1983-01-01

Absolute cross sections were measured for capture or dissociation into the 3s state of atomic hydrogen due to impact of 14-28 keV H + , H +2 and H +3 ions on ethylene, 1-butene and cis-2-butene. The cross sections obtained for the butene targets were almost identical and support the additive rule for cross sections. Ethylene cross sections were 21% lower than the values predicted by the additive rule, which agrees well with the observed trend toward reduction in total electron capture cross sections for protons on these gases at much higher energies

The role of uranium-arene bonding in H2O reduction catalysis

Science.gov (United States)

Halter, Dominik P.; Heinemann, Frank W.; Maron, Laurent; Meyer, Karsten

2018-03-01

The reactivity of uranium compounds towards small molecules typically occurs through stoichiometric rather than catalytic processes. Examples of uranium catalysts reacting with water are particularly scarce, because stable uranyl groups form that preclude the recovery of the uranium compound. Recently, however, an arene-anchored, electron-rich uranium complex has been shown to facilitate the electrocatalytic formation of H2 from H2O. Here, we present the precise role of uranium-arene δ bonding in intermediates of the catalytic cycle, as well as details of the atypical two-electron oxidative addition of H2O to the trivalent uranium catalyst. Both aspects were explored by synthesizing mid- and high-valent uranium-oxo intermediates and by performing comparative studies with a structurally related complex that cannot engage in δ bonding. The redox activity of the arene anchor and a covalent δ-bonding interaction with the uranium ion during H2 formation were supported by density functional theory analysis. Detailed insight into this catalytic system may inspire the design of ligands for new uranium catalysts.

Kinetic Investigation of Homogeneous H(2)-D(2) Equilibration Catalyzed by Pt-Au Cluster Compounds. Characterization of the Cluster [(H)Pt(AuPPh(3))(9)](NO(3))(2).

Science.gov (United States)

Rubinstein, Leon I.; Pignolet, Louis H.

1996-11-06

The new Pt-Au hydrido cluster compound [(H)Pt(AuPPh(3))(9)](NO(3))(2) (3) has been synthesized and characterized by NMR, FABMS, and single-crystal X-ray diffraction [triclinic, P&onemacr;, a = 17.0452(1) Å, b = 17.4045(2) Å, c = 55.2353(1) Å, alpha = 89.891(1) degrees, beta = 85.287(1) degrees, gamma = 75.173(1) degrees, V = 15784.0(2) Å(3), Z = 4 (two molecules in asymmetric unit), residual R = 0.089 for 45 929 observed reflections and 3367 variables, Mo Kalpha radiation]. The Pt(AuP)(9) core geometry is a distorted icosahedron with three vertices vacant. The Pt-Au, Au-Au, and Au-P distances are within the normal ranges observed in other Pt-Au clusters. This cluster is a catalyst for H(2)-D(2) equilibration in homogeneous solution phase and has been used in a general mechanistic study of this reaction catalyzed by Pt-Au clusters. We previously proposed that a key step in the mechanism for catalytic H(2)-D(2) equilibration is the dissociation of a PPh(3) ligand to give a cluster with an open Au site for bonding of H(2) or D(2). This was based on qualitative observations that PPh(3) inhibited the rate of HD production with [Pt(AuPPh(3))(8)](NO(3))(2) (1) as catalyst. In order to test this hypothesis, phosphine inhibition (on the rate of HD production) and phosphine ligand exchange kinetic experiments were carried out with [(H)(PPh(3))Pt(AuPPh(3))(7)](NO(3))(2) (2) and 3. In this paper we show that the rate constant for phosphine dissociation determined from the PPh(3) inhibition rate study of H(2)-D(2) equilibration with cluster 2 is nearly identical to the rate constant for dissociative phosphine ligand exchange. The slower rate for H(2)-D(2) equilibration observed with 3 compared with 2 (5.5 x 10(-3) vs 7.7 x 10(-2) turnover s(-1)) is explained by its smaller rate constant for phosphine dissociation (2.8 x 10(-5) vs 2.9 x 10(-4) s(-1)). The fact that clusters 2 and 3 show similar kinetic behaviors suggests that the PPh(3) dissociation step in the catalytic H(2

Model analysis of molecular conformations in terms of weak interactions between non bonded atoms

International Nuclear Information System (INIS)

Lombardi, E.

1988-01-01

The aim of the present paper is to establish a reliable basis for the evaluation of stable conformations and rotational barriers for molecules, with possible applications to systems of biological interest. It is proceeded in two steps: first, the effect of chemical environment on orbitals of a given atom is studied for diatomic units, adopting a valence-bond approach and considering, as prototypes, the two simplest series of diatomic molecules with one valence electron each, i.e. the alkali diatomics and the alkali hydrides. In the model, the orbital of the hydrogen atom by a simple (''1S'') gaussian function, the valence orbital of an alkali atom by a function (r 2 -a 2 ) times a simple gaussian (''2S'' gaussian). Dissociation energies D e and equilibrium distances R e are calculated using a scanning procedure. Agreement with experiment is quantitative for the alkali diatomics. For alkali hydrides, good agreement is obtained only if validity of a rule β e R e =constant, for the two atoms separately, is postulated; β e is the characteristic parameter of a ''1S'' gaussian (hydrogen) or a ''2S'' gaussian (alkali atom) function. In a second step, the authors assume validity of the same rule in conformational analysis for any single bonded A-B molecule with A=C, O, N, P, Si, Ge and B=H, or a halogen atom. Gauge β e values for H, F and C are obtained by fitting experimental rotational barriers in C 2 H 6 , C 2 F 6 and C 3 H 8 . Stable conformation of, and barriers to rotation in, ethane-like rotors are determined, applying first-order exchange perturbation theory, in terms of two- and many-center exchange interactions in cluster of non-bonded atoms. Some 60 molecules are analyzed. Agreement with experiments is strikngly good except for a few systematic deviation. Reasons for such discrepancies are discussed

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.

Controlling the structure of sequence-defined poly(phosphodiester)s for optimal MS/MS reading of digital information.

Science.gov (United States)

Amalian, J-A; Al Ouahabi, A; Cavallo, G; König, N F; Poyer, S; Lutz, J-F; Charles, L

2017-11-01

Digital polymers are monodisperse chains with a controlled sequence of co-monomers, defined as letters of an alphabet, and are used to store information at the molecular level. Reading such messages is hence a sequencing task that can be efficiently achieved by tandem mass spectrometry. To improve their readability, structure of sequence-controlled synthetic polymers can be optimized, based on considerations regarding their fragmentation behavior. This strategy is described here for poly(phosphodiester)s, which were synthesized as monodisperse chains with more than 100 units but exhibited extremely complex dissociation spectra. In these polymers, two repeating units that differ by a simple H/CH 3 variation were defined as the 0 and 1 bit of the ASCII code and spaced by a phosphate moiety. They were readily ionized in negative ion mode electrospray but dissociated via cleavage at all phosphate bonds upon collisional activation. Although allowing a complete sequence coverage of digital poly(phosphodiester)s, this fragmentation behavior was not efficient for macromolecules with more than 50 co-monomers, and data interpretation was very tedious. The structure of these polymers was then modified by introducing alkoxyamine linkages at appropriate location throughout the chain. A first design consisted of placing these low dissociation energy bonds between each monomeric bit: while cleavage of this sole bond greatly simplified MS/MS spectra, efficient sequencing was limited to chains with up to about 50 units. In contrast, introduction of alkoxyamine bonds between each byte (i.e. a set of eight co-monomers) was a more successful strategy. Long messages (so far, up to 8 bytes) could be read in MS 3 experiments, where single-byte containing fragments released during the first activation stage were further dissociated for sequencing. The whole sequence of such byte-truncated poly(phosphodiester)s could be easily re-constructed based on a mass tagging system which permits

A storage ring study of dissociative excitation and recombination of D3+

International Nuclear Information System (INIS)

Le Padellec, A.; Larson, Aa.; Semaniak, J.; Stroemholm, C.; Larsson, M.; Rosen, S.; Danared, H.; Peterson, J.R.

1998-01-01

Dissociative recombination and excitation of D 3 + have been studied in CRYRING, a heavy-ion storage ring at the Manne Siegbahn laboratory at Stockholm University. The measured cross section for dissociative recombination was used to deduce a 300 K rate constant of 2.7 x 10 -8 cm 3 s -1 . This is a factor of four smaller than the corresponding value for H 3 + measured earlier in CRYRING. Dissociative excitation into both the D and 2D channels (D + D or D 2 ) were studied. The 2D channel occurs at energies below threshold for the ion's dissociative states, which indicates that resonant enhanced dissociative excitation via autoionizing resonances takes place. No measurable effect could be observed for the dissociative recombination cross sections when an electric field of 30 V/cm was applied to the electron-ion interaction region. (orig.)

Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

Science.gov (United States)

Corbin, Joshua R; Schomaker, Jennifer M

2017-04-13

Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

Formation of Irreversible H-bonds in Cellulose Materials

Science.gov (United States)

Umesh P. Agarwal; Sally A. Ralph; Rick S. Reiner; Nicole M. Stark

2015-01-01

Understanding of formation of irreversible Hbonds in cellulose is important in a number of fields. For example, fields as diverse as pulp and paper and enzymatic saccharification of cellulose are affected. In the present investigation, the phenomenon of formation of irreversible H-bonds is studied in a variety of celluloses and under two different drying conditions....

Laser ionization and dissociation of hydrogen

International Nuclear Information System (INIS)

Buck, J.D.

1987-01-01

Experiments undertaken to further characterize the spectroscopic and photophysical properties of some important excited singlet states of molecular hydrogen and its deuterium isotopes are described. Attention was centered on high vibrational levels of the B, C, and B' states within about 1000 cm -1 of the second dissociation limit. A double-resonance excitation scheme was needed to access levels with a large average bond distance from the ground state. Two-photon absorption of tunable uv-laser radiation-pumped ground-state hydrogen molecules into selected rovibronic levels of the metastable EF double-minimum electronic state. A second tunable near-IR probe laser was scanned to generate ions by resonant multiphoton ionization, where the resonant levels were provided by B, C, B', and other levels near the dissociation limit. New information was obtained regarding line shapes and intensities. Time-of-flight ion mass selection permitted observation of additional excitation channels with dissociation superimposed on the ionization process to produce protons

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 < TPSS < BLYP < revPBE < BP86 < PBE ≈ PW91. The orbital interactions ΔEorb, in all studied compounds [Etbnd 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.

Emission of Lyman α radiation in H2 + H*(2s) collisions at thermal energies

International Nuclear Information System (INIS)

Stern, B.

1991-01-01

A previously-published study of the thermal-energy collision between H 2 and metastable H*(2s), which could lead to the emission of Lyman α radiation, is reconsidered to take into account possible polarization effects. The total was function of the system is expanded in terms of the molecular states of the intermediate complex H 2 * , which constitute the minimal basis of the four adiabatic states dissociating into H 2 + H*(n=2) where they are normally degenerate in energy. The results of the calculation show the existence, between three of those states, of average values of the separation distance R (R ≅ 10 atomic units) of long range (ΔR ≅ 2 au) electronic interactions which depend on the geometric form of the H 2 * molecule. From the molecular data the hypothesis of no longer considering H 2 with H*(2s) as a rigid rotator is postulated and justified, after a purely quantum mechanical treatment of the radial equations. The mean ratio of the (oscillating) polarization angular differential cross sections tot he elastic ones is found important (> ∼ 1/10). The inelastic phenomena are anticipated to be more marked in the ortho than in the para hydrogen at a low collision energy (75 meV). (15 refs., 2 tabs., 9 figs.)

Wavepacket theory of collisional dissociation in molecules

International Nuclear Information System (INIS)

Kulander, K.

1980-01-01

An explicit integration scheme is used to solve the time dependent Schroedinger equation for wavepackets which model collisions in the collinear H + H 2 system. A realistic LEPS-type potential energy surface is used. Collision energies considered are above the dissociation threshold and probabilities for collision induced dissociation are reported. Also quantum mechanical state-to-state transition probabilities are generated. These results are compared to extensive classical trajectory calculations performed on this same system. The time evolution of the wavepacket densities is studied to understand the dynamics of the collinear collisional dissociation process

Open chain or chemically bonded structure of H2O4: The hydroperoxyl radical dimer

International Nuclear Information System (INIS)

Fitzgerald, G.; Lee, T.J.; Schaefer, H.F. III; Bartlett, R.J.

1985-01-01

The straight chain isomer H--O--O--O--O--H of H 2 O 4 is of considerable current interest in combustion and atmospheric chemistry. Ab initio quantum mechanical methods have been used to study the geometrical structure, energetics, and vibrational frequencies of this species. Double zeta (DZ) and double zeta plus polarization (DZ+P) basis sets have been used in this theoretical study, the latter designated O(9s5p1d/4s2p1d), H(4s1p/2s1p). These basis sets have been employed in conjunction with self--consistent field (SCF)= and configuration interaction (CI) methods, including variationally up to 470 935 configurations. For the straight chain isomer, stationary points of symmetry C/sub 2h/, C/sub i/, and C 1 have been identified, and correspond to Hessian indices 3,1, and 0, respectively. The equilibrium geometry, having no elements of symmetry at all, is relatively unique. The highest level of theory (unlinked cluster corrected DZ+P CI) predicts the straight chain structure of H 2 O 4 to lie slightly lower in total energy than the cyclic two-hydrogen bond isomer

Influence of Background H2O on the Collision-Induced Dissociation Products Generated from [UO2NO3]+

Science.gov (United States)

Van Stipdonk, Michael J.; Iacovino, Anna; Tatosian, Irena

2018-04-01

Developing a comprehensive understanding of the reactivity of uranium-containing species remains an important goal in areas ranging from the development of nuclear fuel processing methods to studies of the migration and fate of the element in the environment. Electrospray ionization (ESI) is an effective way to generate gas-phase complexes containing uranium for subsequent studies of intrinsic structure and reactivity. Recent experiments by our group have demonstrated that the relatively low levels of residual H2O in a 2-D, linear ion trap (LIT) make it possible to examine fragmentation pathways and reactions not observed in earlier studies conducted with 3-D ion traps (Van Stipdonk et al. J. Am. Soc. Mass Spectrom. 14, 1205-1214, 2003). In the present study, we revisited the dissociation of complexes composed of uranyl nitrate cation [UVIO2(NO3)]+ coordinated by alcohol ligands (methanol and ethanol) using the 2-D LIT. With relatively low levels of background H2O, collision-induced dissociation (CID) of [UVIO2(NO3)]+ primarily creates [UO2(O2)]+ by the ejection of NO. However, CID (using He as collision gas) of [UVIO2(NO3)]+ creates [UO2(H2O)]+ and UO2 + when the 2-D LIT is used with higher levels of background H2O. Based on the results presented here, we propose that product ion spectrum in the previous experiments was the result of a two-step process: initial formation of [UVIO2(O2)]+ followed by rapid exchange of O2 for H2O by ion-molecule reaction. Our experiments illustrate the impact of residual H2O in ion trap instruments on the product ions generated by CID and provide a more accurate description of the intrinsic dissociation pathway for [UVIO2(NO3)]+. [Figure not available: see fulltext.

The micellization and dissociation transitions of thermo-, pH- and sugar-sensitive block copolymer investigated by laser light scattering

Directory of Open Access Journals (Sweden)

Y. C. Tang

2012-08-01

Full Text Available A triple-stimuli responsive polymer, poly(3-acrylamidophenylboronic acid-b-poly(N-isopropylacrylamide (PAAPBA-b-PNIPAM, has been synthesized by reversible addition-fragmentation chain transfer polymerization. Temperature, pH, and fructose induced micellization and dissociation transition of block copolymer was investigated by a combination of static and dynamic laser light scattering. PAAPBA-b-PNIPAM copolymer self-assembles into micelles with PAAPBA block as core and PNIPAM as shell in lower pH aqueous solution at room temperature. Increasing the temperature causes the micelle to shrink due to the dehydration of PNIPAM segments at pH 6.2. After the elevation of solution pH from 6.2 to 10.0, the increase in the hydrophilicity of PAAPBA block leads to an expulsion of unimers from micelles. In addition, the fructose addition further enhances the dissociation of micelles. Our experiments demonstrate that the micelle to unimer transition process proceeds via the step-by-step sequential expulsion of individual chains.

First-principles study of molecular NO dissociation on Ir(100) surface

Science.gov (United States)

Erikat, I. A.; Hamad, B. A.; Khalifeh, J. M.

2014-02-01

The dissociation of NO on Ir(100) surface is investigated using density functional theory (DFT). The pathway and transition state (TS) of the dissociation of NO molecule are determined using climbing image nudge elastic band (CI-NEB). The prerequisite state of NO dissociation is determining the most stable sites of the reactant and products. We found that the most energetically stable sites are the hollow for N atom and the bridge for NO molecule as well as O atom. We found that the bending of NO is the first step of the dissociation reaction due to the increase of the back-donation from the d-band of Ir to 2 π ∗ orbital of NO, which causes the weakening of NO bond. The dissociation energy barrier of NO molecule on Ir(100) surface is 0.49 eV.

Response speed of SnO2-based H2S gas sensors with CuO nanoparticles

International Nuclear Information System (INIS)

Chowdhuri, Arijit; Gupta, Vinay; Sreenivas, K.; Kumar, Rajeev; Mozumdar, Subho; Patanjali, P. K.

2004-01-01

CuO nanoparticles on sputtered SnO 2 thin-film surface exhibit a fast response speed (14 s) and recovery time (61 s) for trace level (20 ppm) H 2 S gas detection. The sensitivity of the sensor (S∼2.06x10 3 ) is noted to be high at a low operating temperature of 130 deg. C. CuO nanoparticles on SnO 2 allow effective removal of excess adsorbed oxygen from the uncovered SnO 2 surface due to spillover of hydrogen dissociated from the H 2 S-CuO interaction

Electron-hole pair effects in methane dissociative chemisorption on Ni(111)

Energy Technology Data Exchange (ETDEWEB)

Luo, Xuan; Jiang, Bin, E-mail: bjiangch@ustc.edu.cn [Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Juaristi, J. Iñaki [Centro de Física de Materiales CFM/MPC(CSIC-UPV/EHU), P. Manuel de Lardizabal 5, 20018 San Sebastián (Spain); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastián (Spain); Departamento de Física de Materiales, Facultad de Químicas, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080 San Sebastián (Spain); Alducin, Maite [Centro de Física de Materiales CFM/MPC(CSIC-UPV/EHU), P. Manuel de Lardizabal 5, 20018 San Sebastián (Spain); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastián (Spain); Guo, Hua [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

2016-07-28

The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitations on the dissociative chemisorption of CH{sub 4}/CH{sub 3}D/CHD{sub 3} on Ni(111). The energy dissipation induced by surface electron-hole pair excitations is modeled as a friction force introduced in the generalized Langevin equation, in which the independent atomic friction coefficients are determined within the local-density friction approximation. Quasi-classical trajectory calculations for CH{sub 4}/CH{sub 3}D/CHD{sub 3} have been carried out on a recently developed twelve-dimensional potential energy surface. Comparing the dissociation probabilities obtained with and without friction, our results clearly indicate that the electron-hole pair effects are generally small, both on absolute reactivity of each vibrational state and on the mode specificity and bond selectivity. Given similar observations in both water and methane dissociation processes, we conclude that electron-hole pair excitations would not play an important role as long as the reaction is direct and the interaction time between the molecule and metal electrons is relatively short.

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.

Mechanisms for the Production of Fast HI from Dissociation of H2 on Saturn

Science.gov (United States)

Liu, Xianming; Johnson, Paul; Malone, Charles; Young, Jason; Kanik, Isik; Shemansky, Donald

2010-05-01

Images of the Saturn system obtained by the Cassini UVIS at a pixel resolution of 0.1 × 0.1 Saturn radii (Rs) reveal atomic hydrogen in ballistic and escaping trajectories sourced at the top of the thermosphere, primarily in the southern sunlit hemisphere. The main feature in the image is a distinctive H Lyman-α plume structure with FWHM of 0.56 Rs at the exobase sub-solar limb at ~ -13.5° latitude constituting the core of the distributed outward flow of atomic hydrogen from the sunlit hemisphere, with a counterpart on the anti-solar side peaking near the equator above the exobase limb. The structure of the image indicates that part of the out-flowing population is sub-orbital and re-enters the thermosphere in ~ 5 hour time scale. A larger and more broadly distributed component fills the magnetosphere to beyond 45 Rs in the orbital plane and 20 Rs latitudinally above and below the plane in an asymmetric distribution in local time. Molecular hydrogen emission in extreme and far ultraviolet regions collected with the H Lyman-α into the image mosaic reveals a distinctive resonance property correlated with the atomic hydrogen plume and shows a strong deviation of H2 X 1Σg+ from local thermodynamic equilibrium in the main source region. The inferred approximate globally averaged energy deposition at the top of the thermosphere from the production of the hot atomic hydrogen accounts for the measured atmospheric temperature. Possible processes for the fast atomic hydrogen formation from dissociation of H2 include the excitation of singlet-ungerade states and doubly excited states by photons and electrons, and the excitation of the singlet-gerade and triplet states by electrons, and chemical reactions involving the formation and dissociative recombination of H3+. Based on the available laboratory measurements and quantum mechanics calculations, the assessment of various mechanisms for H2 - H production, especially those producing H atoms with sufficient energy to

Theoretical estimation of pnicogen bonds and hydrogen bonds in small heterocyclic complexes: Red-shifts and blue-shifts ruled by polarization effects

International Nuclear Information System (INIS)

Oliveira, Boaz G.

2014-01-01

Graphical abstract: - Highlights: • This paper definitively discusses the interaction strength. • Analyses of the red-shifts and blue-shift. • Stretch frequencies of the hydrogen bonds and pnicogen bonds in heterocyclic compounds. • Theoretical calculations derived from topological parameters of the Quantum Theory of Atoms in Molecules (QTAIM). • The analysis of the Natural Bond Orbital (NBO) in line with the Bent’s rule of the chemical bonding. - Abstract: The occurrence of pnicogen bonds (N⋯P) and hydrogen bonds (F⋯H or Cl⋯H) in heterocyclic complexes formed by C 2 H 5 N⋯PH 3 , C 2 H 5 N⋯PH 2 F and C 2 H 5 N⋯PH 2 Cl was investigated at the B3LYP/6-311++G(d,p) level of theory. Analysis of the infrared spectra revealed the appearance of both red and blue shifts for the P–H bonds. However, in the case of the P–F and P–Cl bonds only red shifts were observed. The phenomenology of these vibration modes was interpreted on the basis of the QTAIM atomic radii as well as the contributions of the s and p orbitals determined via NBO calculations. The results of this latter investigation are consistent with the rehybridization theory and the Bent rule for chemical bonding. The charge transfer between N and P was determined in order to verify whether these atoms present an acid or base profile upon the formation of the pnicogen bonds

The dissociation constants of the cytostatic bosutinib by nonlinear least-squares regression of multiwavelength spectrophotometric and potentiometric pH-titration data.

Science.gov (United States)

Meloun, Milan; Nečasová, Veronika; Javůrek, Milan; Pekárek, Tomáš

2016-02-20

Potentiometric and spectrophotometric pH-titration of the multiprotic cytostatics bosutinib for dissociation constants determination were compared. Bosutinib treats patients with positive chronic myeloid leukemia. Bosutinib exhibits four protonatable sites in a pH range from 2 to 11, where two pK are well separated (ΔpK>3), while the other two are near dissociation constants. In the neutral medium, bosutinib occurs in the slightly water soluble form LH that can be protonated to the soluble cation LH4(3+). The molecule LH can be dissociated to still difficultly soluble anion L(-). The set of spectra upon pH from 2 to 11 in the 239.3-375.0nm was divided into two absorption bands: the first one from 239.3 to 290.5nm and the second from 312.3 to 375.0nm, which differ in sensitivity of chromophores to a pH change. Estimates of pK of the entire set of spectra were compared with those of both absorption bands. Due to limited solubility of bosutinib the protonation in a mixed aqueous-methanolic medium was studied. In low methanol content of 3-6% three dissociation constants can be reliably determined with SPECFIT/32 and SQUAD(84) and after extrapolation to zero content of methanol they lead to pKc1=3.43(12), pKc2=4.54(10), pKc3=7.56(07) and pKc4=11.04(05) at 25°C and pKc1=3.44(06), pKc2=5.03(08) pKc3=7.33(05) and pKc4=10.92(06) at 37°C. With an increasing content of methanol in solvent the dissociation of bosutinib is suppressed and the percentage of LH3(2+) decreases and LH prevails. From the potentiometric pH-titration at 25°C the concentration dissociation constants were estimated with ESAB pKc1=3.51(02), pKc2=4.37(02), pKc3=7.97(02) and pKc4=11.05(03) and with HYPERQUAD: pKc1=3.29(12), pKc2=4.24(10), pKc3=7.95(07) and pKc4=11.29(05). Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of aromatization of the ring on intramolecular H-bond in 3-hydroxy-4-formylo derivatives of fulvene

Science.gov (United States)

Oziminski, Wojciech P.; Krygowski, Tadeusz M.

2011-06-01

DFT optimization of H-bonded 3-hydroxy-4-formylo derivatives of fulvene aromatized by amino substitution at C6 or by complexation with Li atom was performed using the B3LYP functional together with 6-311+G(d,p) basis set. Several aromaticity indicators (HOMA, NICS, pEDA and Shannon aromaticity) confirm an increase of aromaticity in the sequence: fulvene, 6-aminofulvene, Li-complex with fulvene and in the case of H-bonded 3-hydroxy-4-formylo derivatives, exhibited in the same sequence an increase of H-bond strength estimated by direct comparison of energy for H-bonded and open conformations, as well as by using AIM based electron densities at bond critical point.

Dissociation of ethane by electron impact

International Nuclear Information System (INIS)

Winters, H.F.

1979-01-01

The absolute total dissociation cross section for ethane is reported for electron energies between 10 and 600 eV. A maximum value of 7.6 X 10 -16 cm 2 occurs at 80 eV while the apparent threshold is approximately 10 eV. Dissociative ionization is more probable than dissociation into neutral fragments at all energies except in the threshold region. The data indicates that fragmentation involving methane elimination (e - +C 2 H 6 → CH 4 + CH 2 ) occurs in less than 2% of the dissociative events for 50 < E < 600 eV. Arguments are presented which suggest that some of the lower excited states of ethane are stable against dissociation. (Auth.)

Collision-Induced Dissociation Study of Strong Hydrogen-Bonded Cluster Ions Y-(HF) n (Y=F, O2) Using Atmospheric Pressure Corona Discharge Ionization Mass Spectrometry Combined with a HF Generator.

Science.gov (United States)

Sakamoto, Kenya; Sekimoto, Kanako; Takayama, Mitsuo

2017-01-01

Hydrogen fluoride (HF) was produced by a homemade HF generator in order to investigate the properties of strong hydrogen-bonded clusters such as (HF) n . The HF molecules were ionized in the form of complex ions associated with the negative core ions Y - produced by atmospheric pressure corona discharge ionization (APCDI). The use of APCDI in combination with the homemade HF generator led to the formation of negative-ion HF clusters Y - (HF) n (Y=F, O 2 ), where larger clusters with n ≥4 were not detected. The mechanisms for the formation of the HF, F - (HF) n , and O 2 - (HF) n species were discussed from the standpoints of the HF generator and APCDI MS. By performing energy-resolved collision-induced dissociation (CID) experiments on the cluster ions F - (HF) n ( n =1-3), the energies for the loss of HF from F - (HF) 3 , F - (HF) 2 , and F - (HF) were evaluated to be 1 eV or lower, 1 eV or higher, and 2 eV, respectively, on the basis of their center-of-mass energy ( E CM ). These E CM values were consistent with the values of 0.995, 1.308, and 2.048 eV, respectively, obtained by ab initio calculations. The stability of [O 2 (HF) n ] - ( n =1-4) was discussed on the basis of the bond lengths of O 2 H-F - (HF) n and O 2 - H-F(HF) n obtained by ab initio calculations. The calculations indicated that [O 2 (HF) 4 ] - separated into O 2 H and F - (HF) 3 .

Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

International Nuclear Information System (INIS)

Lichienberger, D.L.

1990-10-01

This quarter has witnessed further progress both in our experimental methods of photoelectron spectroscopy and in our understanding the fundamental relationships between ionization energies and the chemistry of transition metal species. Progress continues on the new gas phase photoelectron spectrometer that combine improved capabilities for HeI/HeII UPS, XPS, and Auger investigations of organometallic molecules. Several measurements have been accomplished this year that were not possible previously. We have published the formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies, and applied the relationships to homonuclear and heteronuclear diatomic molecules, multiple bonds, and metal-ligand bonds. Studies of C-H bond activation have continued with examination of different degrees of Si-H bond addition to metals. the electronic effects of intermolecular interactions have been observed by comparing the ionizations of metal complexes in the gas phase with the ionizations of monolayer solid organometallic films prepared in ultra-high vacuum. The orientations of the molecules have been determined by scanning tunneling microscopy. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C 60 molecule, buckminsterfullerene. Studies of the following complexes are described : Fe, Os, Nb, Mo, Rh, Re, Al, and Mn. 19 refs

A method for measurements of neutral fragments kinetic energies released to a specific dissociation threshold: optical translational spectroscopy

International Nuclear Information System (INIS)

Roney, A.; Frigon, C.; Larzilliere, M.

1999-01-01

The optical translational spectroscopy technique, based on the principles of fast ion beam laser spectroscopy (FIBLAS) and translational spectroscopy, allows the kinetic energies study of neutral fragments released through free dissociation of a neutral molecule. This method presents interesting features such as near-threshold energy measurements and selection of a specific dissociation limit. The fragments resulting from free dissociation (not induced) of neutral molecules, produced by charge exchange processes with a fast ion beam, are probed by laser radiation. Monitoring of the laser-induced fluorescence allows high-resolution spectra due to the kinematic compression of the velocity spread. Measurements of kinetic energies released to the second limit of dissociation H(1s) + H(2l) of H 2 are put forth and compared with those obtained by means of off-axis translational spectroscopy

Reaction paths of phosphine dissociation on silicon (001)

International Nuclear Information System (INIS)

Warschkow, O.; McKenzie, D. R.; Curson, N. J.; Schofield, S. R.; Marks, N. A.; Wilson, H. F.; Radny, M. W.; Smith, P. V.; Reusch, T. C. G.; 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 (PH 3 ) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH 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 2 fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH 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

Effect of pH on dissociation of casein micelles in yak skim milk.

Science.gov (United States)

Yang, M; Zhang, G D; Yang, J T; Sun, D; Wen, P C; Zhang, W B

2018-04-01

The dissociation of yak casein (CN) micelles was evaluated by scanning electron microscopy, particle size, fluorescence properties, and soluble mineral and CN molecule content at pH 4.6 to 8.2. The results showed that the size of CN micelles remained constant with decreasing pH from 8.2 to 5.8 but sharply increased at pH ≤5.4. Casein micelles began to aggregate at pH 5.4, and the serum magnesium, potassium, iron, zinc, copper, and manganese levels had their minimum values at this pH level. During acidification, colloidal calcium phosphate dramatically disassociated from yak CN micelles, but the soluble CN monomer content decreased slightly. During alkalization, the soluble calcium and phosphorus content decreased below pH 6.8 but increased with pH increases from 6.8 to 8.2. However, the soluble CN content increased markedly during alkalization. The emission wavelength of 8-anilino-1-naphthalenesulfonic acid sodium salt fluorescence decreased during both acidification and alkalization from pH 6.6, whereas the opposite was found for intrinsic fluorescence. Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Raman enhancement effect on two-dimensional layered materials: graphene, h-BN and MoS2.

Science.gov (United States)

Ling, Xi; Fang, Wenjing; Lee, Yi-Hsien; Araujo, Paulo T; Zhang, Xu; Rodriguez-Nieva, Joaquin F; Lin, Yuxuan; Zhang, Jin; Kong, Jing; Dresselhaus, Mildred S

2014-06-11

Realizing Raman enhancement on a flat surface has become increasingly attractive after the discovery of graphene-enhanced Raman scattering (GERS). Two-dimensional (2D) layered materials, exhibiting a flat surface without dangling bonds, were thought to be strong candidates for both fundamental studies of this Raman enhancement effect and its extension to meet practical applications requirements. Here, we study the Raman enhancement effect on graphene, hexagonal boron nitride (h-BN), and molybdenum disulfide (MoS2), by using the copper phthalocyanine (CuPc) molecule as a probe. This molecule can sit on these layered materials in a face-on configuration. However, it is found that the Raman enhancement effect, which is observable on graphene, hBN, and MoS2, has different enhancement factors for the different vibrational modes of CuPc, depending strongly on the surfaces. Higher-frequency phonon modes of CuPc (such as those at 1342, 1452, 1531 cm(-1)) are enhanced more strongly on graphene than that on h-BN, while the lower frequency phonon modes of CuPc (such as those at 682, 749, 1142, 1185 cm(-1)) are enhanced more strongly on h-BN than that on graphene. MoS2 demonstrated the weakest Raman enhancement effect as a substrate among these three 2D materials. These differences are attributed to the different enhancement mechanisms related to the different electronic properties and chemical bonds exhibited by the three substrates: (1) graphene is zero-gap semiconductor and has a nonpolar C-C bond, which induces charge transfer (2) h-BN is insulating and has a strong B-N bond, while (3) MoS2 is semiconducting with the sulfur atoms on the surface and has a polar covalent bond (Mo-S) with the polarity in the vertical direction to the surface. Therefore, the different Raman enhancement mechanisms differ for each material: (1) charge transfer may occur for graphene; (2) strong dipole-dipole coupling may occur for h-BN, and (3) both charge transfer and dipole-dipole coupling may

Study of dissociative collisions of hydrogen-line ions by mean of angular and energy distributions

International Nuclear Information System (INIS)

Martinez, H.; Urquijo, J. de; Cisneros, C.; Alvarez, J.

1988-01-01

Angular and energy distribution of fragments produced in a collision, employed in conjunction with the 'step-model' that means excitation and binary dissociation, are used to determine the binding energy of H 3 (D 3 ) and HD + 2 and also to identify the principal channels in the dissociation processes. (A.C.A.S.) [pt

A computational study on the energetics and mechanisms for the dissociative adsorption of SiH{sub x}(x = 1–4) on W(1 1 1) surface

Energy Technology Data Exchange (ETDEWEB)

Lin, Y.H.; Raghunath, P.; Lin, M.C., E-mail: chemmcl@emory.edu

2016-01-30

Graphical abstract: - Highlights: • Behavior of the SiH{sub x} species on the W surface under cat-CVD conditions. • The adsorption and dissociation mechanisms of SiH{sub x}(x = 1–4) species on W(1 1 1) surface. • H-migration to its neighboring W atoms is more favorable compared to H{sub 2} elimination. - Abstract: The adsorption and dissociation mechanisms of SiH{sub x}(x = 1–4) species on W(1 1 1) surface have been investigated by using the periodic density functional theory with the projector-augmented wave approach. The adsorption of all the species on four surface sites: top (T), bridge (B), shallow (S), and deep (D) sites have been analyzed. For SiH{sub 4} on a top site, T-SiH{sub 4(a)}, it is more stable with an adsorption energy of 2.6 kcal/mol. For SiH{sub 3}, the 3-fold shallow site is most favorable with adsorption energy of 46.0 kcal/mol. For SiH{sub 2}, its adsorption on a bridge site is most stable with 73.0 kcal/mol binding energy, whereas for SiH and Si the most stable adsorption configurations are on 3-fold deep sites with very high adsorption energies, 111.8 and 134.7 kcal/mol, respectively. The potential energy surfaces for the dissociative adsorption of all SiH{sub x} species on the W(1 1 1) surface have been constructed using the CINEB method. The barriers for H-atom migration from SiH{sub x(a)} to its neighboring W atoms, preferentially on B-sites, were predicted to be 0.4, 1.0, 4.5 and, 8.0 kcal/mol, respectively, for x = 4, 3, 2, and 1, respectively. The adsorption energy of the H atom on a bridge site on the clean W(1 1 1) surface was predicted to be 65.9 kcal/mol, which was found to be slightly affected by the co-adsorption of SiH{sub x−1} within ± 1 kcal/mol.

Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

Science.gov (United States)

Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

2018-02-16

A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical investigation of the ultrafast dissociation of core-ionized water and uracil molecules immersed in liquid water

Energy Technology Data Exchange (ETDEWEB)

Stia, C.R.; Fojon, O.A. [Instituto de Fisica Rosario - CONICET-Universidad Nacional de Rosario, Rosario (Argentina); Gaigeot, M.P. [Laboratoire Analyse et Modelisation pour la Biologie et l' Environnement, LAMBE, UMR-CNRS 8587, Universite d' Evry-Val-d' Essonne, 91 - Evry (France); Institut Universitaire de France, 75 - Paris (France); Vuilleumier, R. [Departement de chimie, Ecole Normale Superieure, 75 - Paris (France); Herve du Penhoat, M.A.; Politis, M.F. [Institut de Mineralogie et de Physique des Milieux Condenses, IMPMC, UMR-CNRS 7590, Universite Pierre et Marie Curie, 75 - Paris (France)

2010-10-15

We present a series of ab initio density functional based calculations of the fragmentation dynamics of core-ionized biomolecules. The computations are performed for pure liquid water, aqueous and isolated Uracil. Core ionization is described by replacing the 1s{sup 2} pseudopotential of one atom of the target molecule (C, N or O) with a pseudopotential for a 1s{sup 1} core-hole state. Our results predict that the dissociation of core-ionized water molecules may be reached during the lifetime of inner-shell vacancy (less than 10 fs), leading to OH bond breakage as a primary outcome. We also observe a second fragmentation channel in which total Coulomb explosion of the ionized water molecule occurs. Fragmentation pathways are found similar for pure water or when the water molecule is in the primary hydration shell of the uracil molecule. In the latter case, the proton may be transferred towards the uracil oxygen atoms. When the core hole is located on the uracil molecule, ultrafast dissociation is only observed in the aqueous environment and for nitrogen-K vacancies, resulting in proton transfers towards the hydrogen-bonded water molecule. (authors)

Microsolvation effect and hydrogen-bonding pattern of taurine-water TA-(H2O)n (n = 1-3) complexes.

Science.gov (United States)

Dai, Yumei; Wang, Yuhua; Huang, Zhengguo; Wang, Hongke; Yu, Lei

2012-01-01

The microsolvation of taurine (TA) with one, two or three water molecules was investigated by a density functional theory (DFT) approach. Quantum theory of atoms in molecules (QTAIM) analyses were employed to elucidate the hydrogen bond (H-bond) interaction characteristics in TA-(H(2)O)(n) (n = 1-3) complexes. The results showed that the intramolecular H-bond formed between the hydroxyl and the N atom of TA are retained in most TA-(H(2)O)(n) (n = 1-3) complexes, and are strengthened via cooperative effects among multiple H-bonds from n = 1-3. A trend of proton transformation exists from the hydroxyl to the N atom, which finally results in the cleavage of the origin intramolecular H-bond and the formation of a new intramolecular H-bond between the amino and the O atom of TA. Therefore, the most stable TA-(H(2)O)(3) complex becomes a zwitterionic complex rather than a neutral type. A many-body interaction analysis showed that the major contributors to the binding energies for complexes are the two-body energies, while three-body energies and relaxation energies make significant contributions to the binding energies for some complexes, whereas the four-body energies are too small to be significant.

MRD-CI potential surfaces using balanced basis sets. IV. The H2 molecule and the H3 surface

International Nuclear Information System (INIS)

Wright, J.S.; Kruus, E.

1986-01-01

The utility of midbond functions in molecular calculations was tested in two cases where the correct results are known: the H 2 potential curve and the collinear H 3 potential surface. For H 2 , a variety of basis sets both with and without bond functions was compared to the exact nonrelativistic potential curve of Kolos and Wolniewicz [J. Chem. Phys. 43, 2429 (1965)]. It was found that optimally balanced basis sets at two levels of quality were the double zeta single polarization plus sp bond function basis (BF1) and the triple zeta double polarization plus two sets of sp bond function basis (BF2). These gave bond dissociation energies D/sub e/ = 4.7341 and 4.7368 eV, respectively (expt. 4.7477 eV). Four basis sets were tested for basis set superposition errors, which were found to be small relative to basis set incompleteness and therefore did not affect any conclusions regarding basis set balance. Basis sets BF1 and BF2 were used to construct potential surfaces for collinear H 3 , along with the corresponding basis sets DZ*P and TZ*PP which contain no bond functions. Barrier heights of 12.52, 10.37, 10.06, and 9.96 kcal/mol were obtained for basis sets DZ*P, TZ*PP, BF1, and BF2, respectively, compared to an estimated limiting value of 9.60 kcal/mol. Difference maps, force constants, and relative rms deviations show that the bond functions improve the surface shape as well as the barrier height

The 1600 Å Emission Bump in Protoplanetary Disks: A Spectral Signature of H2O Dissociation

Science.gov (United States)

France, Kevin; Roueff, Evelyne; Abgrall, Hervé

2017-08-01

The FUV continuum spectrum of many accreting pre-main sequence stars, Classical T Tauri Stars (CTTSs), does not continue smoothly from the well-studied Balmer continuum emission in the NUV, suggesting that additional processes contribute to the short-wavelength emission in these objects. The most notable spectral feature in the FUV continuum of some CTTSs is a broad emission approximately centered at 1600 Å, which has been referred to as the “1600 Å Bump.” The origin of this feature remains unclear. In an effort to better understand the molecular properties of planet-forming disks and the UV spectral properties of accreting protostars, we have assembled archival FUV spectra of 37 disk-hosting systems observed by the Hubble Space Telescope-Cosmic Origins Spectrograph. Clear 1600 Å Bump emission is observed above the smooth, underlying 1100-1800 Å continuum spectrum in 19/37 Classical T Tauri disks in the HST-COS sample, with the detection rate in transition disks (8/8) being much higher than that in primordial or non-transition sources (11/29). We describe a spectral deconvolution analysis to separate the Bump (spanning 1490-1690 Å) from the underlying FUV continuum, finding an average Bump luminosity L(Bump) ≈ 7 × 1029 erg s-1. Parameterizing the Bump with a combination of Gaussian and polynomial components, we find that the 1600 Å Bump is characterized by a peak wavelength λ o = 1598.6 ± 3.3 Å, with FWHM = 35.8 ± 19.1 Å. Contrary to previous studies, we find that this feature is inconsistent with models of H2 excited by electron -impact. We show that this Bump makes up between 5%-50% of the total FUV continuum emission in the 1490-1690 Å band and emits roughly 10%-80% of the total fluorescent H2 luminosity for stars with well-defined Bump features. Energetically, this suggests that the carrier of the 1600 Å Bump emission is powered by Lyα photons. We argue that the most likely mechanism is Lyα-driven dissociation of H2O in the inner disk, r �

The electronic donation and frequency shifts on the YCCH⋯BH4- boron-bonded complexes (Y = H, CH3, CF3 and CCl3)

Science.gov (United States)

Pordeus, Renato Q.; Rego, Danilo G.; Oliveira, Boaz G.

2015-06-01

In this theoretical work, the tetrahydroborate ion (BH4-) was used as proton acceptor in the formation of the YCC-H⋯BH4- complexes (Y = H, CH3, CCl3 and CF3). Using B3LYP/6-311++G(d,p) level of theory, the results of structure corroborate with the analyses of infrared spectra showing that the changes in the bond lengths are in good agreement with the frequency shifts of the HCC-H, H3CCC-H, Cl3CCC-H and F3CCC-H proton donors. Based on the calculations carried out by the Quantum Theory of Atoms in Molecules (QTAIM), the reductions of electronic density corroborate with the red shifts in the frequencies of the C-H bonds. In addition to that, the C-H bonds are polarized because the contributions of s orbital diminish whereas of p increase. In line with this, the variations on the atomic radii computed via QTAIM calculations show that carbon outweigh hydrogen as follows (ΔrC > ΔrH). This scenario is indirectly supported by the Bent's rule of the chemical bonding. Although the interaction energies (corrected with BSSE and ZPE) vary between -19 and -67 kJ mol-1, these complexes interact without covalent character.

Cleavage of thymine N3-H bonds by low-energy electrons attached to base π* orbitals

International Nuclear Information System (INIS)

Theodore, Magali; Sobczyk, Monika; Simons, Jack

2006-01-01

In this work, we extend our earlier studies on single strand break (SSB) formation in DNA to consider the possibility of cleaving a thymine N 3 -H bond to generate a nitrogen-centered anion and a hydrogen radical which might proceed to induce further bond cleavages. In earlier studies, we considered SSBs induced by low-energy electrons that attach to DNA bases' π* orbitals or to phosphate P=O π* orbitals to cleave sugar-phosphate C-O bonds or base-sugar N 1 -C bonds. We also studied the effects of base π-stacking on the rates of such bond cleavages. To date, our results suggest that sugar-phosphate C-O bonds have the lowest barriers to cleavage, that attachment of electrons with energies below 2 eV most likely occurs at the base π* orbitals, that electrons with energy above 2 eV can also attach to phosphate P=O π* orbitals, and that base π stacking has a modest but slowing effect on the rates of SSB formation. However, we had not yet examined the possibility that base N 3 -H bonds could rupture subsequent to base π* orbital capture. In the present work, the latter possibility is considered and it is found that the barrier to cleavage of the N 3 -H bond in thymine is considerably higher than for cleaving sugar-phosphate C-O bonds, so our prediction that SSB formation is dominated by C-O bond cleavage remains intact

C-H Bond Functionalization via Hydride Transfer: Direct Coupling of Unactivated Alkynes and sp3 C-H Bonds Catalyzed by Platinum Tetraiodide

Science.gov (United States)

Vadola, Paul A.; Sames, Dalibor

2010-01-01

We report a catalytic intramolecular coupling between terminal unactivated alkynes and sp3 C-H bonds via the through-space hydride transfer (HT-cyclization of alkynes). This method enables one-step preparation of complex heterocyclic compounds by α-alkenylation of readily available cyclic ethers and amines. We show that PtI4 is an effective Lewis acid catalyst for the activation of terminal alkynes for the hydride attack and subsequent C-C bond formation. In addition, we have shown that the activity of neutral platinum salts (PtXn) can be modulated by the halide ligands. This modulation in turn allows for fine-tuning of the platinum center reactivity to match the reactivity and stability of selected substrates and products. PMID:19852462

Dissociative Photoionization of the Elusive Vinoxy Radical.

Science.gov (United States)

Adams, Jonathan D; Scrape, Preston G; Lee, Shih-Huang; Butler, Laurie J

2017-08-24

These experiments report the dissociative photoionization of vinoxy radicals to m/z = 15 and 29. In a crossed laser-molecular beam scattering apparatus, we induce C-Cl bond fission in 2-chloroacetaldehyde by photoexcitation at 157 nm. Our velocity measurements, combined with conservation of angular momentum, show that 21% of the C-Cl photofission events form vinoxy radicals that are stable to subsequent dissociation to CH 3 + CO or H + ketene. Photoionization of these stable vinoxy radicals, identified by their velocities, which are momentum-matched with the higher-kinetic-energy Cl atom photofragments, shows that the vinoxy radicals dissociatively photoionize to give signal at m/z = 15 and 29. We calibrated the partial photoionization cross section of vinoxy to CH 3 + relative to the bandwidth-averaged photoionization cross section of the Cl atom at 13.68 eV to put the partial photoionization cross sections on an absolute scale. The resulting bandwidth-averaged partial cross sections are 0.63 and 1.3 Mb at 10.5 and 11.44 eV, respectively. These values are consistent with the upper limit to the cross section estimated from a study by Savee et al. on the O( 3 P) + propene bimolecular reaction. We note that the uncertainty in these values is primarily dependent on the signal attributed to C-Cl primary photofission in the m/z = 35 (Cl + ) time-of-flight data. While the value is a rough estimate, the bandwidth-averaged partial photoionization cross section of vinoxy to HCO + calculated from the signal at m/z = 29 at 11.53 eV is approximately half that of vinoxy to CH 3 + . We also present critical points on the potential energy surface of the vinoxy cation calculated at the G4//B3LYP/6-311++G(3df,2p) level of theory to support the observation of dissociative ionization of vinoxy to both CH 3 + and HCO + .

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.

Theoretical aspects of methyl acetate and methanol activation on MgO(100) and (501) catalyst surfaces with application in FAME production

Energy Technology Data Exchange (ETDEWEB)

Man, Isabela-Costinela, E-mail: isabela.man@g.unibuc.ro [University of Bucharest, Faculty of Chemistry, Department of Organic Chemistry, Biochemistry and Catalysis, 4-12 Regina Elisabeta Av., S3, 030018 Bucharest (Romania); Romanian Academy, ‘C.D. Nenitzescu’ Center of Organic Chemistry, 202B Spl. Independentei, 060023 Bucharest (Romania); Soriga, Stefan Gabriel [University Politehnica of Bucharest, Centre for Technology Transfer in the Process Industries, 1, Gh. Polizu Street, Building A, Room A056, RO-011061 Bucharest (Romania); Parvulescu, Vasile [University of Bucharest, Faculty of Chemistry, Department of Organic Chemistry, Biochemistry and Catalysis, 4-12 Regina Elisabeta Av., S3, 030018 Bucharest (Romania)

2017-01-15

Highlights: • Energetics of C−O and C−H bond dissociation and formation of MeOAc on MgO(100) indicate that the bond formations are favorable. • Energetics of C−O and C−H bond dissociation and formation of MeOAc on MgO(501) indicate that the C−O bond dissociation and C−H bond formations are favorable. • The coadsorbed MeOH facilitate O−H bond dissociation of MeOH compared to isolated molecule. • Provide further understanding of reactivity of MgO surfaces with application in transesterification and interesterification reactions. - Abstract: Density functional theory (DFT) calculations were carried out to study the activation of methyl acetate and methanol on MgO(100) and MgO(501) surfaces and integrated in the context of transesterification, interesterification and glycerolysis reactions used in biodiesel industry. First results indicate the importance of including of dispersion forces in the calculations. On MgO(100) the reverse reactions steps of C−O and C−H dissociations and on MgO(501) the same reverse reaction step of C−H dissociations of methyl acetate are energetically favorable, while the dissociation of C−O bond into methoxide and acetate fragments on the edge of MgO(501) was found to be exothermic with a low activation energy. For methanol, the dissociation of O−H bond on MgO(100) surface in the presence of the second coadsorbed methanol molecule becomes more energetically favoured compared to the isolated molecule, due to the fact that the methoxide fragment is stabilized by intermolecular hydrogen bonding. This is reflected by the decrease of the activation energy of the forward reaction step and the increase of the activation energy of the backward reaction step, increasing the probability to have dissociated molecules among the undissociated ones. These results represent a step forward for better understanding from atomistic point of view the paths of these reactions on these surfaces for the corresponding catalytic

A Direct Proof of the Resonance-Impaired Hydrogen Bond (RIHB) Concept.

Science.gov (United States)

Lin, Xuhui; Wu, Wei; Mo, Yirong

2018-01-24

The concept of resonance-enhanced hydrogen bond (RAHB) has been widely accepted and applied as it highlights the positive impact of π-conjugation on intramolecular H-bonds. However, electron delocalization is directional and there is a possibility that π-resonance goes from the H-bond acceptor to the H-bond donor, leading to a negative impact on H-bonds. Here we used the block-localized wavefunction (BLW) method which is a variant of ab initio valence bond (VB) theory and able to derive strictly electron-localized structures self-consistently, to quantify the interplay between H-bond and π-resonance in the terms of geometry, energetics and spectral properties. The comparison of geometrical optimizations with and without π-resonance shows that conjugation can indeed either enhance or weaken intramolecular H-bonds. We further experimented with various substituents attached to either the H-bond acceptor and/or H-bond donor side(s) to tune the H-bonding strength in both directions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

International Nuclear Information System (INIS)

Lichtenberger, D.L.

1991-10-01

The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of (η 5 -C 5 H 4 X)Rh(CO) 2 complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C 60 molecule, buckminsterfullerene, and its interaction with a metal surface. The high-resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C 60 reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface. 21 refs

Direct α-C-H bond functionalization of unprotected cyclic amines

Science.gov (United States)

Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel

2018-02-01

Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

Isotope and Electric Field Effects in Dissociative Recombination of D3+

International Nuclear Information System (INIS)

Larsson, M.; Rosen, S.; Danared, H.; Larson, A.; Le Padellec, A.; Semaniak, J.; Stroemholm, C.; Peterson, J.R.

1997-01-01

The cross section for dissociative recombination of vibrationally cold D 3 + has been measured at the ion storage ring CRYRING. The rate constant at 300K, α=2.7x10 -8 cm 3 s -1 , is a factor of 4.3 smaller than the corresponding value for H 3 + measured earlier in CRYRING. An electric field of 30V/cm was introduced in the electron-ion interaction region. This had no measurable effect on the dissociative recombination cross section. This suggests that the cross sections measured in storage rings for H 3 + and its isotopic variants can be directly compared with theoretical results once such results become available. copyright 1997 The American Physical Society

D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

Science.gov (United States)

Foustoukos, Dionysis I.; Mysen, Bjorn O.

2012-06-01

A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the

Effect of pH and dissociation on the fate and exposure of ionizable chemicals

DEFF Research Database (Denmark)

Franco, Antonio; Trapp, Stefan

2010-01-01

Ionizable organic chemicals comprise an important fraction of pharmaceuticals, pesticides as well as industrial chemicals. It has been estimated that 33% of the preregistered REACH substances is mostly ionized at pH 7. To extend the appliccability of existing exposure models, a Multimedia Activity...... parameters. The sensitivity analysis showed that the parameters describing ionization, pH and the dissociation constant (pKa), are among the most sensitive model parameters. The uncertainty analysis, however, indicated that these parameters are not the major source of uncertainty, which statistically...... and sediments. In most cases, the uncertainty of PECs and of persistance is largely explained by the uncertainty of (bio)degradation rates, which may be caused by model assumptions, experimental or estimation errors or by the environmental variability, including the effect of pH....

Optical observations of molecular dissociation in thin foils

International Nuclear Information System (INIS)

Berry, H.G.; Gay, T.J.; Brooks, R.L.

1981-01-01

We have measured the intensity and polarizations of light emitted from atomic excited states of dissociated molecular ions. Using HeH + projectiles, we have observed factors of 1-5 enhancements of the light from n=3, sup(1,3)P,D states of He I and some He II and H I emissions. Observations of Lyman alpha emission after dissociation of H 2 + and H 3 + show rapid variations in light yield for small internuclear separations at the foil surface. (author)

A quantitative relationship for the shock sensitivities of energetic compounds based on X-NO(2) (X=C, N, O) bond dissociation energy.

Science.gov (United States)

Li, Jinshan

2010-08-15

The ZPE-corrected X-NO(2) (X=C, N, O) bond dissociation energies (BDEs(ZPE)) of 11 energetic nitrocompounds of different types have been calculated employing density functional theory methods. Computed results show that using the 6-31G** basis set the UB3LYP calculated BDE(ZPE) is less than the UB3P86. For these typical energetic nitrocompounds the shock-initiated pressure (P(98)) is strongly related to the BDE(ZPE) indeed, and a polynomial correlation of ln(P(98)) with the BDE(ZPE) has been established successfully at different density functional theory levels, which provides a method to address the shock sensitivity problem. Copyright 2010 Elsevier B.V. All rights reserved.

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.

Charge-Shift Corrected Electronegativities and the Effect of Bond Polarity and Substituents on Covalent-Ionic Resonance Energy.

Science.gov (United States)

James, Andrew M; Laconsay, Croix J; Galbraith, John Morrison

2017-07-13

Bond dissociation energies and resonance energies for H n A-BH m molecules (A, B = H, C, N, O, F, Cl, Li, and Na) have been determined in order to re-evaluate the concept of electronegativity in the context of modern valence bond theory. Following Pauling's original scheme and using the rigorous definition of the covalent-ionic resonance energy provided by the breathing orbital valence bond method, we have derived a charge-shift corrected electronegativity scale for H, C, N, O, F, Cl, Li, and Na. Atomic charge shift character is defined using a similar approach resulting in values of 0.42, 1.06, 1.43, 1.62, 1.64, 1.44, 0.46, and 0.34 for H, C, N, O, F, Cl, Li, and Na, respectively. The charge-shift corrected electronegativity values presented herein follow the same general trends as Pauling's original values with the exception of Li having a smaller value than Na (1.57 and 1.91 for Li and Na respectively). The resonance energy is then broken down into components derived from the atomic charge shift character and polarization effects. It is then shown that most of the resonance energy in the charge-shift bonds H-F, H 3 C-F, and Li-CH 3 and borderline charge-shift H-OH is associated with polarity rather than the intrinsic atomic charge-shift character of the bonding species. This suggests a rebranding of these bonds as "polar charge-shift" rather than simply "charge-shift". Lastly, using a similar breakdown method, it is shown that the small effect the substituents -CH 3 , -NH 2 , -OH, and -F have on the resonance energy (<10%) is mostly due to changes in the charge-shift character of the bonding atom.

Reactive pulsed laser deposition of Cu2ZnSnS4 thin films in H2S

International Nuclear Information System (INIS)

Surgina, G.D.; Zenkevich, A.V.; Sipaylo, I.P.; Nevolin, V.N.; Drube, W.; Teterin, P.E.; Minnekaev, M.N.

2013-01-01

Cu 2 ZnSnS 4 (CZTS) thin films have been grown by reactive pulsed laser deposition in H 2 S atmosphere, combining the alternate ablation from the metallic (Cu) and alloyed (Zn x Sn) targets at room temperature. The morphological, structural and optical properties of as grown CZTS thin films with varying compositions as well as upon annealing in N 2 atmosphere are investigated by Rutherford backscattering spectrometry, X-ray diffraction, Raman spectroscopy and optical spectrophotometry. The chemical bonding in the “bulk” of the CZTS films is elucidated via hard X-ray photoemission spectroscopy measurements. The formation of the good quality stoichiometric polycrystalline CZTS films is demonstrated upon optimization of the growth parameters. - Highlights: ► The new method of Cu 2 ZnSnS 4 (CZTS) thin films growth in H 2 S was realized. ► CZTS films were grown by pulsed laser deposition from Cu and alloyed Zn–Sn targets. ► The effect of the processing parameters on the CZTS properties was investigated. ► The chemical bonding in the “bulk” of CZTS films was studied

Elastic and proton dissociative J/ψ photoproduction at low Wγp with the H1 detector at HERA

International Nuclear Information System (INIS)

Huber, Florian

2013-02-01

Elastic and proton dissociative photoproduction of J/ψ mesons is measured with the H1 detector at the HERA electron proton collider in the photon virtuality phase space of Q 2 2 . Two data sets are analysed, one measured with a nominal proton beam energy of 920 GeV, corresponding to an ep centre of mass energy of 318 GeV and one recorded with a reduced beam energy of 460 GeV, corresponding to an ep centre of mass energy of 225 GeV. The combination of the two data sets allow to perform the J/ψ measurement with central tracks in an extended kinematic phase space in a photon proton centre of mass energy range of 20 GeV γp -1 and 10.8 pb -1 , respectively, corresponding to more than two times the statistics used in previous H1 analyses. Due to an online selection purely based on tracks both leptonic decay channels J/ψ→ee and J/ψ→μμ are available for the analysis. Elastic (γp→ J/ψp) and proton dissociative (γp→ J/ψY) differential γp cross sections are determined in a simultaneous measurement as function of the squared momentum transfer at the proton vertex t and as function of W γp by means of an unfolding procedure, taking not only all bin correlations into account, but also the correlation between the elastic and proton dissociative process. The obtained elastic and proton dissociative differential cross sections are analysed in a simultaneous fit, taking the full statistical covariance matrices and systematic uncertainty sources into account.

Dissociative electron attachment to vibrationally excited H2 molecules involving the 2Σg+ resonant Rydberg electronic state

International Nuclear Information System (INIS)

Celiberto, R.; Janev, R.K.; Wadehra, J.M.; Tennyson, J.

2012-01-01

Graphical abstract: Dissociative electron attachment cross sections as a function of the incident electron energy and for the initial vibration levels v i = 0–5, 10 of the H 2 molecule. Highlights: ► We calculated electron–hydrogen dissociative attachment cross sections and rates coefficients. ► Collision processes occurring through a resonant Rydberg state are considered. ► Cross sections and rates were obtained for vibrationally excited hydrogen molecules. ► The cross sections exhibit pronounced oscillatory structures. ► A comparison with the process involving the electron–hydrogen resonant ground state is discussed. - Abstract: Dissociative electron attachment cross sections (DEA) on vibrationally excited H 2 molecule taking place via the 2 Σ g + Rydberg-excited resonant state are studied using the local complex potential (LCP) model for resonant collisions. The cross sections are calculated for all initial vibrational levels (v i = 0–14) of the neutral molecule. In contrast to the previously noted dramatic increase in the DEA cross sections with increasing v i , when the process proceeds via the X 2 Σ u + shape resonance of H 2 , for the 2 Σ g + Rydberg resonance the cross sections increase only gradually up to v i = 3 and then decrease. Moreover, the cross sections for v i ⩾ 6 exhibit pronounced oscillatory structures. A discussion of the origin of the observed behavior of calculated cross sections is given. The DEA rate coefficients for all v i levels are also calculated in the 0.5–1000 eV temperature range.

Activation of C-H bond in methane by Pd atom from the bonding evolution theory perspective.

Science.gov (United States)

Nizovtsev, Anton S

2013-08-15

We report detailed study focused on the electron density redistribution during the simple oxidative addition reaction being the crucial stage of various catalytic processes. The bonding evolution theory based on the electron localization function and Thom's catastrophe theory shows that activation of methane's C-H bond by Pd atom consist of six elementary steps. The important feature revealed is the pronounced reorganization of Pd's outer core maxima corresponding to N-shell electrons of metal. Electronic rearrangements identified in this model reaction are likely to be the case in the more complex reactions of the same type involving transition metal compounds and, in principle, can be observed by modern ultrafast spectroscopy and diffraction techniques. Copyright © 2013 Wiley Periodicals, Inc.

Far-UV photochemical bond cleavage of n-amyl nitrite: bypassing a repulsive surface.

Science.gov (United States)

Minitti, Michael P; Zhang, Yao; Rosenberg, Martin; Brogaard, Rasmus Y; Deb, Sanghamitra; Sølling, Theis I; Weber, Peter M

2012-01-19

We have investigated the deep-UV photoinduced, homolytic bond cleavage of amyl nitrite to form NO and pentoxy radicals. One-color multiphoton ionization with ultrashort laser pulses through the S(2) state resonance gives rise to photoelectron spectra that reflect ionization from the S(1) state. Time-resolved pump-probe photoionization measurements show that upon excitation at 207 nm, the generation of NO in the v = 2 state is delayed, with a rise time of 283 (16) fs. The time-resolved mass spectrum shows the NO to be expelled with a kinetic energy of 1.0 eV, which is consistent with dissociation on the S(1) state potential energy surface. Combined, these observations show that the first step of the dissociation reaction involves an internal conversion from the S(2) to the S(1) state, which is followed by the ejection of the NO radical on the predissociative S(1) state potential energy surface.

DFT simulation on H2 adsorption over Ni-decorated defective h-BN nanosheets

Science.gov (United States)

Zhou, Xuan; Chu, Wei; Zhou, Yanan; Sun, Wenjing; Xue, Ying

2018-05-01

Nickel doped defective h-BN nanosheets and their potential application on hydrogen storage were explored by density functional theory (DFT) calculation. Three types of defective h-BN (SW defect, VB and VN substrates) were modeled. In comparison with the SW defect, the B or N vacancy can improve the interaction between Ni atom and h-BN nanosheet strikingly. Furthermore, the Ni-doped SW defect sheet shows chemisorption on H2 molecules, and the Hsbnd H bond is partially dissociated. While on the VB sheet, Ni adatom interacts with H2 in the range of physisorption. However, the Ni-functionalized VN sheet exhibits a desirable adsorption on H2, and the corresponding energy varies from -0.40 to -0.51 eV, which is favorable for H2 adsorption and release at ambient conditions. As a result, the VN substrate is expected to a desirable support for H2 storage. Our work provides an insight into H2 storage on Ni-functionalized defective h-BN monolayer.

Competition between weak OH···π and CH··O hydrogen bonds: THz spectroscopy of the C2H2—H2O and C2H4—H2O complexes

DEFF Research Database (Denmark)

Andersen, Jonas; Heimdal, Jimmy; Nelander, B.

2017-01-01

an intermolecular CH⋯O hydrogen-bonded configuration of C2v symmetry with the H2O subunit acting as the hydrogen bond acceptor. The observation and assignment of two large-amplitude donor OH librational modes of the C2H4—H2O complex at 255.0 and 187.5 cm−1, respectively, confirms an intermolecular OH⋯π hydrogen...

Thermodynamic analysis of the Cu2S-Cu2Te system using dissociation pressure data

International Nuclear Information System (INIS)

Glazov, V.M.; Pashinkin, A.S.; Burkhanov, A.S.; Saleeva, N.M.

1978-01-01

The Knudsen effusive method has been used for studying the dissociation pressure in the Cu 2 S-Cu 2 Te system, and on the basis of the experimental data obtained, the tellurium activity in the system and the mixing energy have been calculated. The dissociation pressure of pure components and alloys containing 10, 30, 50, 70, and 90 mol% of copper telluride within the temperature range of 750-1200 deg C has been studied. A smooth character of the concentration dependence of tellurium activity is observed, which points to the formation of a continuous series of solid solutions in the Cu 2 S-Cu 2 Te system within the temperature range studied. The data on the mixing energy in the system show a good agreement of the values obtained from the dissociation pressure with those determined from the fusibility diagram. The results indicate that the system in question is described well within the framework of the model of regular solutions

Identification and H(D)-bond energies of C-H(D)Cl interactions in chloride-haloalkane clusters: a combined X-ray crystallographic, spectroscopic, and theoretical study.

Science.gov (United States)

Serebryanskaya, Tatiyana V; Novikov, Alexander S; Gushchin, Pavel V; Haukka, Matti; Asfin, Ruslan E; Tolstoy, Peter M; Kukushkin, Vadim Yu

2016-05-18

The cationic (1,3,5-triazapentadiene)Pt(II) complex [Pt{NH[double bond, length as m-dash]C(N(CH2)5)N(Ph)C(NH2)[double bond, length as m-dash]NPh}2]Cl2 ([]Cl2) was crystallized from four haloalkane solvents giving [][Cl2(CDCl3)4], [][Cl2(CHBr3)4], [][Cl2(CH2Cl2)2], and [][Cl2(C2H4Cl2)2] solvates that were studied by X-ray diffraction. In the crystal structures of [][Cl2(CDCl3)4] and [][Cl2(CHBr3)4], the Cl(-) ion interacts with two haloform molecules via C-DCl(-) and C-HCl(-) contacts, thus forming the negatively charged isostructural clusters [Cl(CDCl3)2](-) and [Cl(CHBr3)2](-). In the structures of [][Cl2(CH2Cl2)2] and [][Cl2(C2H4Cl2)2], cations [](2+) are linked to a 3D-network by a system of H-bondings including one formed by each Cl(-) ion with CH2Cl2 or C2H4Cl2 molecules. The lengths and energies of these H-bonds in the chloride-haloalkane clusters were analyzed by DFT calculations (M06 functional) including AIM analysis. The crystal packing noticeably affected the geometry of the clusters, and energy of C-HCl(-) hydrogen bonds ranged from 1 to 6 kcal mol(-1). An exponential correlation (R(2) > 0.98) between the calculated Cl(-)H distances and the energies of the corresponding contacts was found and used to calculate hydrogen bond energies from the experimental Cl(-)H distances. Predicted energy values (3.3-3.9 kcal mol(-1) for the [Cl(CHCl3)2](-) cluster) are in a reasonable agreement with the energy of the Cl3C-HCl(-) bond estimated using ATRFTIR spectroscopy (2.7 kcal mol(-1)).

X-ray diffraction and chemical bonding

International Nuclear Information System (INIS)

Bats, J.W.

1976-01-01

Chemical bonds are investigated in sulfamic acid (H 3 N-SO 3 ), sodium sulfonlate dihydrate (H 2 NC 6 H 4 SO 3 Na.2H 2 O), 2,5-dimercaptothiadiazole (HS-C 2 N 2 S-SH), sodium cyanide dihydrate (NaCN.2H 2 O), sodium thiocyanate (NaSCN) and ammonium thiocyanate (NH 4 SCN) by X-ray diffraction, and if necessary completed with neutron diffraction. Crystal structures and electron densities are determined together with bond length and angles. Also the effects of thermal motion are discussed

First principles study of NH3 molecular adsorption on LiH (100) surfaces

International Nuclear Information System (INIS)

Lu Xiaoxia; Chen Yuhong; Dong Xiao

2012-01-01

The adsorption of NH 3 on LiH (100) crystal surfaces was studied by first principles method. The preferred adsorption sites, adsorption energy, dissociation energy and electronic structure of the LiH (100)/NH 3 systems were calculated separately. It is found that chemical adsorption happened mainly when NH 3 molecules are on the LiH (100) crystal surfaces. When NH 3 is adsorbed on the Li top site, NH 2 is formed on the LiH (100) crystal surfaces after loss of H atom, the calculated adsorption energy, 0.511 eV, belongs to strong chemical adsorption, then the interaction is strongest. The interaction between NH 2 and the neighboring Li, H are ionic. The covalent bonds are formed between N and H atoms in NH 2 . One H 2 molecule is formed by another H atom in NH 3 and H atom from LiH (100) crystal sur- faces. The covalent bonds are formed between H and H atoms in H 2 . (authors)

Dissociative photoionization of 1,3-butadiene: experimental and theoretical insights.

Science.gov (United States)

Fang, Wenzheng; Gong, Lei; Zhang, Qiang; Shan, Xiaobin; Liu, Fuyi; Wang, Zhenya; Sheng, Liusi

2011-05-07

The vacuum-ultraviolet photoionization and dissociative photoionization of 1,3-butadiene in a region ∼8.5-17 eV have been investigated with time-of-flight photoionization mass spectrometry using tunable synchrotron radiation. The adiabatic ionization energy of 1,3-butadiene and appearance energies for its fragment ions, C(4)H(5)(+), C(4)H(4)(+), C(4)H(3)(+), C(3)H(3)(+), C(2)H(4)(+), C(2)H(3)(+), and C(2)H(2)(+), are determined to be 9.09, 11.72, 13.11, 15.20, 11.50, 12.44, 15.15, and 15.14 eV, respectively, by measurements of photoionization efficiency spectra. Ab initio molecular orbital calculations have been performed to investigate the reaction mechanism of dissociative photoionization of 1,3-butadiene. On the basis of experimental and theoretical results, seven dissociative photoionization channels are proposed: C(4)H(5)(+) + H, C(4)H(4)(+) + H(2), C(4)H(3)(+) + H(2) + H, C(3)H(3)(+) + CH(3), C(2)H(4)(+) + C(2)H(2), C(2)H(3)(+) + C(2)H(2) + H, and C(2)H(2)(+) + C(2)H(2) + H(2). Channel C(3)H(3)(+) + CH(3) is found to be the dominant one, followed by C(4)H(5)(+) + H and C(2)H(4)(+) + C(2)H(2). The majority of these channels occur via isomerization prior to dissociation. Transition structures and intermediates for those isomerization processes were also determined.

Hydrogen bonding in ionic liquids.

Science.gov (United States)

Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

2015-03-07

Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak

Si-H bond dynamics in hydrogenated amorphous silicon

Science.gov (United States)

Scharff, R. Jason; McGrane, Shawn D.

2007-08-01

The ultrafast structural dynamics of the Si-H bond in the rigid solvent environment of an amorphous silicon thin film is investigated using two-dimensional infrared four-wave mixing techniques. The two-dimensional infrared (2DIR) vibrational correlation spectrum resolves the homogeneous line shapes ( 4ps waiting times. The Si-H stretching mode anharmonic shift is determined to be 84cm-1 and decreases slightly with vibrational frequency. The 1→2 linewidth increases with vibrational frequency. Frequency dependent vibrational population times measured by transient grating spectroscopy are also reported. The narrow homogeneous line shape, large inhomogeneous broadening, and lack of spectral diffusion reported here present the ideal backdrop for using a 2DIR probe following electronic pumping to measure the transient structural dynamics implicated in the Staebler-Wronski degradation [Appl. Phys. Lett. 31, 292 (1977)] in a-Si:H based solar cells.

Specific Cα-C Bond Cleavage of β-Carbon-Centered Radical Peptides Produced by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

Science.gov (United States)

Nagoshi, Keishiro; Yamakoshi, Mariko; Sakamoto, Kenya; Takayama, Mitsuo

2018-04-01

Radical-driven dissociation (RDD) of hydrogen-deficient peptide ions [M - H + H]·+ has been examined using matrix-assisted laser dissociation/ionization in-source decay mass spectrometry (MALDI-ISD MS) with the hydrogen-abstracting matrices 4-nitro-1-naphthol (4,1-NNL) and 5-nitrosalicylic acid (5-NSA). The preferential fragment ions observed in the ISD spectra include N-terminal [a] + ions and C-terminal [x]+, [y + 2]+, and [w]+ ions which imply that β-carbon (Cβ)-centered radical peptide ions [M - Hβ + H]·+ are predominantly produced in MALDI conditions. RDD reactions from the peptide ions [M - Hβ + H]·+ successfully explains the fact that both [a]+ and [x]+ ions arising from cleavage at the Cα-C bond of the backbone of Gly-Xxx residues are missing from the ISD spectra. Furthermore, the formation of [a]+ ions originating from the cleavage of Cα-C bond of deuterated Ala(d3)-Xxx residues indicates that the [a]+ ions are produced from the peptide ions [M - Hβ + H]·+ generated by deuteron-abstraction from Ala(d3) residues. It is suggested that from the standpoint of hydrogen abstraction via direct interactions between the nitro group of matrix and hydrogen of peptides, the generation of the peptide radical ions [M - Hβ + H]·+ is more favorable than that of the α-carbon (Cα)-centered radical ions [M - Hα + H]·+ and the amide nitrogen-centered radical ions [M - HN + H]·+, while ab initio calculations indicate that the formation of [M - Hα + H]·+ is energetically most favorable. [Figure not available: see fulltext.

The estimation of H-bond and metal ion-ligand interaction energies in the G-Quadruplex ⋯ Mn+ complexes

Science.gov (United States)

Mostafavi, Najmeh; Ebrahimi, Ali

2018-06-01

In order to characterize various interactions in the G-quadruplex ⋯ Mn+ (G-Q ⋯ Mn+) complexes, the individual H-bond (EHB) and metal ion-ligand interaction (EMO) energies have been estimated using the electron charge densities (ρs) calculated at the X ⋯ H (X = N and O) and Mn+ ⋯ O (Mn+ is an alkaline, alkaline earth and transition metal ion) bond critical points (BCPs) obtained from the atoms in molecules (AIM) analysis. The estimated values of EMO and EHB were evaluated using the structural parameters, results of natural bond orbital analysis (NBO), aromaticity indexes and atomic charges. The EMO value increase with the ratio of ionic charge to radius, e/r, where a linear correlation is observed between EMO and e/r (R = 0.97). Meaningful relationships are also observed between EMO and indexes used for aromaticity estimation. The ENH value is higher than EOH in the complexes; this is in complete agreement with the trend of N⋯Hsbnd N and O⋯Hsbnd N angles, the E (2) value of nN → σ*NH and nO → σ*NH interactions and the difference between the natural charges on the H-bonded atom and the hydrogen atom of guanine (Δq). In general, the O1MO2 angle becomes closer to 109.5° with the increase in EMO and decrease in EHB in the presence of metal ion.

DSM-5's posttraumatic stress disorder with dissociative symptoms: challenges and future directions.

Science.gov (United States)

Dorahy, Martin J; van der Hart, Onno

2015-01-01

The Diagnostic and Statistical Manual of Mental Disorders, Fifth Edition, formally recognizes a dissociative subtype of posttraumatic stress disorder (PTSD; PTSD with dissociative symptoms). This nomenclative move will boost empirical and theoretical efforts to further understand the links between dissociation, trauma, and PTSD. This article examines the empirical literature showing that patients with PTSD can be divided into 2 different groups based on their neurobiology, psychological symptom profile, history of exposure to early relational trauma, and depersonalization/derealization symptoms. It then explores the conceptual and empirical challenges of conceiving 1 of these types as reflecting a "dissociative" type of PTSD. First, this classification is based on the presence of a limited subset of dissociative symptoms (i.e., depersonalization, derealization). This sets aside an array of positive and negative psychoform and somatoform dissociative symptoms that may be related to PTSD. Second, empirical evidence suggests heightened dissociation in PTSD compared to many other disorders, indicating that dissociation is relevant to PTSD more broadly rather than simply to the so-called dissociative subtype. This article sets out important issues to be examined in the future study of dissociation in PTSD, which needs to be informed by solid conceptual understandings of dissociation.

Measurements of the charge exchange and dissociation cross-sections of the H{sub 2}+ ion in a wide energy range; Mesures des sections efficaces d'echange de charge et de dissociation des ions H{sub 2}{sup +} dans une large gamme d'energie (25 - 250 keV)

Energy Technology Data Exchange (ETDEWEB)

Guidini, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1962-07-01

celles qui arrivent en coincidence sur deux detecteurs differents. Les resultats montrent une forte variation de la section efficace d'echange de charge en fonction de l'energie des ions H{sub 2}{sup +}. Les variations des sections efficaces de dissociation et d'ionisation sont moins prononcees. Pour une energie donnee, les valeurs des sections efficaces sont d'autant plus grandes que la masse atomique des particules cibles est plus grande. Ces mesures ont ete etendues au cas d'ions H{sub 2}{sup +} traversant une cible constituee par des particules chargees. Des resultats preliminaires montrent une augmentation de la valeur des sections efficaces par rapport au cas precedent. Enfin la diffusion des produits de reactions a ete etudiee, elle a permis de voir que l'angle de diffusion provient de ce que les molecules formees au cours d'une reaction se trouvent dans un etat instable et les noyaux ou atomes s'ecartent l'un de l'autre. (auteur)

The pure rotational spectrum of ZnS (X 1Σ +)

Science.gov (United States)

Zack, L. N.; Ziurys, L. M.

2009-10-01

The pure rotational spectrum of ZnS (X 1Σ +) has been measured using direct-absorption millimeter/sub-millimeter techniques in the frequency range 372-471 GHz. This study is the first spectroscopic investigation of this molecule. Spectra originating in four zinc isotopologues ( 64ZnS, 66ZnS, 68ZnS, and 67ZnS) were recorded in natural abundance in the ground vibrational state, and data from the v = 1 state were also measured for the two most abundant zinc species. Spectroscopic constants have been subsequently determined, and equilibrium parameters have been estimated. The equilibrium bond length was calculated to be re ˜ 2.0464 Å, which agrees well with theoretical predictions. In contrast, the dissociation energy of DE ˜ 3.12 eV calculated for ZnS, assuming a Morse potential, was significantly higher than past experimental and theoretical estimates, suggesting diabatic interaction with other potentials that lower the effective dissociation energy. Although ZnS is isovalent with ZnO, there appear to be subtle differences in bonding between the two species, as suggested by their respective force constants and bond length trends in the 3d series.

Theoretical studies of molecule surface scattering: Rotationally inelastic diffraction and dissociative dynamics of H2 on metals

International Nuclear Information System (INIS)

Cruz Pol, A.J.

1993-01-01

The interaction of H 2 and its isotopes with metal surfaces has been the subject of many investigations. The scattering experiments provide data such as the final rotational state distribution, sticking coefficients, kinetic energy distribution, and diffraction data. In the first study of this thesis the author implemented a model for looking at the rotationally inelastic diffraction probabilities for H 2 , HD, and D 2 , as a function of surface temperature. The surface is treated in a quantum mechanical fashion using a recently developed formalism. The center of mass translational motion is treated semiclassically using Gaussian wave packets, and the rotations are described quantum mechanically. The phonon summed rotation-diffraction probabilities as well as the probability distribution for a scattering molecule exchanging an amount of energy ΔE with the surface were computed. In the second and third study of this thesis the author implemented a mixed quantum-classical model to compute the probability for dissociation and rotational excitation for H 2 , HD, and D 2 scattered from Ni(100) dimensionally in dynamics simulations. Of the six degrees of freedom for the dissociative adsorption of a diatomic molecule on a static surface, the author treats Z,d the center of mass distance above the surface plan, r, the internuclear separation, θ, the polar orientation angle, quantum mechanically. The remaining three degrees of freedom, X and Y, the center of mass position on the surface plane, and oe, the azimuthal orientation angle, are treated classically. Probabilities for dissociation and ro-vibrational excitation are computed as a function of incident translational energy. Two sudden approximations are tested, in which either the center of mass translation parallel to the surface or the azimuthal orientation of the molecule are frozen. Comparisons are made between low and high dimensionality results and with fully classical results

Metastablity of the undissociated state of dissociated dislocations

International Nuclear Information System (INIS)

Takeuchi, Shin

2005-01-01

Undissociated, metastable dislocations have been observed in various crystals in addition to stable dissociated dislocations by high-resolution transmission electron microscopy. The origin of the metastablity of the undissociated state has been discussed specifically for the dissociation into Shockley partial dislocations in fcc or hcp lattice. It is shown that the metastability is due either to a high Peierls-Nabarro stress larger than a few percent of the shear modulus of the partial dislocations and/or to the increase of the total core energy by an increase of the dangling bonds. The metastablity of undissociated dislocations in zincblende III-V compounds is concluded to be due to a contribution of the latter effect

The 1600 Å Emission Bump in Protoplanetary Disks: A Spectral Signature of H{sub 2}O Dissociation

Energy Technology Data Exchange (ETDEWEB)

France, Kevin [Laboratory for Atmospheric and Space Physics, University of Colorado, 600 UCB, Boulder, CO 80309 (United States); Roueff, Evelyne; Abgrall, Hervé, E-mail: kevin.france@colorado.edu [LERMA, Observatoire de Paris, PSL Research University, CNRS, Sorbonne Universités, UPMC Univ. Paris 06, F-92190, Meudon (France)

2017-08-01

is Ly α -driven dissociation of H{sub 2}O in the inner disk, r ≲ 2 au. We demonstrate that non-thermally populated H{sub 2}O fragments can qualitatively account for the observed emission (discrete and continuum) and find that the average Ly α -driven H{sub 2}O dissociation rate is 1.7 × 10{sup 42} water molecules s{sup −1}.

Rh(III-catalyzed directed C–H bond amidation of ferrocenes with isocyanates

Directory of Open Access Journals (Sweden)

Satoshi Takebayashi

2012-10-01

Full Text Available [RhCp*(OAc2(H2O] [Cp* = pentamethylcyclopentadienyl] catalyzed the C–H bond amidation of ferrocenes possessing directing groups with isocyanates in the presence of 2 equiv/Rh of HBF4·OEt2. A variety of disubstituted ferrocenes were prepared in high yields, or excellent diastereoselectivities.

Origin of the Ability of α-Fe2 O3 Mesopores to Activate C-H Bonds in Methane.

Science.gov (United States)

Dong, Bing; Han, Zhen; Zhang, Yongbo; Yu, Youyi; Kong, Aiguo; Shan, Yongkui

2016-02-01

Methane is a most abundant and inexpensive hydrocarbon feedstock for the production of chemicals and fuels. However, it is extremely difficult to directly convert methane to higher hydrocarbons because the C-H bonds in methane are the most stable C-H bonds of all hydrocarbons. The activation of the C-H bonds in methane by using an efficient and mild route remains a daunting challenge. Here, we show that the inner surface structures of the pore walls in mesoporous α-Fe 2 O 3 possess excellent catalytic performance for methane activation and convert C-H bonds into the C-O bonds in an O 2 atmosphere at 140 °C. We found that such unusual structures are mainly comprised of turbostratic ribbons and K crystal faces and have higher catalytic activity than the (110) plane. These results are without precedent in the history of catalysis chemistry and will provide a new pathway for designing and preparing highly efficient catalytic materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A genetically-encoded chloride and pH sensor for dissociating ion dynamics in the nervous system.

Science.gov (United States)

Raimondo, Joseph V; Joyce, Bradley; Kay, Louise; Schlagheck, Theresa; Newey, Sarah E; Srinivas, Shankar; Akerman, Colin J

2013-01-01

Within the nervous system, intracellular Cl(-) and pH regulate fundamental processes including cell proliferation, metabolism, synaptic transmission, and network excitability. Cl(-) and pH are often co-regulated, and network activity results in the movement of both Cl(-) and H(+). Tools to accurately measure these ions are crucial for understanding their role under physiological and pathological conditions. Although genetically-encoded Cl(-) and pH sensors have been described previously, these either lack ion specificity or are unsuitable for neuronal use. Here we present ClopHensorN-a new genetically-encoded ratiometric Cl(-) and pH sensor that is optimized for the nervous system. We demonstrate the ability of ClopHensorN to dissociate and simultaneously quantify Cl(-) and H(+) concentrations under a variety of conditions. In addition, we establish the sensor's utility by characterizing activity-dependent ion dynamics in hippocampal neurons.

Effects of metals doping on the removal of Hg and H{sub 2}S over ceria

Energy Technology Data Exchange (ETDEWEB)

Ling, Lixia, E-mail: linglixia@tyut.edu.cn [College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Zhao, Zhongbei; Zhao, Senpeng [College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Wang, Qiang [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China); Wang, Baojun, E-mail: wangbaojun@tyut.edu.cn [Key Laboratory of Coal Science and Technology (Taiyuan University of Technology), Ministry of Education and Shanxi Province, Taiyuan 030024, Shanxi (China); Zhang, Riguang [Key Laboratory of Coal Science and Technology (Taiyuan University of Technology), Ministry of Education and Shanxi Province, Taiyuan 030024, Shanxi (China); Li, Debao [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China)

2017-05-01

Highlights: • Mn and Fe doped CeO{sub 2}(111) surfaces favor Hg capture via strong interaction. • HgS adsorbs on Mn and Fe/CeO{sub 2}(111) surfaces with molecule mode. • Hg is easily oxidized by the active S on Mn and Fe/CeO{sub 2}(111) surfaces. • Mn and Fe doped ceria have the potential to simultaneous remove Hg and H{sub 2}S. - Abstract: The effects of Mn and Fe doping into the CeO{sub 2}(111) surface on the simultaneous removal of Hg and H{sub 2}S was investigated, a density functional theory calculation with the on-site Coulomb interaction taken into account was adopted. The adsorptions of Hg-containing species on perfect CeO{sub 2}(111), Mn/CeO{sub 2}(111) and Fe/CeO{sub 2}(111) surfaces were studied, the results showed that Mn and Fe dopants facilitated Hg adsorption, and more charge transferred from Hg atom to the metal doped surfaces; HgS preferred to adsorb on the perfect surface with the dissociated mode, while with the molecular mode on Mn/CeO{sub 2}(111) and Fe/CeO{sub 2}(111) surfaces. The reaction mechanism show that the dissociated S by H{sub 2}S can easily react with Hg leading to the formation of HgS on Mn/CeO{sub 2}(111) and Fe/CeO{sub 2}(111) surfaces, which is crucial to capture mercury.

Synthesis, spectroscopic characterization and structural studies of a new proton transfer (H-bonded) complex of o-phenylenediamine with L-tartaric acid

Science.gov (United States)

Khan, Ishaat M.; Ahmad, Afaq

2013-10-01

A proton transfer or H-bonded (CT) complex of o-phenylenediamine (OPD) as donor with L-tartaric acid (TART) as acceptor was synthesized and characterized by spectral techniques such as FTIR, 1H NMR, elemental analysis, TGA-TDA, X-ray crystallography and spectrophotometric studies. The structural investigations exhibit that the cation [OPD+] and anion [TART-] are linked together through strong N+-H⋯O- type hydrogen bonds due to transfer of proton from acceptor to donor. Formed H-bonded complex exhibits well resolved proton transfer bands in the regions where neither donor nor acceptor has any absorption. The stoichiometry of the H-bonded complex (HBC) was found to be 1:1, determined by straight line methods. Spectrophotometric studies have been performed at room temperature and Benesi-Hildebrand equation was used to determine formation constant (KCT), molar extinction coefficient (ɛCT) and also transition energy (ECT) of the H-bonded complex. Spectrophotomeric and crystallographic studies have ascertained the formation of 1:1 H-bonded complex. Thermal analysis (TGA-DTA) was also used to confirm the thermal fragmentation and the stability of the synthesized H-bonded complex.

Genetic and Environmental Basis of the Relationship Between Dissociative Experiences and Cloninger’s Temperament and Character Dimensions – Pilot Study

Directory of Open Access Journals (Sweden)

Domozych Wojciech

2016-12-01

Full Text Available Dissociation is commonly regarded as a disruption in the normally integrated functions of memory, knowledge, affect, sensation or behavior. The present study utilized behavioral genetics’ methodology to investigate genetic and environmental basis of the relationship between dissociation and Cloninger’s temperament and character traits. A sample of 83 monozygotic and 65 dizygotic twins were administered self-report measures which assessed dissociative experiences along with personality dimensions. Significant correlations and high loads of common genetic variance between dissociative experiences and personality traits of novelty seeking, self-directedness, cooperativeness and self-transcendence were identified. Heritability of dissociative experiences was estimated at 62%. The study shows that there exists a considerable amount of genetic variance overlap between dissociation and personality dimensions. It also supports the hypothesis that propensity to dissociate is highly heritable

Dissociation from beloved unhealthy brands decreases preference for and consumption of vegetables.

Science.gov (United States)

Trump, Rebecca K; Connell, Paul M; Finkelstein, Stacey R

2015-09-01

Many people form strong bonds with brands, including those for unhealthy foods. Thus, prompting people to dissociate from beloved but unhealthy food brands is an intuitively appealing means to shift consumption away from unhealthy options and toward healthy options. Contrary to this position, we demonstrate that dissociating from unhealthy but beloved brands diminishes people's interest in consuming vegetables because the dissociation depletes self-regulatory resources. Across three experimental studies, we manipulate dissociation from two beloved brands both implicitly (studies 1-2) and explicitly (study 3) and observe effects on both preference for vegetables (studies 2-3) and actual vegetable consumption (study 1). In study 1, participants consumed fewer vegetables following dissociation from (vs. association with) a beloved candy brand. Study 2 demonstrates that the effect of depletion on preference for vegetables is more pronounced for those who strongly identify with the brand, as these individuals are most depleted by the dissociation attempt. Finally, study 3 illustrates that the difficulty experienced when trying to dissociate from beloved brands drives the observed effects on vegetable preference and consumption for those who strongly (vs. weakly) identify with the brand. Copyright © 2015 Elsevier Ltd. All rights reserved.

New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

KAUST Repository

Samantaray, Manoja

2015-08-18

In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a way to rationalize mechanism of heterogeneous catalysis and to achieve structure activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With surface organometallic chemistry one can coordinate to the metal which can play a role in different elementary steps leading for example to C–H activation and Olefin metathesis. Because of the development of SOMC there is a lot of space for the improvement of homogeneous catalysis. After the 1997 discovery of alkane metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150ºC) the focus in this area was shifted to the discovery of more and more challenging surface complexes active in the application of C–H and C–C bond activation. Here we describe the evolution of well-defined metathesis catalyst with time as well as the effect of support on catalysis. We also describe here which metal–ligand combinations are responsible for a variety of C–H and C–C bond activation.

The effects of pH on N-methacryloyl glycine primer on bond strength to acid-etched dentin.

Science.gov (United States)

Nishiyama, N; Suzuki, K; Asakura, T; Nakai, H; Yasuda, S; Nemoto, K

1996-07-01

To develop a more effective adhesive primer, it is imperative to understand the adhesion mechanisms of the resin to the demineralized dentin through a dentin primer. When the bonding agent was directly applied to the dentin etched by 40 wt % phosphoric acid without a primer pretreatment, the bond strength of the resin to the dentin was 5 MPa. Conversely, when the demineralized dentin was pretreated with the N-methacryloyl glycine (NM alpha A) primer solution with a pH value of 1.5, the bond strength increased considerably to 15 MPa. However, the bond strength dropped dramatically from 15 to 3 MPa when the sodium salt of NM alpha A was added, thereby increasing the pH value of the NM alpha A primer solution from 3.2 to 5.0. When the pH value was increased above 3.5 (pKa value), the number of ionized NM alpha A species increased in the solution. As a result, the bond strength of the resin fell to approximately 3 MPa. This result was obtained despite the 5-micron-thick hybrid layer that was created in the subsurface of the intertubular dentin. The number of unionized NM alpha A species increased by lowering the pH value below 3.5. As a result, the NM alpha A primer provided a higher bond strength of the resin to the demineralized dentin. In contrast, when 10 wt % citric acid containing 3 wt % ferric chloride was applied to the dentin, maximum bond strength was obtained when the pH value of the NM alpha A primer solution was 3.5. The pH dependency of the bond strength obtained following 10 wt % citric acid containing 3 wt % ferric chloride etching is different from the results obtained from 40 wt % phosphoric acid etching. This can be attributed to the difference in the characteristics of the demineralized collageous layer.

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.

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.

C and Si delta doping in Ge by CH_3SiH_3 using reduced pressure chemical vapor deposition

International Nuclear Information System (INIS)

Yamamoto, Yuji; Ueno, Naofumi; Sakuraba, Masao; Murota, Junichi; Mai, Andreas; Tillack, Bernd

2016-01-01

C and Si delta doping in Ge are investigated using a reduced pressure chemical vapor deposition system to establish atomic-order controlled processes. CH_3SiH_3 is exposed at 250 °C to 500 °C to a Ge on Si (100) substrate using H_2 or N_2 carrier gas followed by a Ge cap layer deposition. At 350 °C, C and Si are uniformly adsorbed on the Ge surface and the incorporated C and Si form steep delta profiles below detection limit of SIMS measurement. By using N_2 as carrier gas, the incorporated C and Si doses in Ge are saturated at one mono-layer below 350 °C. At this temperature range, the incorporated C and Si doses are nearly the same, indicating CH_3SiH_3 is adsorbed on the Ge surface without decomposing the C−Si bond. On the other hand, by using H_2 as carrier gas, lower incorporated C is observed in comparison to Si. CH_3SiH_3 injected with H_2 carrier gas is adsorbed on Ge without decomposing the C−Si bond and the adsorbed C is reduced by dissociation of the C−Si bond during temperature ramp up to 550 °C. The adsorbed C is maintained on the Ge surface in N_2 at 550 °C. - Highlights: • C and Si delta doping in Ge is investigated using RPCVD system by CH_3SiH_3 exposure. • Atomically flat C and Si delta layers are fabricated at 350 °C. • Incorporated C and Si doses are saturated at one mono-layer below 350 °C. • CH_3SiH_3 adsorption occurred without decomposing C−Si bond. • Adsorbed C is desorbed due to dissociation by hydrogen during postannealing at 550 °C.

Thiocarbamate-Directed Tandem Olefination-Intramolecular Sulfuration of Two Ortho C-H Bonds: Application to Synthesis of a COX-2 Inhibitor.

Science.gov (United States)

Li, Wendong; Zhao, Yingwei; Mai, Shaoyu; Song, Qiuling

2018-02-16

A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

A genetically-encoded chloride and pH sensor for dissociating ion dynamics in the nervous system

Science.gov (United States)

Raimondo, Joseph V.; Joyce, Bradley; Kay, Louise; Schlagheck, Theresa; Newey, Sarah E.; Srinivas, Shankar; Akerman, Colin J.

2013-01-01

Within the nervous system, intracellular Cl− and pH regulate fundamental processes including cell proliferation, metabolism, synaptic transmission, and network excitability. Cl− and pH are often co-regulated, and network activity results in the movement of both Cl− and H+. Tools to accurately measure these ions are crucial for understanding their role under physiological and pathological conditions. Although genetically-encoded Cl− and pH sensors have been described previously, these either lack ion specificity or are unsuitable for neuronal use. Here we present ClopHensorN—a new genetically-encoded ratiometric Cl− and pH sensor that is optimized for the nervous system. We demonstrate the ability of ClopHensorN to dissociate and simultaneously quantify Cl− and H+ concentrations under a variety of conditions. In addition, we establish the sensor's utility by characterizing activity-dependent ion dynamics in hippocampal neurons. PMID:24312004

Surface Defect Passivation and Reaction of c-Si in H2S.

Science.gov (United States)

Liu, Hsiang-Yu; Das, Ujjwal K; Birkmire, Robert W

2017-12-26

A unique passivation process of Si surface dangling bonds through reaction with hydrogen sulfide (H 2 S) is demonstrated in this paper. A high-level passivation quality with an effective minority carrier lifetime (τ eff ) of >2000 μs corresponding to a surface recombination velocity of passivation by monolayer coverage of S on the Si surface. However, S passivation of the Si surface is highly unstable because of thermodynamically favorable reaction with atmospheric H 2 O and O 2 . This instability can be eliminated by capping the S-passivated Si surface with a protective thin film such as low-temperature-deposited amorphous silicon nitride.

Dipole-Guided Electron Capture Causes Abnormal Dissociations of Phosphorylated Pentapeptides

DEFF Research Database (Denmark)

Moss, Christopher L.; Chung, Thomas W.; Wyer, Jean

2011-01-01

energies and fluoranthene anion radicals in an ion trap resulted in the loss of a hydrogen atom, ammonia, and backbone cleavages forming complete series of sequence z ions. Elimination of phosphoric acid was negligible. In contrast, capture of lowenergy electrons by doubly charged ions in a Penning ion...... mapping of the potential energy surface provided structures for the precursor phosphopeptide dications. Electron attachment produces a multitude of low lying electronic states in charge-reduced ions that determine their reactivity in backbone dissociations and H- atom loss. The predominant loss of H atoms......Abstract Electron transfer and capture mass spectra of a series of doubly charged ions that were phosphorylated pentapeptides of a tryptic type (pS,A,A,A,R) showed conspicuous differences in dissociations of charge-reduced ions. Electron transfer from both gaseous cesium atoms at 100 keV kinetic...

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

Effects of Carbonyl Bond and Metal Cluster Dissociation and Evaporation Rates on Predictions of Nanotube Production in HiPco

Science.gov (United States)

Scott, Carl D.; Smalley, Richard E.

2002-01-01

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNT) 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 co-formation of CO2. It is shown that the production of CO2 is significantly greater for FeCO due to its lower bond energy as compared with that ofNiCO. 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.

Enantioselective carbenoid insertion into C(sp3–H bonds

Directory of Open Access Journals (Sweden)

J. V. Santiago

2016-05-01

Full Text Available The enantioselective carbenoid insertion into C(sp3–H bonds is an important tool for the synthesis of complex molecules due to the high control of enantioselectivity in the formation of stereogenic centers. This paper presents a brief review of the early issues, related mechanistic studies and recent applications on this chemistry area.

Alkane Activation at Ambient Temperatures: Unusual Selectivities, C-C, C-H Bond Scission versus C-C Bond Coupling

NARCIS (Netherlands)

Trionfetti, C.; Agiral, A.; Gardeniers, Johannes G.E.; Lefferts, Leonardus; Seshan, Kulathuiyer

2008-01-01

Activating bonds: A cold plasma generated by dielectric barrier discharge in a microreactor converts alkanes (C1–C3) at atmospheric pressure. Large amounts of products with higher molecular weight than the starting hydrocarbons are observed showing that C-H activation at lower T favourably leads to

[4,6-Dimethylpyrimidine-2(1H-thione-κS]iodidobis(triphenylphosphane-κPcopper(I

Directory of Open Access Journals (Sweden)

Chaveng Pakawatchai

2012-06-01

Full Text Available In the mononuclear title complex, [CuI(C6H8N2S(C18H15P2], the CuI ion is in a slightly distorted tetrahedral coordination geometry formed by two P atoms from two triphenylphosphane ligands, one S atom from a 4,6-dimethylpyrimidine-2(1H-thione ligand and one iodide ion. There is an intramolecular N—H...I hydrogen bond. In the crystal, π–π stacking interactions [centroid–centroid distance = 3.594 (1 Å] are observed.

Bonding effectiveness of self-etch adhesives to dentin after 24 h water storage.

Science.gov (United States)

Sarr, Mouhamed; Benoist, Fatou Leye; Bane, Khaly; Aidara, Adjaratou Wakha; Seck, Anta; Toure, Babacar

2018-01-01

This study evaluated the immediate bonding effectiveness of five self-etch adhesive systems bonded to dentin. The microtensile bond strength of five self-etch adhesives systems, including one two-step and four one-step self-etch adhesives to dentin, was measured. Human third molars had their superficial dentin surface exposed, after which a standardized smear layer was produced using a medium-grit diamond bur. The selected adhesives were applied according to their respective manufacturer's instructions for μTBS measurement after storage in water at 37°C for 24 h. The μTBS varied from 11.1 to 44.3 MPa; the highest bond strength was obtained with the two-step self-etch adhesive Clearfil SE Bond and the lowest with the one-step self-etch adhesive Adper Prompt L-Pop. Pretesting failures mainly occurring during sectioning with the slow-speed diamond saw were observed only with the one-step self-etch adhesive Adper Prompt L-Pop (4 out of 18). When bonded to dentin, the self-etch adhesives with simplified application procedures (one-step self-etch adhesives) still underperform as compared to the two-step self-etch adhesive Clearfil SE Bond.

Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage.

Science.gov (United States)

Wang, Teng; Jiao, Ning

2014-04-15

Because of the importance of nitrogen-containing compounds in chemistry and biology, organic chemists have long focused on the development of novel methodologies for their synthesis. For example, nitrogen-containing compounds show up within functional materials, as top-selling drugs, and as bioactive molecules. To synthesize these compounds in a green and sustainable way, researchers have focused on the direct functionalization of hydrocarbons via C-H or C-C bond cleavage. Although researchers have made significant progress in the direct functionalization of simple hydrocarbons, direct C-N bond formation via C-H or C-C bond cleavage remains challenging, in part because of the unstable character of some N-nucleophiles under oxidative conditions. The nitriles are versatile building blocks and precursors in organic synthesis. Recently, chemists have achieved the direct C-H cyanation with toxic cyanide salts in the presence of stoichiometric metal oxidants. In this Account, we describe recent progress made by our group in nitrile synthesis. C-H or C-C bond cleavage is a key process in our strategy, and azides or DMF serve as the nitrogen source. In these reactions, we successfully realized direct nitrile synthesis using a variety of hydrocarbon groups as nitrile precursors, including methyl, alkenyl, and alkynyl groups. We could carry out C(sp(3))-H functionalization on benzylic, allylic, and propargylic C-H bonds to produce diverse valuable synthetic nitriles. Mild oxidation of C═C double-bonds and C≡C triple-bonds also produced nitriles. The incorporation of nitrogen within the carbon skeleton typically involved the participation of azide reagents. Although some mechanistic details remain unclear, studies of these nitrogenation reactions implicate the involvement of a cation or radical intermediate, and an oxidative rearrangement of azide intermediate produced the nitrile. We also explored environmentally friendly oxidants, such as molecular oxygen, to make our

Relaxation of the chemical bond skin chemisorption size matter ZTP mechanics H2O myths

CERN Document Server

Sun, Chang Q

2014-01-01

The aim of this book is to explore the detectable properties of a material to the parameters of bond and non-bond involved and to clarify the interdependence of various properties. This book is composed of four parts; Part I deals with the formation and relaxation dynamics of bond and non-bond during chemisorptions with uncovering of the correlation among the chemical bond, energy band, and surface potential barrier (3B) during reactions; Part II is focused on the relaxation of bonds between atoms with fewer neighbors than the ideal in bulk with unraveling of the bond order-length-strength (BOLS) correlation mechanism, which clarifies the nature difference between nanostructures and bulk of the same substance; Part III deals with the relaxation dynamics of bond under heating and compressing with revealing of rules on the temperature-resolved elastic and plastic properties of low-dimensional materials; Part IV is focused on the asymmetric relaxation dynamics of the hydrogen bond (O:H-O) and the anomalous behav...

Elastic and proton-dissociative photoproduction of J/ψ mesons at HERA

International Nuclear Information System (INIS)

Alexa, C.; Dobre, M.; Rotaru, M.; Stoicea, G.; Andreev, V.; Belousov, A.; Fomenko, A.; Gogitidze, N.; Lebedev, A.; Malinovski, E.; Rusakov, S.; Vazdik, Y.; Baghdasaryan, A.; Baghdasaryan, S.; Zohrabyan, H.; Bartel, W.; Belov, P.; Brinkmann, M.; Britzger, D.; Campbell, A.J.; Eckerlin, G.; Elsen, E.; Felst, R.; Fischer, D.J.; Fleischer, M.; Gayler, J.; Ghazaryan, S.; Glazov, A.; Gouzevitch, M.; Grebenyuk, A.; Habib, S.; Haidt, D.; Kleinwort, C.; Kraemer, M.; Krueger, K.; Levonian, S.; Lipka, K.; List, B.; List, J.; Lobodzinski, B.; Meyer, A.B.; Meyer, J.; Niebuhr, C.; Olsson, J.E.; Ozerov, D.; Pahl, P.; Petrukhin, A.; Pitzl, D.; Placakyte, R.; Radescu, V.; Schmitt, S.; Sefkow, F.; Shushkevich, S.; South, D.; Steder, M.; Wuensch, E.; Begzsuren, K.; Ravdandorj, T.; Tseepeldorj, B.; Boudry, V.; Specka, A.; Bozovic-Jelisavcic, I.; Pandurovic, M.; Brandt, G.; Brisson, V.; Jacquet, M.; Pascaud, C.; Zhang, Z.; Zomer, F.; Buniatyan, A.; Huber, F.; Pirumov, H.; Sauter, M.; Schoening, A.; Bylinkin, A.; Bystritskaya, L.; Fedotov, A.; Lubimov, V.; Rostovtsev, A.; Cantun Avila, K.B.; Contreras, J.G.; Ruiz Tabasco, J.E.; Ceccopieri, F.; Wolf, E.A. de; Favart, L.; Hreus, T.; Janssen, X.; Roosen, R.; Staykova, Z.; Mechelen, P. van; Cerny, K.; Pokorny, B.; Polifka, R.; Salek, D.; Valkarova, A.; Zacek, J.; Zlebcik, R.; Chekelian, V.; Grindhammer, G.; Kiesling, C.; Cvach, J.; Hladky, J.; Reimer, P.; Zalesak, J.; Dainton, J.B.; Gabathuler, E.; Greenshaw, T.; Klein, M.; Kretzschmar, J.; Laycock, P.; Maxfield, S.J.; Mehta, A.; Patel, G.D.; Daum, K.; Meyer, H.; Diaconu, C.; Hoffmann, D.; Sauvan, E.; Vallee, C.; Dodonov, V.; Dossanov, A.; Egli, S.; Hildebrandt, M.; Horisberger, R.; Feltesse, J.; Perez, E.; Schoeffel, L.; Ferencei, J.; Goerlich, L.; Mikocki, S.; Milcewicz-Mika, I.; Nowak, G.; Sopicki, P.; Turnau, J.; Grab, C.; Henderson, R.C.W.; Hennekemper, E.; Herbst, M.; Schultz-Coulon, H.C.; Herrera, G.; Lopez-Fernandez, R.; Hiller, K.H.; Kostka, P.; Lange, W.; Naumann, T.; Joensson, L.; Jung, H.; Kapichine, M.; Morozov, A.; Nikitin, D.; Palichik, V.; Spaskov, V.; Kogler, R.; Nowak, K.; Landon, M.P.J.; Rizvi, E.; Traynor, D.; Martyn, H.U.; Morris, J.V.; Sankey, D.P.C.; Mueller, K.; Robmann, P.; Straumann, U.; Truoel, P.; Newman, P.R.; Thompson, P.D.; Picuric, I.; Raicevic, N.; Soloviev, Y.; Stella, B.; Sykora, T.; Tsakov, I.; Wegener, D.

2013-01-01

Cross sections for elastic and proton-dissociative photoproduction of J/ψ mesons are measured with the H1 detector in positron-proton collisions at HERA. The data were collected at ep centre-of-mass energies √(s) ∼ 318 GeV and √(s) ∼ 225 GeV, corresponding to integrated luminosities of L = 130 pb -1 and L = 10.8 pb -1 , respectively. The cross sections are measured as a function of the photon-proton centre-of-mass energy in the range 25 γp 2 for the elastic process and vertical stroke t vertical stroke 2 for proton dissociation. The results are compared to other measurements. The W γp and t-dependences are parametrised using phenomenological fits. (orig.)

Cobalt-Catalyzed, Aminoquinoline-Directed sp2 C-H Bond Alkenylation by Alkynes**

Science.gov (United States)

Grigorjeva, Liene; Daugulis, Olafs

2014-01-01

We have developed a method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed sp2 C-H bond alkenylation by alkynes. Method shows excellent functional group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs Co(OAc)2*4H2O catalyst, Mn(OAc)2 cocatalyst, and oxygen from air as a terminal oxidant. PMID:25060365

Dissociation pathways of a single dimethyl disulfide on Cu(111): Reaction induced by simultaneous excitation of two vibrational modes

Energy Technology Data Exchange (ETDEWEB)

Motobayashi, Kenta, E-mail: kmotobayashi@cat.hokudai.ac.jp [Catalysis Research Center, Hokkaido University, Sapporo 001-0021 (Japan); Department of Advanced Materials Science, The University of Tokyo, Kashiwa 277-8561 (Japan); Surface and Interface Science Laboratory, RIKEN, Wako 351-0198 (Japan); Kim, Yousoo [Surface and Interface Science Laboratory, RIKEN, Wako 351-0198 (Japan); Arafune, Ryuichi [International Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba 305-0044 (Japan); Ohara, Michiaki; Ueba, Hiromu; Kawai, Maki, E-mail: maki@k.u-tokyo.ac.jp [Department of Advanced Materials Science, The University of Tokyo, Kashiwa 277-8561 (Japan)

2014-05-21

We present a novel reaction mechanism for a single adsorbed molecule that proceeds via simultaneous excitation of two different vibrational modes excited by inelastic tunneling electrons from a scanning tunneling microscope. Specifically, we analyze the dissociation of a single dimethyl disulfide (DMDS, (CH{sub 3}S){sub 2}) molecule on Cu(111) by using a versatile theoretical method, which permits us to simulate reaction rates as a function of sample bias voltage. The reaction is induced by the excitation of C-H stretch and S-S stretch modes by a two-electron process at low positive bias voltages. However, at increased voltages, the dissociation becomes a single-electron process that excites a combination mode of these stretches, where excitation of the C-H stretch is the energy source and excitation of the S-S stretch mode enhances the anharmonic coupling rate. A much smaller dissociation yield (few orders of magnitude) at negative bias voltages is understood in terms of the projected density of states of a single DMDS on Cu(111), which reflects resonant excitation through the molecular orbitals.

A van der Waals DFT study of PtH_2 systems absorbed on pristine and defective graphene

International Nuclear Information System (INIS)

López-Corral, Ignacio; Piriz, Sebastián; Faccio, Ricardo; Juan, Alfredo; Avena, Marcelo

2016-01-01

Highlights: • We performed DFT calculations including van der Waals interactions. • Kubas-type Pt-H2 complex is stable on defective graphene. • Carbon vacancy decreases the reactivity of the metal decoration. • The interaction between σ-H and π-C states favors the Kubas-type complex. - Abstract: We used a density functional that incorporates van der Waals interactions to study hydrogen adsorption onto Pt atoms attached to carbon-vacancies on graphene layers, considering molecular and dissociated hydrogen-platinum coordination structures. PtH_2 complexes adsorbed on several sites of pristine graphene were also studied for comparison. Our results indicate that both a Kubas-type dihydrogen complex and a classic hydride without H−H bond are the preferential PtH_2 systems on the vacancy site of graphene. In contrast, the Kubas complex is unstable onto pristine graphene and the hydride is obtained at all adsorption sites. Our simulations suggest that the C-vacancy decreases the reactivity of the metal decoration, allowing a non-dissociative hydrogen adsorption. The H_2 molecule is oriented almost perpendicular to the outermost C−Pt bond, interacting also with the graphene surface through σ-H and π-C states. This stabilization of the Kubas-type complex could play a very important role for hydrogen storage in Pt-decorated carbon adsorbents with vacancies.

Rydberb bonding in (NH4)2

International Nuclear Information System (INIS)

Boldyrev, A.I.; Simons, J.

1992-01-01

Chemical binding of two monovalent Rydberg species to form a singlet-state Rydberg dimer molecule is predicted to be possible Ab initio electronic structure methods that include electron correlation (at levels up through QCISD(T)/6-31++G** MP2(full)/6-31++G** + ZPE) are shown to be essential to achieving a proper description of such bonding. The (NH 4 ) molecule, selected as the prototype for this study, is shown to be bound with respect to its Rydberg-species fragments, 2NH 4 by 7.5-9.7 kcal/mol, depending on the level of treatment of electron correlation, and to be electronically stable (by ca.4 eV) with respect to (NH 4 ) 2 + at the neutral's equilibrium geometry. The (NH 4 ) 2 Rydberg dimer is thermodynamically unstable with respect to 2NH 3 + H 2 by 86-89 kcal/mol mol yet possesses all real vibrational frequencies; it is thus a metastable molecular held together by a weak Rydberg bond. The dissociation energy of the (NH 4 ) 2 + cation to form NH 4 + + NH 4 is found to be larger than that of the neutral (NH 4 ) 2 . 12 refs., 4 figs., 9 tabs

Dissociative Recombination and Excitation of CH+5 : Absolute Cross Sections and Branching Fractions

International Nuclear Information System (INIS)

Semaniak, J.; Larson, A.; Le Padellec, A.; Stroemholm, C.; Larsson, M.; Rosen, S.; Peverall, R.; Danared, H.; Djuric, N.; Dunn, G.H.; Datz, S.

1998-01-01

The heavy-ion storage ring CRYRING was used to measure the absolute dissociative recombination and dissociative excitation cross sections for collision energies below 50 eV. Deduced thermal rates coefficients are consistent with previous beams data but are lower by a factor of 3 than the rates measured by means of the flowing afterglow Langmuir probe technique. A resonant structure in dissociative recombination cross section was found at 9 eV. We have determined the branching fractions in DR of CH + 5 below 0.2 eV. The branching is dominated by three-body CH 3 + H + H and CH 2 + H 2 + H dissociation channels, which occur with branching ratios of ∼0.7 and ∼0.2, respectively; thus methane is a minor species among dissociation products. Both the measured absolute cross sections and branching in dissociative recombination of CH + 5 can have important implications for the models of dense interstellar clouds and abundance of CH 2 , CH 3 and CH 4 in these media. copyright copyright 1998. The American Astronomical Society

Cobalt-catalyzed, aminoquinoline-directed C(sp²)-H bond alkenylation by alkynes.

Science.gov (United States)

Grigorjeva, Liene; Daugulis, Olafs

2014-09-15

A method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed C(sp(2))-H bond alkenylation by alkynes was developed. The method shows excellent functional-group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs a Co(OAc)2⋅4 H2O catalyst, Mn(OAc)2 co-catalyst, and oxygen (from air) as a terminal oxidant. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Infrared and Raman spectroscopy and quantum chemistry calculation studies of C-H...O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoate

Czech Academy of Sciences Publication Activity Database

Sato, H.; Dybal, Jiří; Murakami, R.; Noda, I.; Ozaki, Y.

744-747, - (2005), s. 35-46 ISSN 0022-2860 R&D Projects: GA AV ČR IAA4050208 Keywords : infrared and Raman spectroscopy * quantum chemical calculation * C-H...O hydrogen bonding Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.440, year: 2005

Borylnitrenes: electrophilic reactive intermediates with high reactivity towards C-H bonds.

Science.gov (United States)

Bettinger, Holger F; Filthaus, Matthias

2010-12-21

Borylnitrenes (catBN 3a and pinBN 3b; cat = catecholato, pin = pinacolato) are reactive intermediates that show high tendency towards insertion into the C-H bonds of unactivated hydrocarbons. The present article summarizes the matrix isolation investigations that were aimed at identifying, characterizing and investigating the chemical behaviour of 3a by spectroscopic means, and of the experiments in solution and in the gas phase that were performed with 3b. Comparison with the reactivity reported for difluorovinylidene 1a in solid argon indicates that 3a shows by and large similar reactivity, but only after photochemical excitation. The derivative 3b inserts into the C-H bonds of hydrocarbon solvents in high yields and thus allows the formation of primary amines, secondary amines, or amides from "unreactive" hydrocarbons. It can also be used for generation of methylamine or methylamide from methane in the gas phase at room temperature. Remaining challenges in the chemistry of borylnitrenes are briefly summarized.

Nicotinamidase/pyrazinamidase of Mycobacterium tuberculosis forms homo-dimers stabilized by disulfide bonds.

Science.gov (United States)

Rueda, Daniel; Sheen, Patricia; Gilman, Robert H; Bueno, Carlos; Santos, Marco; Pando-Robles, Victoria; Batista, Cesar V; Zimic, Mirko

2014-12-01

Recombinant wild-pyrazinamidase from H37Rv Mycobacterium tuberculosis was analyzed by gel electrophoresis under differential reducing conditions to evaluate its quaternary structure. PZAse was fractionated by size exclusion chromatography under non-reducing conditions. PZAse activity was measured and mass spectrometry analysis was performed to determine the identity of proteins by de novo sequencing and to determine the presence of disulfide bonds. This study confirmed that M. tuberculosis wild type PZAse was able to form homo-dimers in vitro. Homo-dimers showed a slightly lower specific PZAse activity compared to monomeric PZAse. PZAse dimers were dissociated into monomers in response to reducing conditions. Mass spectrometry analysis confirmed the existence of disulfide bonds (C72-C138 and C138-C138) stabilizing the quaternary structure of the PZAse homo-dimer. Copyright © 2014 Elsevier Ltd. All rights reserved.

Threshold collision-induced dissociation of diatomic molecules: a case study of the energetics and dynamics of O2- collisions with Ar and Xe.

Science.gov (United States)

Ahu Akin, F; Ree, Jongbaik; Ervin, Kent M; Kyu Shin, Hyung

2005-08-08

The energetics and dynamics of collision-induced dissociation of O2- with Ar and Xe targets are studied experimentally using guided ion-beam tandem mass spectrometry. The cross sections and the collision dynamics are modeled theoretically by classical trajectory calculations. Experimental apparent threshold energies are 2.1 and 1.1 eV in excess of the thermochemical O2- bond dissociation energy for argon and xenon, respectively. Classical trajectory calculations confirm the observed threshold behavior and the dependence of cross sections on the relative kinetic energy. Representative trajectories reveal that the bond dissociation takes place on a short time scale of about 50 fs in strong direct collisions. Collision-induced dissociation is found to be remarkably restricted to the perpendicular approach of ArXe to the molecular axis of O2-, while collinear collisions do not result in dissociation. The higher collisional energy-transfer efficiency of xenon compared with argon is attributed to both mass and polarizability effects.

Threshold collision-induced dissociation of diatomic molecules: A case study of the energetics and dynamics of O2- collisions with Ar and Xe

International Nuclear Information System (INIS)

Ahu Akin, F.; Ree, Jongbaik; Ervin, Kent M.; Hyung, Kyu Shin

2005-01-01

The energetics and dynamics of collision-induced dissociation of O 2 - with Ar and Xe targets are studied experimentally using guided ion-beam tandem mass spectrometry. The cross sections and the collision dynamics are modeled theoretically by classical trajectory calculations. Experimental apparent threshold energies are 2.1 and 1.1 eV in excess of the thermochemical O 2 - bond dissociation energy for argon and xenon, respectively. Classical trajectory calculations confirm the observed threshold behavior and the dependence of cross sections on the relative kinetic energy. Representative trajectories reveal that the bond dissociation takes place on a short time scale of about 50 fs in strong direct collisions. Collision-induced dissociation is found to be remarkably restricted to the perpendicular approach of Ar/Xe to the molecular axis of O 2 - , while collinear collisions do not result in dissociation. The higher collisional energy-transfer efficiency of xenon compared with argon is attributed to both mass and polarizability effects

A dissociation mechanism for the [a+c] dislocation in GaN

International Nuclear Information System (INIS)

Nellist, P D; Hirsch, P B; Lozano, J G; Rhode, S; Zhang, S; Kappers, M J; Humphreys, C J; Horton, M K; Moram, M A; Yasuhara, A; Okunishi, E; Sahonta, S-L

2014-01-01

Mixed-type [a+c] dislocations can be identified in atomic-resolution high-angle annular dark-field scanning transmission electron microscope images of GaN viewed along [0001] by use of a Burgers loop analysis and by observation of the depth-dependent displacements associated with the Eshelby twist. These dislocations are found to be able to dissociate resulting in a fault that lies perpendicular to the dislocation glide plane. Consideration of the bonding that occurs in such a fault allows the dissociation reaction to be proposed, and the proposed fault agrees with the experimental images when kinks are incorporated into the model

Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.

Science.gov (United States)

Mo, Lixin; Zeng, Yanli; Li, Xiaoyan; Zhang, Xueying; Meng, Lingpeng

2016-07-01

The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex.