Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies

Czech Academy of Sciences Publication Activity Database

Bardhan, J. P.; Jungwirth, Pavel; Makowski, L.

Roč. 137, č. 12 ( 2012 ), 124101/1-124101/6 ISSN 0021-9606 R&D Projects: GA MŠk LH12001 Institutional research plan: CEZ:AV0Z40550506 Keywords : ion solvation * continuum models * linear response Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.164, year: 2012

Towards a stable ion-solvating polymer electrolyte for advanced alkaline water electrolysis

DEFF Research Database (Denmark)

Aili, David; Wright, Andrew G.; Kraglund, Mikkel Rykær

2017-01-01

Advanced alkaline water electrolysis using ion-solvating polymer membranes as electrolytes represents a new direction in the field of electrochemical hydrogen production. Polybenzimidazole membranes equilibrated in aqueous KOH combine the mechanical robustness and gas-tightness of a polymer...... stability in alkaline environments. The novel electrolytes are extensively characterized with respect to physicochemical and electrochemical properties and the chemical stability is assessed in 0-50 wt% aqueous KOH for more than 6 months at 88 degrees C. In water electrolysis tests using porous 3...

Preferential solvation of single ions in mixed solvents: Part 1. New experimental approach and solvation of monovalent ions in methanol-water and acetonitrile-water mixture. Part 2. Theoretical computation and comparison with experimental data

International Nuclear Information System (INIS)

Rege, Aarti C.; Venkataramani, B.; Gupta, A.R.

1999-06-01

Preferential solvation of single ion solutions has been studied with Li + , Na + , K + and Ag +- forms of Dowex 50W resins of different cross-linkings in methanol-water and acetonitrile (AN)- water mixtures. The solvent uptake by this alkali metal ionic forms of Dowex 50W resins was studied in an isopiestic set-up using 2,4,6 and 8 m LiCl solutions in 11.0, 20.8, 44.3 and 70.2 % (w/w) methanol-water mixtures and that of Na +- and Ag +- forms using 14.6 to 94.3 % (w/w) AN - water mixtures. The solvent sorbed in the resin phase was extracted by Rayleigh-type distillation and analysed gas chromatographically. The data were analysed by the N s (mole fraction of the organic solvent in the resin phase) vs n t au (total solvent content in the resin phase) plots and separation factor, alpha(ratio of mole fraction of the solvents in the resin and solution phases) or N s vs m (molality in the resin phase) plots. The limiting values of these plots gave the composition of the solvent in the primary solvation shell around the single ion. The compositions of the primary solvation shell around Li + , Na + , and K + in methanol-water mixtures and Na + and Ag + in acetonitrile (AN) - water mixtures have been computed using Franks equation and the approach of Marcus and compared with the experimental results obtained with the above mentioned ionic forms of Dowex 50W resins in different mixed solvents. The experimental results for Li + showed good agreement with the values computed using Franks equation for all methanol-water composition. However, in the case of Na + and K + in methanol-water mixtures and Na + in AN-water mixtures, there was agreement only at lower organic solvent content and the Franks equation predicted higher values for the organic solvent in the primary solvation shell around the cation at higher organic solvent content as compared to experimental results

Solvation thermodynamics and heat capacity of polar and charged solutes in water

Science.gov (United States)

Sedlmeier, Felix; Netz, Roland R.

2013-03-01

The solvation thermodynamics and in particular the solvation heat capacity of polar and charged solutes in water is studied using atomistic molecular dynamics simulations. As ionic solutes we consider a F- and a Na+ ion, as an example for a polar molecule with vanishing net charge we take a SPC/E water molecule. The partial charges of all three solutes are varied in a wide range by a scaling factor. Using a recently introduced method for the accurate determination of the solvation free energy of polar solutes, we determine the free energy, entropy, enthalpy, and heat capacity of the three different solutes as a function of temperature and partial solute charge. We find that the sum of the solvation heat capacities of the Na+ and F- ions is negative, in agreement with experimental observations, but our results uncover a pronounced difference in the heat capacity between positively and negatively charged groups. While the solvation heat capacity ΔCp stays positive and even increases slightly upon charging the Na+ ion, it decreases upon charging the F- ion and becomes negative beyond an ion charge of q = -0.3e. On the other hand, the heat capacity of the overall charge-neutral polar solute derived from a SPC/E water molecule is positive for all charge scaling factors considered by us. This means that the heat capacity of a wide class of polar solutes with vanishing net charge is positive. The common ascription of negative heat capacities to polar chemical groups might arise from the neglect of non-additive interaction effects between polar and apolar groups. The reason behind this non-additivity is suggested to be related to the second solvation shell that significantly affects the solvation thermodynamics and due to its large spatial extent induces quite long-ranged interactions between solvated molecular parts and groups.

Studies of base pair sequence effects on DNA solvation based on all

Indian Academy of Sciences (India)

Detailed analyses of the sequence-dependent solvation and ion atmosphere of DNA are presented based on molecular dynamics (MD) simulations on all the 136 unique tetranucleotide steps obtained by the ABC consortium using the AMBER suite of programs. Significant sequence effects on solvation and ion localization ...

Luminescence study on solvation of americium(III), curium(III) and several lanthanide(III) ions in nonaqueous and binary mixed solvents

International Nuclear Information System (INIS)

Kimura, T.; Nagaishi, R.; Kato, Y.; Yoshida, Z.

2001-01-01

The luminescence lifetimes of An(III) and Ln(III) ions [An=Am and Cm; Ln=Nd, Sm, Eu, Tb and Dy] were measured in dimethyl sulfoxide(DMSO), N,N-dimethylformamide(DMF), methanol(MeOH), water and their perdeuterated solvents. Nonradiative decay rates of the ions were in the order of H 2 O > MeOH > DMF > DMSO, indicating that O-H vibration is more effective quencher than C-H, C=O, and S=O vibrations in the solvent molecules. Maximal lifetime ratios τ D /τ H were observed for Eu(III) in H 2 O, for Sm(III) in MeOH and DMF, and for Sm(III) and Dy(III) in DMSO. The solvent composition in the first coordination sphere of Cm(III) and Ln(III) in binary mixed solvents was also studied by measuring the luminescence lifetime. Cm(III) and Ln(III) were preferentially solvated by DMSO in DMSO-H 2 O, by DMF in DMF-H 2 O, and by H 2 O in MeOH-H 2 O over the whole range of the solvent composition. The order of the preferential solvation, i.e., DMSO > DMF > H 2 O > MeOH, correlates with the relative basicity of these solvents. The Gibbs free energy of transfer of ions from water to nonaqueous solvents was further estimated from the degree of the preferential solvation. (orig.)

Proton solvation and proton transfer in chemical and electrochemical processes

International Nuclear Information System (INIS)

Lengyel, S.; Conway, B.E.

1983-01-01

This chapter examines the proton solvation and characterization of the H 3 O + ion, proton transfer in chemical ionization processes in solution, continuous proton transfer in conductance processes, and proton transfer in electrode processes. Topics considered include the condition of the proton in solution, the molecular structure of the H 3 O + ion, thermodynamics of proton solvation, overall hydration energy of the proton, hydration of H 3 O + , deuteron solvation, partial molal entropy and volume and the entropy of proton hydration, proton solvation in alcoholic solutions, analogies to electrons in semiconductors, continuous proton transfer in conductance, definition and phenomenology of the unusual mobility of the proton in solution, solvent structure changes in relation to anomalous proton mobility, the kinetics of the proton-transfer event, theories of abnormal proton conductance, and the general theory of the contribution of transfer reactions to overall transport processes

Study of the effect hydrogen binding in the solvation of alkaline earth cations with MeOH in nitromethane using 1 H NMR technique and determination of ionic solvation number

CERN Document Server

Alizadeh, N

2001-01-01

A proton NMR method for the study of the effect hydrogen binding and determination of solvation numbers of alkaline earth cations with methanol (MeOH) in in tromethane (NM) as diluent is described. The method is based on monitoring the resonance frequency of MeOH protons as a function of MeOH to metal ion mole ratio at constant metal ion concentration. the average solvation number of cation, n, at any MeOH/ metal ion mole ration was calculated from the NMR chemical shift-mole ration data and was plotted against the mole ration values. The solvation numbers of alkaline earth cations were obtained from the limiting values of the corresponding n, vs. mole ratio plots.

Study of the effect hydrogen binding in the solvation of alkaline earth cations with MeOH in nitromethane using 1 H NMR technique and determination of ionic solvation number

International Nuclear Information System (INIS)

Alizadeh, N.

2001-01-01

A proton NMR method for the study of the effect hydrogen binding and determination of solvation numbers of alkaline earth cations with methanol (MeOH) in in tromethane (NM) as diluent is described. The method is based on monitoring the resonance frequency of MeOH protons as a function of MeOH to metal ion mole ratio at constant metal ion concentration. the average solvation number of cation, n, at any MeOH/ metal ion mole ration was calculated from the NMR chemical shift-mole ration data and was plotted against the mole ration values. The solvation numbers of alkaline earth cations were obtained from the limiting values of the corresponding n, vs. mole ratio plots

Nonpolar solvation dynamics for a nonpolar solute in room ...

Indian Academy of Sciences (India)

Sandipa Indra

2018-01-30

Jan 30, 2018 ... Keywords. Solvation dynamics; nonpolar solvation; ionic liquid; molecular dynamics; linear response theory. 1. ... J. Chem. Sci. (2018) 130:3 spectrum of the excited probe molecule for imida- .... Therefore, the solute and the RTIL ions interact only ... interval of 30 ps from a long equilibrium trajectory of dura-.

Preferential Solvation of Silver (I) Bromate in Methanol-Dimethylsulfoxide Mixtures

Science.gov (United States)

Janardhanan, S.; Kalidas, C.

1984-06-01

The solubiltiy of silver bromate, the Gibbs transfer energy of Ag+ and BrO3- and the solvent transport number in methanol-dimethyl sulfoxide mixtures are reported. The solubility of silver bromate increases with addition of DMSO. The Gibbs energy of transfer of the silver ion (based on the ferrocene reference method) decreases, while that of the bromate ion becomes slightly negative with the addition of DMSO. The solvent transport number A passes through a maximum (⊿ = 1.0 at XDMSO = 0.65. From these results, it is concluded that the silver ion is preferentially solvated by DMSO whereas the bromate ion shows no preferential solvation.

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

Energy Technology Data Exchange (ETDEWEB)

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne, E-mail: egarand@chem.wisc.edu [Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706 (United States)

2015-11-28

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ions having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D{sub 2}-tagged GlyGlyH{sup +} ⋅ (H{sub 2}O){sub 1−4} are presented. They display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.

Understanding Lithium Solvation and Diffusion through Topological Analysis of First-Principles Molecular Dynamics

Energy Technology Data Exchange (ETDEWEB)

Bhatia, Harsh [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Gyulassy, Attila [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ong, Mitchell [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lordi, Vincenzo [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Draeger, Erik [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Pask, John [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Pascucci, Valerio [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Bremer, Peer -Timo [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2016-09-27

The performance of lithium-ion batteries is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact, both, the solvation and diffusivity of Li ions. In this work, we present our application of the topological techniques to extract and predict such behavior in the data generated by the first-principles molecular dynamics simulation of Li ions in an important organic solvent -ethylene carbonate. More specifically, we use the scalar topology of the electron charge density field to analyze the evolution of the solvation structures. This allows us to derive a parameter-free bond definition for lithium-oxygen bonds, to provide a quantitative measure for bond strength, and to understand the regions of influence of each atom in the simulation. This has provided new insights into how and under what conditions certain bonds may form and break. As a result, we can identify and, more importantly, predict, unstable configurations in solvation structures. This can be very useful in understanding when small changes to the atoms' movements can cause significantly different bond structures to evolve. Ultimately, this promises to allow scientists to explore lithium ion solvation and diffusion more systematically, with the aim of new insights and potentially accelerating the calculations themselves.

Formation of clusters (ions solvated with products of radiolysis) during irradiation of certain chloralkanes in the condensed phase

International Nuclear Information System (INIS)

Sukhov, F.F.; Karatun, A.A.; Slovokhotova, N.A.

1983-01-01

Using the infrared spectroscopy method, the radiolysis of the 2-chloropropane and 2-chloro-2-methylpropane was investigated in various phase states and in argon matrix at 15 and 77 K. A conclusion is drawn that the reaction of the radiation dehydrochlorination in the chloralkanes investigated occurs under certain conditions in the vicinity of ions, mostly; as this takes place, unique clusters composed of radiolysis products, i.e. ions solvated with complexes of alkane and hydrogen chloride are being formed. (author)

Primary and secondary kinetic isotope effects in the acid-catalyzed dehydration of 1,1'-diadamantylmethylcarbinol in aqueous acetic acid

International Nuclear Information System (INIS)

Lomas, J.S.

1981-01-01

The sulfuric acid catalyzed dehydration of 1,1'-diadamantyl-methylcarbinol in anhydrous acetic acid proceeds exclusively to 1,1'-bis(1-adamantyl)ethylene. The secondary deuterium isotope effect of 1.32 found for this reaction shows that carbonium ion formation from the protonated alcohol is rate determining. In the presence of water, however, capture of the carbonium ion competes with deprotonation, introducing a primary isotope effect. Consequently, the overall KIE rises, reaching 3.18 for 80% aqueous acetic acid. Analysis of the KIE for 80 to 100% aqueous acetic acid is consistent with a simple classical mechanism involving reversible formation of the intermediate carbonium ion. The primary isotope effect upon deprotonation is at the most 2.98, indicative of an asymmetric transition state close to the carbonium ion

Internal energy effects on the solvation and reactivity of multiply charged biomolecules for electrospray ionization mass spectroscopy. [Bovine ubiquitin

Energy Technology Data Exchange (ETDEWEB)

Light-Wahl, K.J.; Winger, B.E.; Rockwood, A.L.; Smith, R.D.

1992-06-01

Mild (capillary) interface conditions which do not completely desolvate the ions of proteins in electrospray ionization mass spectrometry (ESI-MS) may be required to probe the higher order structures and weak associations. For the small protein bovine ubiquitin, two ion distributions (unsolvated ions and unresolved solvated ions) were observed. The resolvable solvation for leucine-enkephalin with methanol and water shows that the use of countercurrent N{sub 2} flow at the capillary affects the solvation observed. 2 figs. (DLC)

Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

Science.gov (United States)

Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.; Mundy, Chistopher J.

2017-10-01

Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. Here, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing to the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. This suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.

Competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion by acetonitrile and water

DEFF Research Database (Denmark)

Chaban, Vitaly

2014-01-01

Competitive solvation of an ion by two or more solvents is one of the key phenomena determining the identity of our world. Solvation in polar solvents frequently originates from non-additive non-covalent interactions. Pre-parametrized potentials poorly capture these interactions, unless the force...

Solvation of positive ions in water: the dominant role of water-water interaction

International Nuclear Information System (INIS)

Krekeler, Christian; Site, Luigi Delle

2007-01-01

Local polarization effects, induced by monovalent and divalent positive ions in water, influence (and in turn are influenced by) the large-scale structural properties of the solvent. Experiments can only distinguish this process of interplay in a generic qualitative way. Instead, first-principles calculations can address the question at both the electronic and atomistic scale, accounting for electronic polarization as well as geometrical conformations. For this reason we study the extension of the scales' interconnection by means of first-principle Car-Parrinello molecular dynamics applied to systems of different size. In this way we identify the general aspects dominating the physics of the first solvation shell and their connection to the effects related to the formation of the outer shells and eventually the bulk. We show that while the influence of the ions is extended to the first shell only, the water-water interaction is instead playing a dominant role even within the first shell independently of the size or the charge of the ion. (fast track communication)

Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

Science.gov (United States)

Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

2015-01-01

The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

Theoretical Investigation of the Effect of the Rare Gas Matrices on the Vibrational Spectra of Solvated Molecular Ions: Cu+CO

Czech Academy of Sciences Publication Activity Database

Bludský, Ota; Šilhan, Martin; Nachtigall, Petr

2002-01-01

Roč. 117, č. 20 (2002), s. 9298-9305 ISSN 0021-9606 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : vibrational spectra * solvated molecular ions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.998, year: 2002

Incorporating Born solvation energy into the three-dimensional Poisson-Nernst-Planck model to study ion selectivity in KcsA K+ channels

Science.gov (United States)

Liu, Xuejiao; Lu, Benzhuo

2017-12-01

Potassium channels are much more permeable to potassium than sodium ions, although potassium ions are larger and both carry the same positive charge. This puzzle cannot be solved based on the traditional Poisson-Nernst-Planck (PNP) theory of electrodiffusion because the PNP model treats all ions as point charges, does not incorporate ion size information, and therefore cannot discriminate potassium from sodium ions. The PNP model can qualitatively capture some macroscopic properties of certain channel systems such as current-voltage characteristics, conductance rectification, and inverse membrane potential. However, the traditional PNP model is a continuum mean-field model and has no or underestimates the discrete ion effects, in particular the ion solvation or self-energy (which can be described by Born model). It is known that the dehydration effect (closely related to ion size) is crucial to selective permeation in potassium channels. Therefore, we incorporated Born solvation energy into the PNP model to account for ion hydration and dehydration effects when passing through inhomogeneous dielectric channel environments. A variational approach was adopted to derive a Born-energy-modified PNP (BPNP) model. The model was applied to study a cylindrical nanopore and a realistic KcsA channel, and three-dimensional finite element simulations were performed. The BPNP model can distinguish different ion species by ion radius and predict selectivity for K+ over Na+ in KcsA channels. Furthermore, ion current rectification in the KcsA channel was observed by both the PNP and BPNP models. The I -V curve of the BPNP model for the KcsA channel indicated an inward rectifier effect for K+ (rectification ratio of ˜3 /2 ) but indicated an outward rectifier effect for Na+ (rectification ratio of ˜1 /6 ) .

Interfacial solvation thermodynamics

International Nuclear Information System (INIS)

Ben-Amotz, Dor

2016-01-01

Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air–water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute–solvent) and indirect (solvent–solvent) contributions to adsorption thermodynamics, of relevance to solvation at air–water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. (paper)

Zero-point energy effects in anion solvation shells.

Science.gov (United States)

Habershon, Scott

2014-05-21

By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

Solvation and Ion Pair Association in Aqueous Metal Sulfates: Interpretation of NDIS raw data by isobaric-isothermal molecular dynamics simulation

International Nuclear Information System (INIS)

Chialvo, Ariel A.; Simonson, J. Michael

2010-01-01

We analyzed the solvation behavior of aqueous lithium, nickel, and ytterbium sulfates at ambient conditions in terms of the relevant radial distributions functions and the corresponding first-order difference of the sulfur-site neutron weighted distribution functions generated by isothermal-isobaric molecular dynamics simulation. We determined of the partial contributions to the neutron weighted distribution functions, to identify the main peaks, and the effect of the contact ion-pair configuration on the resulting H-S coordination number. Finally, we assessed the extent of the ion-pair formation according to Poirier-DeLap formalism and highlighted the significant increase of the ion-pair association exhibited by these salts with cation charge.

Rotation and solvation of ammonium ion

International Nuclear Information System (INIS)

Perrin, C.L.; Gipe, R.K.

1987-01-01

From nitrogen-15 spin-lattice relaxation times and nuclear Overhauser enhancements, the rotational correlations time tau/sub c/ for 15 NH 4 + was determined in s series of solvents. Values of tau/sub c/ range from 0.46 to 20 picoseconds. The solvent dependent of tau/sub c/ cannot be explained in terms of solvent polarity, molecular dipole moment, solvent basicity, solvent dielectric relaxation, or solvent viscosity. The rapid rotation and the variation with solvent can be accounted for by a model that involves hydrogen bonding of an NH proton to more than one solvent molecule in a disordered solvation environment. 25 references, 1 table

Corrosion Thermodynamics of Magnesium and Alloys from First Principles as a Function of Solvation

Science.gov (United States)

Limmer, Krista; Williams, Kristen; Andzelm, Jan

Thermodynamics of corrosion processes occurring on magnesium surfaces, such as hydrogen evolution and water dissociation, have been examined with density functional theory (DFT) to evaluate the effect of impurities and dilute alloying additions. The modeling of corrosion thermodynamics requires examination of species in a variety of chemical and electronic states in order to accurately represent the complex electrochemical corrosion process. In this study, DFT calculations for magnesium corrosion thermodynamics were performed with two DFT codes (VASP and DMol3), with multiple exchange-correlation functionals for chemical accuracy, as well as with various levels of implicit and explicit solvation for surfaces and solvated ions. The accuracy of the first principles calculations has been validated against Pourbaix diagrams constructed from solid, gas and solvated charged ion calculations. For aqueous corrosion, it is shown that a well parameterized implicit solvent is capable of accurately representing all but the first coordinating layer of explicit water for charged ions.

Intensity of f-f bands of neodymium chloride alcohol solvates

International Nuclear Information System (INIS)

Bukietynska, K.; Jezowski-Trzebiatowska, B.; Keller, B.

1981-01-01

Recent results revealed that in alcohol solutions of lanthanide chlorides, at least in the case of Eu 3+ and Yb 3+ ions, there exist mixed solvates, i.e. both chloride ions and solvent molecules are present in the Ln 3+ ion first coordination sphere. This conclusion was drawn from an analysis of the charge transfer transitions in the spectra of Eu 3+ and Yb 3+ chlorides in alcohols (methyl, ethyl, n-propyl), where two separate C.T.bands were observed and identified as C.T. transitions from the alcohol molecule and chloride ion to the Ln 3+ ion. In our previous paper we have reported that the energy of the first f-d transition in the Pr 3+ chloride alcohol solvates varied for different alcohols. These data also confirmed our suggestion that alcohol molecules are present in the first coordination sphere of the lanthanide ion. In the work reported here, we have tried to apply the intensity analysis method to the solution spectra of neodymium chloride dissolved in simple aliphatic alcohols like methanol, ethanol and n-propanol. Experimental details are given. Results are presented and discussed. (author)

Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane.

Science.gov (United States)

Chaban, Vitaly

2015-07-01

Electrolyte solutions based on the propylene carbonate (PC)-dimethoxyethane (DME) mixtures are of significant importance and urgency due to emergence of lithium-ion batteries. Solvation and coordination of the lithium cation in these systems have been recently attended in detail. However, analogous information concerning anions (tetrafluoroborate, hexafluorophosphate) is still missed. This work reports PM7-MD simulations (electronic-structure level of description) to include finite-temperature effects on the anion solvation regularities in the PC-DME mixture. The reported result evidences that the anions appear weakly solvated. This observation is linked to the absence of suitable coordination sites in the solvent molecules. In the concentrated electrolyte solutions, both BF4(-) and PF6(-) prefer to exist as neutral ion pairs (LiBF4, LiPF6).

Cluster expansion of the solvation free energy difference: Systematic improvements in the solvation of single ions

Science.gov (United States)

Pliego, Josefredo R.

2017-07-01

The cluster expansion method has been used in the imperfect gas theory for several decades. This paper proposes a cluster expansion of the solvation free energy difference. This difference, which results from a change in the solute-solvent potential energy, can be written as the logarithm of a finite series. Similar to the Mayer function, the terms in the series are related to configurational integrals, which makes the integrand relevant only for configurations of the solvent molecules close to the solute. In addition, the terms involve interaction of solute with one, two, and so on solvent molecules. The approach could be used for hybrid quantum mechanical and molecular mechanics methods or mixed cluster-continuum approximation. A simple form of the theory was applied for prediction of pKa in methanol; the results indicated that three explicit methanol molecules and the dielectric continuum lead to a root of mean squared error (RMSE) of only 1.3 pKa units, whereas the pure continuum solvation model based on density method leads to a RMSE of 6.6 pKa units.

Competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion by acetonitrile and water

Science.gov (United States)

Chaban, Vitaly

2014-10-01

Competitive solvation of an ion by two or more solvents is one of the key phenomena determining the identity of our world. Solvation in polar solvents frequently originates from non-additive non-covalent interactions. Pre-parametrized potentials poorly capture these interactions, unless the force field derivation is repeated for every new system. Development cost increases drastically as new chemical species are supplied. This work represents an alternative simulation approach, PM7-MD, by coupling the latest semiempirical parametrization, PM7, with equation-of-motion propagation scheme and temperature coupling. Using a competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion in acetonitrile and water, the work demonstrates efficiency and robustness of PM7-MD.

Electrical resistivities and solvation enthalpies for solutions of salts in liquid alkali metals

International Nuclear Information System (INIS)

Hubberstey, P.; Dadd, A.T.

1982-01-01

An empirical correlation is shown to exist between the resistivity coefficients drho/dc for solutes in liquid alkali metals and the corresponding solvation enthalpies Usub(solvn) of the neutral gaseous solute species. Qualitative arguments based on an electrostatic solvation model in which the negative solute atom is surrounded by a solvation sphere of positive solvent ion cores are used to show that both parameters are dependent on the charge density of the solute atom and hence on the extent of charge transfer from solvent to solute. Thus as the charge density of the solute increases, the solvation enthalpy increases regularly and the resistivity coefficients pass through a maximum to give the observed approximately parabolic drho/dc versus Usub(solvn) relationship. (Auth.)

Preferential solvation: dividing surface vs excess numbers.

Science.gov (United States)

Shimizu, Seishi; Matubayasi, Nobuyuki

2014-04-10

How do osmolytes affect the conformation and configuration of supramolecular assembly, such as ion channel opening and actin polymerization? The key to the answer lies in the excess solvation numbers of water and osmolyte molecules; these numbers are determinable solely from experimental data, as guaranteed by the phase rule, as we show through the exact solution theory of Kirkwood and Buff (KB). The osmotic stress technique (OST), in contrast, purposes to yield alternative hydration numbers through the use of the dividing surface borrowed from the adsorption theory. However, we show (i) OST is equivalent, when it becomes exact, to the crowding effect in which the osmolyte exclusion dominates over hydration; (ii) crowding is not the universal driving force of the osmolyte effect (e.g., actin polymerization); (iii) the dividing surface for solvation is useful only for crowding, unlike in the adsorption theory which necessitates its use due to the phase rule. KB thus clarifies the true meaning and limitations of the older perspectives on preferential solvation (such as solvent binding models, crowding, and OST), and enables excess number determination without any further assumptions.

Solvation structure determination of nickel(II) ion in six nitriles using extended X-ray absorption fine structure spectroscopy

International Nuclear Information System (INIS)

Inada, Yasuhiro; Funahashi, Shigenobu

1997-01-01

The solvation structures of the nickel(II) ion in six nitriles have been determined using X-ray absorption fine structure spectroscopy. The coordination number and the Ni-N bond length are 6 and 206.9 ± 0.6 pm in acetonitrile, 5.9 ± 0.2 and 206.9 ± 0.6 pm in propionitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in butyronitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in isobutyronitrile, 6.0 ± 0.2 and 206.8 ± 0.6 pm in valeronitrile, and 6.0 ± 0.2 and 206.5 ± 0.7 pm in benzonitrile, respectively. The structure parameters around the nickel(II) ion in all the nitriles are not affected by the bulkiness of the nitrile molecules. On the basis of the obtained structure parameters, we have discussed the structural characteristics around the nickel(II) ion with nitrogen and oxygen donor solvents and the reaction mechanisms for nitrile exchange on the nickel(II) ion. (author)

Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids

Science.gov (United States)

Shinoda, Wataru; Hatanaka, Yuta; Hirakawa, Masashi; Okazaki, Susumu; Tsuzuki, Seiji; Ueno, Kazuhide; Watanabe, Masayoshi

2018-05-01

Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)]+ complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)]+ complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)]+ complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)]+ pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li+ ions.

The dynamics of Ca2+ ions within the solvation shell of calbindin D9k.

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Elad Project

Full Text Available The encounter of a Ca(2+ ion with a protein and its subsequent binding to specific binding sites is an intricate process that cannot be fully elucidated from experimental observations. We have applied Molecular Dynamics to study this process with atomistic details, using Calbindin D9k (CaB as a model protein. The simulations show that in most of the time the Ca(2+ ion spends within the Debye radius of CaB, it is being detained at the 1st and 2nd solvation shells. While being detained near the protein, the diffusion coefficient of the ion is significantly reduced. However, due to the relatively long period of detainment, the ion can scan an appreciable surface of the protein. The enhanced propagation of the ion on the surface has a functional role: significantly increasing the ability of the ion to scan the protein's surface before being dispersed to the bulk. The contribution of this mechanism to Ca(2+ binding becomes significant at low ion concentrations, where the intervals between successive encounters with the protein are getting longer. The efficiency of the surface diffusion is affected by the distribution of charges on the protein's surface. Comparison of the Ca(2+ binding dynamics in CaB and its E60D mutant reveals that in the wild type (WT protein the carboxylate of E60 function as a preferred landing-site for the Ca(2+ arriving from the bulk, followed by delivering it to the final binding site. Replacement of the glutamate by aspartate significantly reduced the ability to transfer Ca(2+ ions from D60 to the final binding site, explaining the observed decrement in the affinity of the mutated protein to Ca(2+.

Selective solvation extraction of gold from alkaline cyanide solution by alkyl phosphorus esters

Energy Technology Data Exchange (ETDEWEB)

Miller, J.D.; Wan, R.Y.; Mooiman, M.B.; Sibrell, P.L.

1987-01-01

Research efforts have shown that solvation extraction of gold from alkaline cyanide solution is possible by alkyl phosphorus esters. Both tributyl phosphate (TBP) and dibutyl butyl phosphonate (DBBP) appear to be effective extractants for gold and exhibit high loading capacities exceeding 30 gpl. Selective solvation extraction of gold from alkaline cyanide solution can be achieved with selectivity factors relative to other cyanoanions as high as 1000 under certain circumstances. Variables influencing the selectivity such as ionic strength, temperature, and extractant structure, are discussed in terms of the extraction chemistry, which seems to involve the solvation of a M dot, dot, dot Au(CN)2 ion pair.

Solvation thermodynamics

CERN Document Server

Ben-Naim, Arieh

1987-01-01

This book deals with a subject that has been studied since the beginning of physical chemistry. Despite the thousands of articles and scores of books devoted to solvation thermodynamics, I feel that some fundamen­ tal and well-established concepts underlying the traditional approach to this subject are not satisfactory and need revision. The main reason for this need is that solvation thermodynamics has traditionally been treated in the context of classical (macroscopic) ther­ modynamics alone. However, solvation is inherently a molecular pro­ cess, dependent upon local rather than macroscopic properties of the system. Therefore, the starting point should be based on statistical mechanical methods. For many years it has been believed that certain thermodynamic quantities, such as the standard free energy (or enthalpy or entropy) of solution, may be used as measures of the corresponding functions of solvation of a given solute in a given solvent. I first challenged this notion in a paper published in 1978 b...

On the coupling between molecular diffusion and solvation shell exchange

DEFF Research Database (Denmark)

Møller, Klaus Braagaard; Rey, Rossend; Masia, Marco

2005-01-01

The connection between diffusion and solvent exchanges between first and second solvation shells is studied by means of molecular dynamics simulations and analytic calculations, with detailed illustrations for water exchange for the Li+ and Na+ ions, and for liquid argon. First, two methods...

Multiple time step molecular dynamics in the optimized isokinetic ensemble steered with the molecular theory of solvation: Accelerating with advanced extrapolation of effective solvation forces

International Nuclear Information System (INIS)

Omelyan, Igor; Kovalenko, Andriy

2013-01-01

steered by effective solvation forces allows huge outer time steps up to tens of picoseconds without affecting the equilibrium and conformational properties, and thus provides a 100- to 500-fold effective speedup in comparison to conventional MD with explicit solvent. With the statistical-mechanical 3D-RISM-KH account for effective solvation forces, the method provides efficient sampling of biomolecular processes with slow and/or rare solvation events such as conformational transitions of hydrated alanine dipeptide with the mean life times ranging from 30 ps up to 10 ns for “flip-flop” conformations, and is particularly beneficial for biomolecular systems with exchange and localization of solvent and ions, ligand binding, and molecular recognition

Silver atom solvation and desolvation in ice matrices: study of solvation shell geometry by electron spin resonance and electron spin echo methods

Energy Technology Data Exchange (ETDEWEB)

Kevan, L; Narayana, P A

1978-01-01

Results of studies of the solvation shell structure of silver atoms in ice matrix at 4/sup 0/K by electron spin resonance (ESR) and electron spin echo spectrometry are reported. Drastic change in the hyperfine coupling constant of the silver atom was noted when the silver atom initially produced at 4/sup 0/K was warmed to 77/sup 0/K and reexamined by ESR at 4/sup 0/K. This suggested a very drastic rearrangement of the water molecules surrounding the silver atom. The geometric arrangement of water molecules around the silver atom produced at 4/sup 0/K was what would be expected for a solvated silver ion, indicating that no rearrangement had occurred after the silver atom formed. The addition of a little thermal excitation (heating to 77/sup 0/K) results in the geometry changes than can be explained by assuming either that a water molecule rotates around one of its OH bands or by the development of a hydrogen bond between the silver atom and one of the first solvation shell water molecules. Optical excitation in the absorption band of the silver atom in the ice matrix at 400nm resulted in desolvation of the silver ion or a reversion to the structure originally obtained by reaction of solver salts in ic matrix with radiation produced electrons. This was best explained by a charge transfer mechanism. (BLM)

Isotope effect in enthalpy of solvation of the lithium ion

International Nuclear Information System (INIS)

Krestov, G.A.; Egorov, G.I.; Korolev, V.P.

1989-01-01

At 298.15 K, the authors determined the standard enthalpies of solution for 6 LiCl and 7 LiCl in water, heavy water, dimethylsulfoxide (DMSO) and aqueous solutions of DMSO. The authors have established that solvation of 6 Li + is differentiated in water and DMSO to a greater degree than for 7 Li +

Ionic association and solvation in solutions of magnesium and nickel perchlorates in acetonitrile

Science.gov (United States)

Kalugin, O. N.; Agieienko, V. N.; Otroshko, N. A.; Moroz, V. V.

2009-02-01

The paper presents the conductometric data on solutions of Mg(ClO4)2 and Ni(ClO4)2 in acetonitrile over the temperature ranges 5-55°C for Mg(ClO4)2 and 25-75°C for Ni(ClO4)2. The extended Lee-Wheaton equation for unsymmetrical electrolytes was used to determine the limiting equivalent conductivities of the Mg2+, Ni2+, and ClO{4/-} ions and first-step ionic association constants with the formation of [KtClO4]+ ion pairs. Lower ionic association constants for Ni(ClO4)2 compared with Mg(ClO4)2 were a consequence of stronger non-Coulomb repulsion in the formation of [KtClO4]+ ion pairs because of the formation of a firmer solvation shell by the nickel compared with magnesium cation. The structure-dynamic parameter of ionic solvation was estimated. It was found that spatial-time correlations in the nearest environment of ions increased in the series ClO{4/-} > Mg2+ > Ni2+.

Evidence for Reduced Hydrogen-Bond Cooperativity in Ionic Solvation Shells from Isotope-Dependent Dielectric Relaxation

Science.gov (United States)

Cota, Roberto; Ottosson, Niklas; Bakker, Huib J.; Woutersen, Sander

2018-05-01

We find that the reduction in dielectric response (depolarization) of water caused by solvated ions is different for H2O and D2O . This isotope dependence allows us to reliably determine the kinetic contribution to the depolarization, which is found to be significantly smaller than predicted by existing theory. The discrepancy can be explained from a reduced hydrogen-bond cooperativity in the solvation shell: we obtain quantitative agreement between theory and experiment by reducing the Kirkwood correlation factor of the solvating water from 2.7 (the bulk value) to ˜1.6 for NaCl and ˜1 (corresponding to completely uncorrelated motion of water molecules) for CsCl.

Solvated Positron Chemistry. Competitive Positron Reactions with Halide Ions in Water

DEFF Research Database (Denmark)

Christensen, Palle; Pedersen, Niels Jørgen; Andersen, J. R.

1979-01-01

It is shown by means of the angular correlation technique that the binding of positrons to halides is strongly influenced by solvation effects. For aqueous solutions we find increasing values for the binding energies between the halide and the positron with increasing mass of the halide...

Li+ solvation and kinetics of Li+-BF4-/PF6- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

Science.gov (United States)

Chang, Tsun-Mei; Dang, Liem X.

2017-10-01

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+-[BF4] and Li+-[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li+ ions varied from 60 to 450 ps, depending on the correction method used. We found that the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.

Solvation of actinide salts in water using a polarizable continuum model.

Science.gov (United States)

Kumar, Narendra; Seminario, Jorge M

2015-01-29

In order to determine how actinide atoms are dressed when solvated in water, density functional theory calculations have been carried out to study the equilibrium structure of uranium plutonium and thorium salts (UO2(2+), PuO2(2+), Pu(4+), and Th(4+)) both in vacuum as well as in solution represented by a conductor-like polarizable continuum model. This information is of paramount importance for the development of sensitive nanosensors. Both UO2(2+) and PuO2(2+) ions show coordination number of 4-5 with counterions replacing one or two water molecules from the first coordination shell. On the other hand, Pu(4+), has a coordination number of 8 both when completely solvated and also in the presence of chloride and nitrate ions with counterions replacing water molecules in the first shell. Nitrates were found to bind more strongly to Pu(IV) than chloride anions. In the case of the Th(IV) ion, the coordination number was found to be 9 or 10 in the presence of chlorides. Moreover, the Pu(IV) ion shows greater affinity for chlorides than the Th(IV) ion. Adding dispersion and ZPE corrections to the binding energy does not alter the trends in relative stability of several conformers because of error cancelations. All structures and energetics of these complexes are reported.

[Experimental and computation studies of polar solvation

International Nuclear Information System (INIS)

1990-01-01

This report from the Pennsylvania State University contains seven sections: (1) radiative rate effects in solvatlvatochromic probes; (2) intramolecular charge transfer reactions; (3) Solvation dynamics in low temperature alcohols; (4) Ionic solvation dynamics; (5) solvation and proton-transfer dynamics in 7-azaindole; (6) computer simulations of solvation dynamics; (7) solvation in supercritical fluids. 20 refs., 11 figs

The role of solvation in the binding selectivity of the L-type calcium channel.

Science.gov (United States)

Boda, Dezső; Henderson, Douglas; Gillespie, Dirk

2013-08-07

We present grand canonical Monte Carlo simulation results for a reduced model of the L-type calcium channel. While charged residues of the protein amino acids in the selectivity filter are treated explicitly, most of the degrees of freedom (including the rest of the protein and the solvent) are represented by their dielectric response, i.e., dielectric continua. The new aspect of this paper is that the dielectric coefficient in the channel is different from that in the baths. The ions entering the channel, thus, cross a dielectric boundary at the entrance of the channel. Simulating this case has been made possible by our recent methodological development [D. Boda, D. Henderson, B. Eisenberg, and D. Gillespie, J. Chem. Phys. 135, 064105 (2011)]. Our main focus is on the effect of solvation energy (represented by the Born energy) on monovalent vs. divalent ion selectivity in the channel. We find no significant change in selectivity by changing the dielectric coefficient in the channel because the larger solvation penalty is counterbalanced by the enhanced Coulomb attraction inside the channel as soon as we use the Born radii (fitted to experimental hydration energies) to compute the solvation penalty from the Born equation.

Electrolyte Suitable for Use in a Lithium Ion Cell or Battery

Science.gov (United States)

McDonald, Robert C. (Inventor)

2014-01-01

Electrolyte suitable for use in a lithium ion cell or battery. According to one embodiment, the electrolyte includes a fluorinated lithium ion salt and a solvent system that solvates lithium ions and that yields a high dielectric constant, a low viscosity and a high flashpoint. In one embodiment, the solvent system includes a mixture of an aprotic lithium ion solvating solvent and an aprotic fluorinated solvent.

A molecular dynamics study for the isomerization of Ar solvated (benzene){sub 2}-K{sup +} heteroclusters

Energy Technology Data Exchange (ETDEWEB)

Alberti, M. [CERQT, Departament de Quimica Fisica Parc Cientific, Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain); Pacifici, L. [Department of Mathematics and Computer Science, University of Perugia, via Vanvitelli, 1 06123 Perugia (Italy); Lagana, A. [Department of Chemistry, University of Perugia, via Elce di Sotto, 8 06123 Perugia (Italy)], E-mail: lag@dyn.unipg.it; Aguilar, A. [CERQT, Departament de Quimica Fisica Parc Cientific, Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain)

2006-08-21

A dynamical study of the (benzene){sub 2}-K{sup +} heteroclusters solvated by Ar atoms has been performed using an analytical force field of the atom (ion)-bond type. An analysis of the relevant calculated structural and energetic properties of these systems is made to understand involved molecular processes. The key effect found in the calculations is the tieing up of the two rings to sandwich K{sup +} and the weaking of this effect by solvation.

Solvation in supercritical water

International Nuclear Information System (INIS)

Cochran, H.D.; Cummings, P.T.; Karaborni, S.

1991-01-01

The aim of this work is to determine the solvation structure in supercritical water composed with that in ambient water and in simple supercritical solvents. Molecular dynamics studies have been undertaken of systems that model ionic sodium and chloride, atomic argon, and molecular methanol in supercritical aqueous solutions using the simple point charge model of Berendsen for water. Because of the strong interactions between water and ions, ionic solutes are strongly attractive in supercritical water, forming large clusters of water molecules around each ion. Methanol is found to be a weakly-attractive solute in supercritical water. The cluster of excess water molecules surrounding a dissolved ion or polar molecule in supercritical aqueous solutions is comparable to the solvent clusters surrounding attractive solutes in simple supercritical fluids. Likewise, the deficit of water molecules surrounding a dissolved argon atom in supercritical aqueous solutions is comparable to that surrounding repulsive solutes in simple supercritical fluids. The number of hydrogen bonds per water molecule in supercritical water was found to be about one third the number in ambient water. The number of hydrogen bonds per water molecule surrounding a central particle in supercritical water was only mildly affected by the identify of the central particle--atom, molecule, or ion. These results should be helpful in developing a qualitative understanding of important processes that occur in supercritical water. 29 refs., 6 figs

Benzonitrile: Electron affinity, excited states, and anion solvation

Science.gov (United States)

Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei

2015-10-01

We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O)n- and (NH3)n-

International Nuclear Information System (INIS)

Lee, G.H.; Arnold, S.T.; Eaton, J.G; Sarkas, H.W.; Bowen, K.H.; Ludewigt, C.; Haberland, H.

1991-01-01

The photodetachment spectra of (H 2 O) - n=2-69 and (NH 3 ) - n=41-1100 have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3 , extrapolating to a VDE (n = ∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons. (orig.)

Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O){/n -} and (NH3){/n -}

Science.gov (United States)

Lee, G. H.; Arnold, S. T.; Eaton, J. G.; Sarkas, H. W.; Bowen, K. H.; Ludewigt, C.; Haberland, H.

1991-03-01

The photodetachment spectra of (H2O){/n =2-69/-} and (NH3){/n =41-1100/-} have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3, extrapolating to a VDE ( n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

Science.gov (United States)

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; Mundy, Christopher J.

2018-01-01

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus' philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4--water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

Applications of the solvation parameter model in reversed-phase liquid chromatography.

Science.gov (United States)

Poole, Colin F; Lenca, Nicole

2017-02-24

The solvation parameter model is widely used to provide insight into the retention mechanism in reversed-phase liquid chromatography, for column characterization, and in the development of surrogate chromatographic models for biopartitioning processes. The properties of the separation system are described by five system constants representing all possible intermolecular interactions for neutral molecules. The general model can be extended to include ions and enantiomers by adding new descriptors to encode the specific properties of these compounds. System maps provide a comprehensive overview of the separation system as a function of mobile phase composition and/or temperature for method development. The solvation parameter model has been applied to gradient elution separations but here theory and practice suggest a cautious approach since the interpretation of system and compound properties derived from its use are approximate. A growing application of the solvation parameter model in reversed-phase liquid chromatography is the screening of surrogate chromatographic systems for estimating biopartitioning properties. Throughout the discussion of the above topics success as well as known and likely deficiencies of the solvation parameter model are described with an emphasis on the role of the heterogeneous properties of the interphase region on the interpretation and understanding of the general retention mechanism in reversed-phase liquid chromatography for porous chemically bonded sorbents. Copyright © 2016 Elsevier B.V. All rights reserved.

Elucidating the Solvation Structure and Dynamics of Lithium Polysulfides Resulting from Competitive Salt and Solvent Interactions

Energy Technology Data Exchange (ETDEWEB)

Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shin, Yongwoo; Han, Kee Sung; Lau, Kah Chun; Chen, Junzheng; Liu, Jun; Curtiss, Larry A.; Mueller, Karl T.; Persson, Kristin A.

2017-04-10

Fundamental molecular level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applica-tions. In particular, exhaustive knowledge of solvation structure, stability and transport properties is critical for developing stable electrolytes for fast charging and high energy density next-generation energy storage systems. Here we report the correlation between solubility, solvation structure and translational dynamics of a lithium salt (Li-TFSI) and polysulfides species using well-benchmarked classical molecular dynamics simulations combined with nuclear magnetic resonance (NMR). It is observed that the polysulfide chain length has a significant effect on the ion-ion and ion-solvent interaction as well as on the diffusion coefficient of the ionic species in solution. In particular, extensive cluster formation is observed in lower order poly-sulfides (Sx2-; x≤4), whereas the longer polysulfides (Sx2-; x>4) show high solubility and slow dynamics in the solu-tion. It is observed that optimal solvent/salt ratio is essen-tial to control the solubility and conductivity as the addi-tion of Li salt increases the solubility but decreases the mo-bility of the ionic species. This work provides a coupled theoretical and experimental study of bulk solvation struc-ture and transport properties of multi-component electro-lyte systems, yielding design metrics for developing optimal electrolytes with improved stability and solubility.

Barium isotope fractionation during the experimental transformation of aragonite to witherite and of gypsum to barite, and the effect of ion (de)solvation.

Science.gov (United States)

Böttcher, Michael E; Neubert, Nadja; von Allmen, Katja; Samankassou, Elias; Nägler, Thomas F

2018-06-01

In this study, we present the experimental results for stable barium (Ba) isotope fractionation ( 137 Ba/ 134 Ba) during the transformation of aragonite (CaCO 3 ) and gypsum (CaSO 4 ·2H 2 O) in Ba-bearing aqueous solution to witherite (BaCO 3 ) and barite (BaSO 4 ), respectively. The process was studied at three temperatures between 4 and 60 °C. In all cases, the transformation leads to a relative enrichment of the lighter 134 Ba isotope in the solid compared to the aqueous solution, with 137/134 Ba enrichment factors between -0.11 and -0.17 ‰ for BaCO 3 , and -0.21 and -0.26 ‰ for BaSO 4 . The corresponding mass-dependent 138/134 Ba enrichment factors are -0.15 to -0.23 ‰ for BaCO 3 , and -0.28 to -0.35 ‰ for BaSO 4 . The magnitude of isotope fractionation is within the range of recent reports for witherite and barite formation, as well as trace Ba incorporation into orthorhombic aragonite, and no substantial impact of temperature can be found between 4 and 80 °C. In previous studies, ion (de)solvation has been suggested to impact both the crystallization process of Ba-bearing solids and associated Ba isotope fractionation. Precipitation experiments of BaSO 4 and BaCO 3 using an methanol-containing aqueous solution indicate only a minor effect of ion and crystal surface (de)solvation on the overall Ba isotope fractionation process.

Compound forming extractants, solvating solvents and inert solvents IUPAC chemical data series

CERN Document Server

Marcus, Y; Kertes, A S

2013-01-01

Equilibrium Constants of Liquid-Liquid Distribution Reactions, Part III: Compound Forming Extractants, Solvating Solvents, and Inert Solvents focuses on the compilation of equilibrium constants of various compounds, such as acids, ions, salts, and aqueous solutions. The manuscript presents tables that show the distribution reactions of carboxylic and sulfonic acid extractants and their dimerization and other reactions in the organic phase and extraction reactions of metal ions from aqueous solutions. The book also states that the inorganic anions in these solutions are irrelevant, since they d

On the solvation of actinide ions

International Nuclear Information System (INIS)

Hagberg, D.

2007-01-01

Complete text of publication follows: Simulation of the universal ions in water solution is a standardized tool commonly used today. The route to simulation of actinide ions is normally tough because the evaluation of the simulation parameters are normally not given empirically and standard Hartree-Fock calculations are not accurate enough. We use multiconfigurational quantum chemical calculations when deriving the parameters for actinide ion-water potential [1]. The parameters are then simulated using classical molecular dynamics. A case study of the Cm 3+ ion will be presented on the poster. Results from the simulations will be also be discussed, e.g. the radial distribution functions and the coordination number. [1] D. Hagberg, G. Karlstrom, B.O. Roos and L. Gagliardi The coordination of uranyl in water: a combined quantum chemical and molecular simulation study J. Am. Chem. Soc. 127, 14250-14256 (2005)

Sparingly Solvating Electrolytes for High Energy Density Lithium-Sulfur Batteries

Energy Technology Data Exchange (ETDEWEB)

Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R.; Gewirth, Andrew A.; Shao, Yuyan; Gallagher, Kevin

2016-07-11

Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systems that fundamentally decouple electrolyte volume from reaction mechanism. This perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.

Solvates of silico-12-molybdic acid with alcohols

International Nuclear Information System (INIS)

Punchuk, I.N.; Chuvaev, V.F.

1984-01-01

With the aim of investigating interaction processes of solid heteropolyacids and organic compounds, solvates are prepared. Solvates are products of adding gaseous methanol, ethanol and isopropanol to silico-12-molybdic acid. The compounds are studied by IR and PMR spectroscopy methods. Possible models for solvate structure are considered, as well as their connection with solvate properties and thermal decomposition

Electron spin resonance of the solvation of radiation-produced silver atoms in alcohol-water mixtures

International Nuclear Information System (INIS)

Li, A.S.W.; Kevan, L.

1982-01-01

Frozen solutions of silver salts exposed to 60 Co γ-irradiation form silver atoms by reaction of radiation-produced electrons with the silver ion. At 4 K the silver atoms are initially produced in a nonequilibrium or presolvated state and upon brief thermal excitation to 77 K the first solvation shell geometry changes towards an equilibrium or solvated silver atom. This is most pronounced in water but also occurs in methanol, ethanol and n-propanol matrices. The changes in the electron spin resonance magnetic parameters upon silver atom solvation have been determined. In alcohol-water mixtures Ag 0 is preferentially solvated by polycrystalline water at low alcohol concentration. Above a particular alcohol mole percent Ag 0 suddenly changes its environment to a glassy alcohol one. This sudden change occurs at 17, 13 and 6 mol % methanol, ethanol and n-propanol, respectively. These mole percents correlate with the minimum of the excess enthalpy of mixing and with the hydrogen atom trapping ability of these alcohol-water mixtures. The results also suggest that the local environmental disorder around Ag 0 increases with alcohol chain length in alcohol-water frozen solutions. (author)

Fragmentation study of isolated and nano-solvated biomolecules induced by collision with multiply charged ions and neutral particles

International Nuclear Information System (INIS)

Bernigaud, V.

2009-01-01

This thesis concerns a gas phase study of the fragmentation of bio-molecular systems induced by slow collisions with multiply charged ions (in the keV-region), alkali atoms and rare gases. The main objective was to study the physical processes involved in the dissociation of highly electronically excited systems. In order to elucidate the intrinsic properties of certain biomolecules (porphyrins and amino acids) we have performed experiments in the gas phase with isolated systems. The obtained results demonstrate the high stability of porphyrins after electron removal and attachment. Furthermore, a dependence of the fragmentation pattern produced by multiply charged ions on the isomeric structure of the alanine molecule has been shown. In a second part of the thesis, a strong influence of the environment of the biomolecule on the fragmentation channels, their modification and their new opening, has been clearly proven. This phenomenon occurs in the presence of other surrounding biomolecules (clusters of nucleobases) as well as for molecules of a solvent (molecules of water, methanol and acetonitrile) in which the biomolecule is embedded. In order to extend these studies to larger systems, a new experimental set-up, based on an electro-spray ion source combined with a quadrupole mass filter has been developed. Due to the successful tests and proposed improvements of the device future experiments will become available concerning the fragmentation of large charged and solvated bio-molecular systems induced by collision processes. (author) [fr

Some properties of ion and cluster plasma

International Nuclear Information System (INIS)

Gudzenko, L.I.; Derzhiev, V.I.; Yakovlenko, S.I.

1982-01-01

The aggregate of problems connected with the physics of ion and cluster plasma is qualitatively considered. Such a plasma can exist when a dense gas is ionized by a hard ionizer. The conditions for the formation of an ion plasma and the difference between its characteristics and those of an ordinary electron plasma are discussed; a solvated-ion model and the distribution of the clusters with respect to the number of solvated molecules are considered. The recombination rate of the positively and negatively charged clusters is roughly estimated. The parameters of a ball-lightning plasma are estimated on the basis of the cluster model

Computational solvation analysis of biomolecules in aqueous ionic liquid mixtures : From large flexible proteins to small rigid drugs.

Science.gov (United States)

Zeindlhofer, Veronika; Schröder, Christian

2018-06-01

Based on their tunable properties, ionic liquids attracted significant interest to replace conventional, organic solvents in biomolecular applications. Following a Gartner cycle, the expectations on this new class of solvents dropped after the initial hype due to the high viscosity, hydrolysis, and toxicity problems as well as their high cost. Since not all possible combinations of cations and anions can be tested experimentally, fundamental knowledge on the interaction of the ionic liquid ions with water and with biomolecules is mandatory to optimize the solvation behavior, the biodegradability, and the costs of the ionic liquid. Here, we report on current computational approaches to characterize the impact of the ionic liquid ions on the structure and dynamics of the biomolecule and its solvation layer to explore the full potential of ionic liquids.

Ion Correlation Effects in Salt-Doped Block Copolymers

Science.gov (United States)

Brown, Jonathan R.; Seo, Youngmi; Hall, Lisa M.

2018-03-01

We apply classical density functional theory to study how salt changes the microphase morphology of diblock copolymers. Polymers are freely jointed and one monomer type favorably interacts with ions, to account for the selective solvation that arises from different dielectric constants of the microphases. By including correlations from liquid state theory of an unbound reference fluid, the theory can treat chain behavior, microphase separation, ion correlations, and preferential solvation, at the same coarse-grained level. We show good agreement with molecular dynamics simulations.

The inhibition of positronium by the chloride ion in water and the positron: Chloride reaction

International Nuclear Information System (INIS)

Beling, C.D.; Smith, F.A.

1983-01-01

A discussion is made of existing theories of Ps inhibition in the presence of Cl - ions. Our favoured interpretation of the data uses the thermalised pre-solvated positron as a common precursor of Ps and e + Cl - . Consideration is given to the prevention of solvation by the strong electric fields in the vicinity of Cl - ions, assuming best estimates for the solvation time, positron mobility and intermolecular spacing. An expression for the Ps inhibition constant K is derived on the basis of diffusive capture. The observed enhancement of Ps yield at higher Cl - concentrations is attributed to the scavenging by the Cl - ion of highly mobile species such as H 2 + O within times approx.=10 -14 s. Dissociation between e + Cl - and the solvated state esub(s) + is suggested as the cause of the ''missing fraction''. (orig.)

Solvation of hydrocarbons in aqueous-organic mixtures

International Nuclear Information System (INIS)

Sedov, I.A.; Magsumov, T.I.; Solomonov, B.N.

2016-01-01

Highlights: • Thermodynamic functions of solvation in mixtures of water with acetone and acetonitrile are measured at T = 298.15 K. • Solvation of n-octane and toluene in aqueous-organic mixtures is studied. • When increasing water content, Gibbs free energies grow up steadily, while enthalpies have a maximum. • Hydrocarbons are preferentially solvated with organic cosolvent even in mixtures with rather high water content. • Acetonitrile suppresses the hydrophobic effect less than acetone. - Abstract: We study the solvation of two hydrocarbons, n-octane and toluene, in binary mixtures of water with organic cosolvents. Two polar aprotic cosolvents that are miscible with water in any proportions, acetonitrile and acetone, were considered. We determine the magnitudes of thermodynamic functions of dissolution and solvation at T = 298.15 K in the mixtures with various compositions. Solution calorimetry was used to measure the enthalpies of solution, and GC headspace analysis was applied to obtain limiting activity coefficients of solutes in the studied systems. For the first time, the enthalpies of solution of alkane in the mixtures with high water content were measured directly. We observed well-pronounced maxima of the dependencies of enthalpies of solvation from the composition of solvent and no maxima for the Gibbs free energies of solvation. Two factors are concluded to be important to explain the observed tendencies: high energy cost of reorganization of binary solvent upon insertion of solute molecules and preferential surrounding of hydrocarbons with the molecules of organic cosolvent. Enthalpy-entropy compensation leads to a steady growth of the Gibbs free energies with increasing water content. On the other hand, consideration of the plots of the Gibbs free energy against enthalpy of solvation clearly shows that the solvation properties are changed dramatically after addition of a rather small amount of organic cosolvents. It is shown that they

Spectroscopic and computational studies of ionic clusters as models of solvation and atmospheric reactions

Science.gov (United States)

Kuwata, Keith T.

Ionic clusters are useful as model systems for the study of fundamental processes in solution and in the atmosphere. Their structure and reactivity can be studied in detail using vibrational predissociation spectroscopy, in conjunction with high level ab initio calculations. This thesis presents the applications of infrared spectroscopy and computation to a variety of gas-phase cluster systems. A crucial component of the process of stratospheric ozone depletion is the action of polar stratospheric clouds (PSCs) to convert the reservoir species HCl and chlorine nitrate (ClONO2) to photochemically labile compounds. Quantum chemistry was used to explore one possible mechanism by which this activation is effected: Cl- + ClONO2 /to Cl2 + NO3- eqno(1)Correlated ab initio calculations predicted that the direct reaction of chloride ion with ClONO2 is facile, which was confirmed in an experimental kinetics study. In the reaction a weakly bound intermediate Cl2-NO3- is formed, with ~70% of the charge localized on the nitrate moiety. This enables the Cl2-NO3- cluster to be well solvated even in bulk solution, allowing (1) to be facile on PSCs. Quantum chemistry was also applied to the hydration of nitrosonium ion (NO+), an important process in the ionosphere. The calculations, in conjunction with an infrared spectroscopy experiment, revealed the structure of the gas-phase clusters NO+(H2O)n. The large degree of covalent interaction between NO+ and the lone pairs of the H2O ligands is contrasted with the weak electrostatic bonding between iodide ion and H2O. Finally, the competition between ion solvation and solvent self-association is explored for the gas-phase clusters Cl/-(H2O)n and Cl-(NH3)n. For the case of water, vibrational predissociation spectroscopy reveals less hydrogen bonding among H2O ligands than predicted by ab initio calculations. Nevertheless, for n /ge 5, cluster structure is dominated by water-water interactions, with Cl- only partially solvated by the

Relative Free Energies for Hydration of Monovalent Ions from QM and QM/MM Simulations.

Science.gov (United States)

Lev, Bogdan; Roux, Benoît; Noskov, Sergei Yu

2013-09-10

Methods directly evaluating the hydration structure and thermodynamics of physiologically relevant cations (Na(+), K(+), Cl(-), etc.) have wide ranging applications in the fields of inorganic, physical, and biological chemistry. All-atom simulations based on accurate potential energy surfaces appear to offer a viable option for assessing the chemistry of ion solvation. Although MD and free energy simulations of ion solvation with classical force fields have proven their usefulness, a number of challenges still remain. One of them is the difficulty of force field benchmarking and validation against structural and thermodynamic data obtained for a condensed phase. Hybrid quantum mechanical/molecular mechanical (QM/MM) models combined with sampling algorithms have the potential to provide an accurate solvation model and to incorporate the effects from the surrounding, which is often missing in gas-phase ab initio computations. Herein, we report the results from QM/MM free energy simulations of Na(+)/K(+) and Cl(-)/Br(-) hydration where we simultaneously characterized the relative thermodynamics of ion solvation and changes in the solvation structure. The Flexible Inner Region Ensemble Separator (FIRES) method was used to impose a spatial separation between QM region and the outer sphere of solvent molecules treated with the CHARMM27 force field. FEP calculations based on QM/MM simulations utilizing the CHARMM/deMon2k interface were performed with different basis set combinations for K(+)/Na(+) and Cl(-)/Br(-) perturbations to establish the dependence of the computed free energies on the basis set level. The dependence of the computed relative free energies on the size of the QM and MM regions is discussed. The current methodology offers an accurate description of structural and thermodynamic aspects of the hydration of alkali and halide ions in neat solvents and can be used to obtain thermodynamic data on ion solvation in condensed phase along with underlying

Enhanced free energy of extraction of Eu3+ and Am3+ ions towards diglycolamide appended calix[4]arene: insights from DFT-D3 and COSMO-RS solvation models.

Science.gov (United States)

Ali, Sk Musharaf

2017-08-22

Density functional theory in conjunction with COSMO and COSMO-RS solvation models employing dispersion correction (DFT-D3) has been applied to gain an insight into the complexation of Eu 3+ /Am 3+ with diglycolamide (DGA) and calix[4]arene appended diglycolamide (CAL4DGA) in ionic liquids by studying structures, energetics, thermodynamics and population analysis. The calculated Gibbs free energy for both Eu 3+ and Am 3+ ions with DGA was found to be smaller than that with CAL4DGA. The entropy of complexation was also found to be reduced to a large extent with DGA compared to complexation with CAL4DGA. The solution phase free energy was found to be negative and was higher for Eu 3+ ion. The entropy of complexation was not only found to be further reduced but also became negative in the case of DGA alone. Though the entropy was found to be negative it could not outweigh the high negative enthalpic contribution. The same trend was observed in the solution where the free energy of extraction, ΔG, for Eu 3+ ions was shown to be higher than that for Am 3+ ions towards free DGA. But the values of ΔG and ΔΔG(= ΔG Eu -ΔG Am ) were found to be much higher with CAL4DGA (-12.58 kcal mol -1 ) in the presence of nitrate ions compared to DGA (-1.69 kcal mol -1 ) due to enhanced electronic interaction and positive entropic contribution. Furthermore, both the COSMO and COSMO-RS models predict very close values of ΔΔΔG (= ΔΔG CAL4DGA - ΔΔG nDGA ), indicating that both solvation models could be applied for evaluating the metal ion selectivity. The value of the reaction free energy was found to be higher after dispersion correction. The charge on the Eu and Am atoms for the complexes with DGA and CAL4DGA indicates the charge-dipole type interaction leading to strong binding energy. The present theoretical results support the experimental findings and thus might be of importance in the design of functionalized ligands.

MTS-MD of Biomolecules Steered with 3D-RISM-KH Mean Solvation Forces Accelerated with Generalized Solvation Force Extrapolation.

Science.gov (United States)

Omelyan, Igor; Kovalenko, Andriy

2015-04-14

We developed a generalized solvation force extrapolation (GSFE) approach to speed up multiple time step molecular dynamics (MTS-MD) of biomolecules steered with mean solvation forces obtained from the 3D-RISM-KH molecular theory of solvation (three-dimensional reference interaction site model with the Kovalenko-Hirata closure). GSFE is based on a set of techniques including the non-Eckart-like transformation of coordinate space separately for each solute atom, extension of the force-coordinate pair basis set followed by selection of the best subset, balancing the normal equations by modified least-squares minimization of deviations, and incremental increase of outer time step in motion integration. Mean solvation forces acting on the biomolecule atoms in conformations at successive inner time steps are extrapolated using a relatively small number of best (closest) solute atomic coordinates and corresponding mean solvation forces obtained at previous outer time steps by converging the 3D-RISM-KH integral equations. The MTS-MD evolution steered with GSFE of 3D-RISM-KH mean solvation forces is efficiently stabilized with our optimized isokinetic Nosé-Hoover chain (OIN) thermostat. We validated the hybrid MTS-MD/OIN/GSFE/3D-RISM-KH integrator on solvated organic and biomolecules of different stiffness and complexity: asphaltene dimer in toluene solvent, hydrated alanine dipeptide, miniprotein 1L2Y, and protein G. The GSFE accuracy and the OIN efficiency allowed us to enlarge outer time steps up to huge values of 1-4 ps while accurately reproducing conformational properties. Quasidynamics steered with 3D-RISM-KH mean solvation forces achieves time scale compression of conformational changes coupled with solvent exchange, resulting in further significant acceleration of protein conformational sampling with respect to real time dynamics. Overall, this provided a 50- to 1000-fold effective speedup of conformational sampling for these systems, compared to conventional MD

Solvent effects on ion-receptor interactions in the presence of an external electric field.

Science.gov (United States)

Novák, Martin; Foroutan-Nejad, Cina; Marek, Radek

2016-11-09

In this work we investigated the influence of an external electric field on the arrangement of the solvent shells around ions interacting with a carbon-based receptor. Our survey reveals that the mechanism of interaction between a monoatomic ion and a π-type ion receptor varies by the variation in the solvent polarity, the nature of the ion, and the strength of the external field. The characteristics of the ion-surface interaction in nonpolar solvents are similar to those observed in a vacuum. However, in water, we identified two mechanisms. Soft and polarizable ions preferentially interact with the π-receptor. In contrast, two bonded states were found for hard ions. A fully solvated ion, weakly interacting with the receptor at weak field, and a strong π-complex at the strong-field regime were identified. An abrupt variation in the potential energy surface (PES) associated with the rearrangement of the solvation shell on the surface of the receptor induced by an external field was observed both in implicit and explicit solvent environments. The electric field at which the solvation shell breaks is proportional to the hardness of the ion as has been suggested recently based on experimental observations.

Solvated protein–DNA docking using HADDOCK

International Nuclear Information System (INIS)

Dijk, Marc van; Visscher, Koen M.; Kastritis, Panagiotis L.; Bonvin, Alexandre M. J. J.

2013-01-01

Interfacial water molecules play an important role in many aspects of protein–DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the docking of protein–DNA complexes and demonstrate its feasibility on a benchmark of 30 high-resolution protein–DNA complexes containing crystallographically-determined water molecules at their interfaces. Our protocol is capable of reproducing the solvation pattern at the interface and recovers hydrogen-bonded water-mediated contacts in many of the benchmark cases. Solvated docking leads to an overall improvement in the quality of the generated protein–DNA models for cases with limited conformational change of the partners upon complex formation. The applicability of this approach is demonstrated on real cases by docking a representative set of 6 complexes using unbound protein coordinates, model-built DNA and knowledge-based restraints. As HADDOCK supports the inclusion of a variety of NMR restraints, solvated docking is also applicable for NMR-based structure calculations of protein–DNA complexes.

Solvated protein-DNA docking using HADDOCK

Energy Technology Data Exchange (ETDEWEB)

Dijk, Marc van; Visscher, Koen M.; Kastritis, Panagiotis L.; Bonvin, Alexandre M. J. J., E-mail: a.m.j.j.bonvin@uu.nl [Utrecht University, Bijvoet Center for Biomolecular Research, Faculty of Science-Chemistry (Netherlands)

2013-05-15

Interfacial water molecules play an important role in many aspects of protein-DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the docking of protein-DNA complexes and demonstrate its feasibility on a benchmark of 30 high-resolution protein-DNA complexes containing crystallographically-determined water molecules at their interfaces. Our protocol is capable of reproducing the solvation pattern at the interface and recovers hydrogen-bonded water-mediated contacts in many of the benchmark cases. Solvated docking leads to an overall improvement in the quality of the generated protein-DNA models for cases with limited conformational change of the partners upon complex formation. The applicability of this approach is demonstrated on real cases by docking a representative set of 6 complexes using unbound protein coordinates, model-built DNA and knowledge-based restraints. As HADDOCK supports the inclusion of a variety of NMR restraints, solvated docking is also applicable for NMR-based structure calculations of protein-DNA complexes.

Updated Abraham solvation parameters for polychlorinated biphenyls

NARCIS (Netherlands)

van Noort, P.C.M.; Haftka, J.J.H.; Parsons, J.R.

2010-01-01

This study shows that the recently published polychlorinated biphenyl (PCB) Abraham solvation parameters predict PCB air−n-hexadecane and n-octanol−water partition coefficients very poorly, especially for highly ortho-chlorinated congeners. Therefore, an updated set of PCB solvation parameters was

Updated Abraham solvation parameters for polychlorinated biphenyls

NARCIS (Netherlands)

Noort, van P.C.M.; Haftka, J.J.H.; Parsons, J.R.

2010-01-01

This study shows that the recently published polychlorinated biphenyl (PCB) Abraham solvation parameters predict PCB air-n-hexadecane and n-octanol-water partition coefficients very poorly, especially for highly ortho-chlorinated congeners. Therefore, an updated set of PCB solvation parameters was

Estimate of electrostatic solvation free energy of electron in various polar solvents by using modified born equation

International Nuclear Information System (INIS)

Yamashita, Kazuo; Kitamura, Mitsutaka; Imai, Hideo

1976-01-01

The modified Born equation was tentatively applied to estimate the electrostatic free energies of solvation of the electron in various polar solvents. The related data of halide ions and a datum of the hydration free energy of the electron obtained by radiation chemical studies were used for the numerical calculations. (auth.)

Preferential solvation of ions in mixed solvents. 6: Univalent anions in aqueous organic solvents according to the inverse Kirkwood-Buff integral (IKBI) approach

International Nuclear Information System (INIS)

Marcus, Yizhak

2007-01-01

The inverse Kirkwood-Buff integral (IKBI) approach is applied to the preferential solvation of F - , Cl - , Br - , I - , and ClO 4 - in aqueous mixtures of the co-solvents (S) methanol (MeOH), ethanol (EtOH), t-butanol (t-BuOH), 1,2-ethanediol (EG), glycerol (Gly), acetone (Me 2 CO), acetonitrile (MeCN), formamide (FA), N,N-dimethylformamide (DMF), N,N,N',N',N'',N''-hexamethyl phosphoric triamide (HMPT), and dimethylsulfoxide (DMSO), as far as the relevant data exist in the literature. Fluoride anions are selectively solvated by the water up to large mole fractions (x S ≥ 0.4) of S = EtOH, t-BuOH, Me 2 CO, MeCN, and DMF, and up to lower contents (x S ∼ 0.1) of MeOH, EG, FA, and DMSO. The other anions are preferentially solvated by water to diminishing extent as their sizes become larger, and the largest ones show some preference for S in water-rich mixtures of MeOH and FA, whereas in aqueous Gly even chloride is preferentially solvated by the Gly. The competition between the co-solvent and the anion for the hydrogen bonds that water molecules donate is the main cause for the observed preferential solvation behaviour

Organic chemistry in Titan's upper atmosphere and its astrobiological consequences: I. Views towards Cassini plasma spectrometer (CAPS) and ion neutral mass spectrometer (INMS) experiments in space

Science.gov (United States)

Ali, A.; Sittler, E. C.; Chornay, D.; Rowe, B. R.; Puzzarini, C.

2015-05-01

radicals. These radical species subsequently might form carbanions via radiative electron attachment at low temperatures with thermal electrons. The classic example is the perinaphthenyl anion in Titan's upper atmosphere. Therefore, future astronomical observations of selected carbocations and corresponding carbanions are required to settle the key issue of molecular anion chemistry on Titan. Other than earth, Titan is the only planetary body in our solar system that is known to have reservoirs of permanent liquids on its surface. The synthesis of complex biomolecules either by organic catalysis of precipitated solutes “on hydrocarbon solvent” on Titan or through the solvation process indeed started in its upper atmosphere. The most notable examples in Titan's prebiotic atmospheric chemistry are conjugated and aromatic polycyclic molecules, N-heterocycles including the presence of imino >Cdbnd N-H functional group in the carbonium chemistry. Our major conclusion in this paper is that the synthesis of organic compounds in Titan's upper atmosphere is a direct consequence of the chemistry of carbocations involving the ion-molecule reactions. The observations of complexity in the organic chemistry on Titan from the Cassini-Huygens mission clearly indicate that Titan is so far the only planetary object in our solar system that will most likely provide an answer to the question of the synthesis of complex biomolecules on the primitive earth and the origin of life.

Differential geometry based solvation model II: Lagrangian formulation.

Science.gov (United States)

Chen, Zhan; Baker, Nathan A; Wei, G W

2011-12-01

Solvation is an elementary process in nature and is of paramount importance to more sophisticated chemical, biological and biomolecular processes. The understanding of solvation is an essential prerequisite for the quantitative description and analysis of biomolecular systems. This work presents a Lagrangian formulation of our differential geometry based solvation models. The Lagrangian representation of biomolecular surfaces has a few utilities/advantages. First, it provides an essential basis for biomolecular visualization, surface electrostatic potential map and visual perception of biomolecules. Additionally, it is consistent with the conventional setting of implicit solvent theories and thus, many existing theoretical algorithms and computational software packages can be directly employed. Finally, the Lagrangian representation does not need to resort to artificially enlarged van der Waals radii as often required by the Eulerian representation in solvation analysis. The main goal of the present work is to analyze the connection, similarity and difference between the Eulerian and Lagrangian formalisms of the solvation model. Such analysis is important to the understanding of the differential geometry based solvation model. The present model extends the scaled particle theory of nonpolar solvation model with a solvent-solute interaction potential. The nonpolar solvation model is completed with a Poisson-Boltzmann (PB) theory based polar solvation model. The differential geometry theory of surfaces is employed to provide a natural description of solvent-solute interfaces. The optimization of the total free energy functional, which encompasses the polar and nonpolar contributions, leads to coupled potential driven geometric flow and PB equations. Due to the development of singularities and nonsmooth manifolds in the Lagrangian representation, the resulting potential-driven geometric flow equation is embedded into the Eulerian representation for the purpose of

Partial solvation parameters and LSER molecular descriptors

International Nuclear Information System (INIS)

Panayiotou, Costas

2012-01-01

Graphical abstract: The one-to-one correspondence of LSER molecular descriptors and partial solvation parameters (PSPs) for propionic acid. Highlights: ► Quantum-mechanics based development of a new QSPR predictive method. ► One-to-one correspondence of partial solvation parameters and LSER molecular descriptors. ► Development of alternative routes for the determination of partial solvation parameters and solubility parameters. ► Expansion and enhancement of solubility parameter approach. - Abstract: The partial solvation parameters (PSP) have been defined recently, on the basis of the insight derived from modern quantum chemical calculations, in an effort to overcome some of the inherent restrictions of the original definition of solubility parameter and expand its range of applications. The present work continues along these lines and introduces two new solvation parameters, the van der Waals and the polarity/refractivity ones, which may replace both of the former dispersion and polar PSPs. Thus, one may use either the former scheme of PSPs (dispersion, polar, acidic, and basic) or, equivalently, the new scheme (van der Waals, polarity/refractivity, acidic, basic). The new definitions are made in a simple and straightforward manner and, thus, the strength and appeal of the widely accepted concept of solubility parameter is preserved. The inter-relations of the various PSPs are critically discussed and their values are tabulated for a variety of common substances. The advantage of the new scheme of PSPs is the bridge that makes with the corresponding Abraham’s LSER descriptors. With this bridge, one may exchange information between PSPs, LSER experimental scales, and quantum mechanics calculations such as via the COSMO-RS theory. The proposed scheme is a predictive one and it is applicable to, both, homo-solvated and hetero-solvated compounds. The new scheme is tested for the calculation of activity coefficients at infinite dilution, for octanol

Preferential solvation of ions in mixed solvents. 6: Univalent anions in aqueous organic solvents according to the inverse Kirkwood-Buff integral (IKBI) approach

Energy Technology Data Exchange (ETDEWEB)

Marcus, Yizhak [Department of Inorganic and Analytical Chemistry, Hebrew University of Jerusalem, Jerusalem 91904 (Israel)], E-mail: ymarcus@vms.huji.ac.il

2007-10-15

The inverse Kirkwood-Buff integral (IKBI) approach is applied to the preferential solvation of F{sup -}, Cl{sup -}, Br{sup -}, I{sup -}, and ClO{sub 4}{sup -} in aqueous mixtures of the co-solvents (S) methanol (MeOH), ethanol (EtOH), t-butanol (t-BuOH), 1,2-ethanediol (EG), glycerol (Gly), acetone (Me{sub 2}CO), acetonitrile (MeCN), formamide (FA), N,N-dimethylformamide (DMF), N,N,N',N',N'',N''-hexamethyl phosphoric triamide (HMPT), and dimethylsulfoxide (DMSO), as far as the relevant data exist in the literature. Fluoride anions are selectively solvated by the water up to large mole fractions (x{sub S} {>=} 0.4) of S = EtOH, t-BuOH, Me{sub 2}CO, MeCN, and DMF, and up to lower contents (x{sub S} {approx} 0.1) of MeOH, EG, FA, and DMSO. The other anions are preferentially solvated by water to diminishing extent as their sizes become larger, and the largest ones show some preference for S in water-rich mixtures of MeOH and FA, whereas in aqueous Gly even chloride is preferentially solvated by the Gly. The competition between the co-solvent and the anion for the hydrogen bonds that water molecules donate is the main cause for the observed preferential solvation behaviour.

A shell-resolved analysis of preferential solvation of coffee ingredients in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate

Science.gov (United States)

Zeindlhofer, Veronika; Berger, Magdalena; Steinhauser, Othmar; Schröder, Christian

2018-05-01

Ionic liquids increase the solubility of various coffee ingredients in aqueous solution but little is known about the underlying mechanism. Kirkwood-Buff integrals as well as the potential of mean force indicate that the imidazolium cations are accumulated at the surface of the solutes, removing water molecules from the solute surface. Although hydrogen bonding of the anions to hydroxy groups of the solutes can be detected, their concentration at the surface is less enhanced compared to the cations. The decomposition into solvation shells by Voronoi tessellation reveals that structural features are only observed in the first solvation shell. Nevertheless, the depletion of water and the excess concentration of the ions and, in particular, of the cations are visible in the next solvation shells as well. Therefore, classical arguments of hydrotropic theory fail to explain this behavior.

Solvated electron structure in glassy matrices

International Nuclear Information System (INIS)

Kevan, L.

1981-01-01

Current knowledge of the detailed geometrical structure of solvated electrons in aqueous and organic media is summarized. The geometry of solvated electrons in glassy methanol, ethanol, and 2-methyltetrahydrofuran is discussed. Advanced electron magnetic resonance methods and development of new methods of analysis of electron spin echo modulation patterns, second moment line shapes, and forbidden photon spin-flip transitions for paramagnetic species in these disordered systems are discussed. 66 references are cited

Studies of base pair sequence effects on DNA solvation based on all-atom molecular dynamics simulations.

Science.gov (United States)

Dixit, Surjit B; Mezei, Mihaly; Beveridge, David L

2012-07-01

Detailed analyses of the sequence-dependent solvation and ion atmosphere of DNA are presented based on molecular dynamics (MD) simulations on all the 136 unique tetranucleotide steps obtained by the ABC consortium using the AMBER suite of programs. Significant sequence effects on solvation and ion localization were observed in these simulations. The results were compared to essentially all known experimental data on the subject. Proximity analysis was employed to highlight the sequence dependent differences in solvation and ion localization properties in the grooves of DNA. Comparison of the MD-calculated DNA structure with canonical A- and B-forms supports the idea that the G/C-rich sequences are closer to canonical A- than B-form structures, while the reverse is true for the poly A sequences, with the exception of the alternating ATAT sequence. Analysis of hydration density maps reveals that the flexibility of solute molecule has a significant effect on the nature of observed hydration. Energetic analysis of solute-solvent interactions based on proximity analysis of solvent reveals that the GC or CG base pairs interact more strongly with water molecules in the minor groove of DNA that the AT or TA base pairs, while the interactions of the AT or TA pairs in the major groove are stronger than those of the GC or CG pairs. Computation of solvent-accessible surface area of the nucleotide units in the simulated trajectories reveals that the similarity with results derived from analysis of a database of crystallographic structures is excellent. The MD trajectories tend to follow Manning's counterion condensation theory, presenting a region of condensed counterions within a radius of about 17 A from the DNA surface independent of sequence. The GC and CG pairs tend to associate with cations in the major groove of the DNA structure to a greater extent than the AT and TA pairs. Cation association is more frequent in the minor groove of AT than the GC pairs. In general, the

Molecular Dynamics Simulations on the solvation and interfacial behaviour of hydrophobic species. Applications to the TATB hypothesis and to the liquid/liquid extraction of cations to supercritical CO2

International Nuclear Information System (INIS)

Schurhammer, R.

2001-12-01

We report molecular dynamics studies on the solvation of charged hydrophobic molecules in pure liquids and at liquid / liquid interfaces. The first part of the thesis deals with the TATB hypothesis according to which the Asφ 4 + (TA + ) and Bφ 4 - (TB - ) ions have the same free energy of solvation in any solvent. The two ions are found to be solvated differently in pure liquids (water, chloroform, acetonitrile) as at a chloroform / water interface. These results are confirmed by free energy calculations and by simulations on iso-volume spherical S + and S - ions, which perfectly meet the TATB criteria. The many methodological tests performed show the importance of (i) the corrected treatment of 'long range interactions' (ii) the precise repartition of atomic charges (iii) the solvent models, especially for water, on the + / - charge discrimination by solvent. In the second part, in relation to the liquid / liquid extraction of cations from water to supercritical CO 2 , we report the behaviour of ions (Cs + , UO 2 2+ , Eu 3+ ), of un-complexed extractants molecules (tri-n-butylphosphate, calixarene), of their complexes with the cations and nitric acid at a preformed chloroform / water interface and during de-mixing simulations which started from a perfectly mixed CO 2 / water solutions. These studies demonstrate the importance of interfacial phenomena, of simulation conditions and acid and extractant concentrations, in assisted ion extraction to supercritical CO 2 . (author)

Theories of the solvated electron

International Nuclear Information System (INIS)

Kestner, N.R.

1987-01-01

In this chapter the authors address only the final state of the electron, that is, the solvated state, which, if no chemical reaction would occur, is a stable entity with well-defined characteristics. Except for some metal-ammonia solutions, and possible a few other cases, such stable species, in reality, exist but a short time (often as short as microseconds). Nevertheless, this chapter only deals with this final time-independent,'' completely solvated,'' equilibrium species. The last statement is added to indicate that the solvent around the electron has also come to thermal equilibrium with the field of the charge

Rapid heating evaporation of Pb(NO3)2. Evidence for heterogeneous ion-molecule reactions

International Nuclear Information System (INIS)

Radus, T.P.; Udseth, H.R.; Friedman, L.

1979-01-01

A mass spectrometric investigation of the lead nitrate system is reported in which the lead nitrate was evaporated from a probe filament that was heated as rapidly as 5000 0 C/s. Both electron impact (EI) and chemical ionization (CI) source techniques were used in this study. Fragment ions and decomposition products were observed under EI conditions. Under CI conditions solvated fragment ions and protonated solvated molecular ions were detected. Temperature measurements of rates of evaporation were made by monitoring the resistance of the probe filament as it was heated. Activation energies calculated by using these temperature coefficients of evaporation rates indicate that evaporations under CI conditions are assisted by heterogeneous ion-molecule reactions

Role of trapped and solvated electrons in Ps formation

International Nuclear Information System (INIS)

Stepanov, S.V.; Byakov, V.M.; Mikhin, K.V.; He, C.; Hirade, T.

2005-01-01

Role of trapped and solvated electrons in Ps formation is discussed. Combination of thermalized positron with such electrons is possible from the view point of the energy balance and may results in Ps formation. This process proceeds during all e = lifetime matter. Fitting of raw experimental e + -e - annihilation spectra has to be based on an adequate physical input, which often leads to necessity of nonexponential deconvolution of the spectra. We have interpreted the Ps formation data in polyethylene, ethylene-methylmethacrylate and polymethylmethacrylate in dark and in light vs. tome of the measurement and temperature. parameters characterized accumulation of trapped electrons and their recombination with counter ions and positrons are obtained. (author)

Theory of competitive solvation of polymers by two solvents and entropy-enthalpy compensation in the solvation free energy upon dilution with the second solvent.

Science.gov (United States)

Dudowicz, Jacek; Freed, Karl F; Douglas, Jack F

2015-06-07

We develop a statistical mechanical lattice theory for polymer solvation by a pair of relatively low molar mass solvents that compete for binding to the polymer backbone. A theory for the equilibrium mixture of solvated polymer clusters {AiBCj} and free unassociated molecules A, B, and C is formulated in the spirit of Flory-Huggins mean-field approximation. This theoretical framework enables us to derive expressions for the boundaries for phase stability (spinodals) and other basic properties of these polymer solutions: the internal energy U, entropy S, specific heat CV, extent of solvation Φsolv, average degree of solvation 〈Nsolv〉, and second osmotic virial coefficient B2 as functions of temperature and the composition of the mixture. Our theory predicts many new phenomena, but the current paper applies the theory to describe the entropy-enthalpy compensation in the free energy of polymer solvation, a phenomenon observed for many years without theoretical explanation and with significant relevance to liquid chromatography and other polymer separation methods.

Minimization of Ion-Solvent Clusters in Gel Electrolytes Containing Graphene Oxide Quantum Dots for Lithium-Ion Batteries.

Science.gov (United States)

Chen, Yen-Ming; Hsu, Shih-Ting; Tseng, Yu-Hsien; Yeh, Te-Fu; Hou, Sheng-Shu; Jan, Jeng-Shiung; Lee, Yuh-Lang; Teng, Hsisheng

2018-03-01

This study uses graphene oxide quantum dots (GOQDs) to enhance the Li + -ion mobility of a gel polymer electrolyte (GPE) for lithium-ion batteries (LIBs). The GPE comprises a framework of poly(acrylonitrile-co-vinylacetate) blended with poly(methyl methacrylate) and a salt LiPF 6 solvated in carbonate solvents. The GOQDs, which function as acceptors, are small (3-11 nm) and well dispersed in the polymer framework. The GOQDs suppress the formation of ion-solvent clusters and immobilize PF6- anions, affording the GPE a high ionic conductivity and a high Li + -ion transference number (0.77). When assembled into Li|electrolyte|LiFePO 4 batteries, the GPEs containing GOQDs preserve the battery capacity at high rates (up to 20 C) and exhibit 100% capacity retention after 500 charge-discharge cycles. Smaller GOQDs are more effective in GPE performance enhancement because of the higher dispersion of QDs. The minimization of both the ion-solvent clusters and degree of Li + -ion solvation in the GPEs with GOQDs results in even plating and stripping of the Li-metal anode; therefore, Li dendrite formation is suppressed during battery operation. This study demonstrates a strategy of using small GOQDs with tunable properties to effectively modulate ion-solvent coordination in GPEs and thus improve the performance and lifespan of LIBs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Breaking the polar-nonpolar division in solvation free energy prediction.

Science.gov (United States)

Wang, Bao; Wang, Chengzhang; Wu, Kedi; Wei, Guo-Wei

2018-02-05

Implicit solvent models divide solvation free energies into polar and nonpolar additive contributions, whereas polar and nonpolar interactions are inseparable and nonadditive. We present a feature functional theory (FFT) framework to break this ad hoc division. The essential ideas of FFT are as follows: (i) representability assumption: there exists a microscopic feature vector that can uniquely characterize and distinguish one molecule from another; (ii) feature-function relationship assumption: the macroscopic features, including solvation free energy, of a molecule is a functional of microscopic feature vectors; and (iii) similarity assumption: molecules with similar microscopic features have similar macroscopic properties, such as solvation free energies. Based on these assumptions, solvation free energy prediction is carried out in the following protocol. First, we construct a molecular microscopic feature vector that is efficient in characterizing the solvation process using quantum mechanics and Poisson-Boltzmann theory. Microscopic feature vectors are combined with macroscopic features, that is, physical observable, to form extended feature vectors. Additionally, we partition a solvation dataset into queries according to molecular compositions. Moreover, for each target molecule, we adopt a machine learning algorithm for its nearest neighbor search, based on the selected microscopic feature vectors. Finally, from the extended feature vectors of obtained nearest neighbors, we construct a functional of solvation free energy, which is employed to predict the solvation free energy of the target molecule. The proposed FFT model has been extensively validated via a large dataset of 668 molecules. The leave-one-out test gives an optimal root-mean-square error (RMSE) of 1.05 kcal/mol. FFT predictions of SAMPL0, SAMPL1, SAMPL2, SAMPL3, and SAMPL4 challenge sets deliver the RMSEs of 0.61, 1.86, 1.64, 0.86, and 1.14 kcal/mol, respectively. Using a test set of 94

Quantum-chemical study of hydride transfer in catalytic transformation of paraffins on zeolites

NARCIS (Netherlands)

Kazansky, V.B.; Frash, M.V.; Santen, van R.A.; Chon, H.; Ihm, S.-K.; Uh, Y.S.

1997-01-01

Ab initio quantum-chemical cluster calculations demonstrate that the activated complexes of hydride transfer reaction in catalytic transformation of paraffins on zeolites very much resembles adsorbed nonclassical carbonium ions. The calculated activation energies for reactions involving propane and

Molecular Dynamics Simulations on the solvation and interfacial behaviour of hydrophobic species. Applications to the TATB hypothesis and to the liquid/liquid extraction of cations to supercritical CO{sub 2}; Simulations par dynamique moleculaire de la solvatation et du comportement interfacial d'especes hydrophobes: application a l'hypothese TATB et a l'extraction liquide/liquide de cations par le CO{sub 2} supercritique

Energy Technology Data Exchange (ETDEWEB)

Schurhammer, R

2001-12-15

We report molecular dynamics studies on the solvation of charged hydrophobic molecules in pure liquids and at liquid / liquid interfaces. The first part of the thesis deals with the TATB hypothesis according to which the As{phi}{sub 4}{sup +} (TA{sup +}) and B{phi}{sub 4}{sup -} (TB{sup -}) ions have the same free energy of solvation in any solvent. The two ions are found to be solvated differently in pure liquids (water, chloroform, acetonitrile) as at a chloroform / water interface. These results are confirmed by free energy calculations and by simulations on iso-volume spherical S{sup +} and S{sup -} ions, which perfectly meet the TATB criteria. The many methodological tests performed show the importance of (i) the corrected treatment of 'long range interactions' (ii) the precise repartition of atomic charges (iii) the solvent models, especially for water, on the + / - charge discrimination by solvent. In the second part, in relation to the liquid / liquid extraction of cations from water to supercritical CO{sub 2}, we report the behaviour of ions (Cs{sup +}, UO{sub 2}{sup 2+}, Eu{sup 3+}), of un-complexed extractants molecules (tri-n-butylphosphate, calixarene), of their complexes with the cations and nitric acid at a preformed chloroform / water interface and during de-mixing simulations which started from a perfectly mixed CO{sub 2} / water solutions. These studies demonstrate the importance of interfacial phenomena, of simulation conditions and acid and extractant concentrations, in assisted ion extraction to supercritical CO{sub 2}. (author)

Polarization and charge transfer in the hydration of chloride ions

International Nuclear Information System (INIS)

Zhao Zhen; Rogers, David M.; Beck, Thomas L.

2010-01-01

A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters. The quantum theory of atoms in molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. The clusters extracted from the AMOEBA simulations exhibit high probabilities of anisotropic solvation for chloride ions in bulk water. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared to the quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2-level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.

Ionic strength independence of charge distributions in solvation of biomolecules

Energy Technology Data Exchange (ETDEWEB)

Virtanen, J. J. [Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States); James Franck Institute, University of Chicago, Chicago, Illinois 60637 (United States); Sosnick, T. R. [Department of Biochemistry and Molecular Biology, Institute for Biophysical Dynamics, University of Chicago, Chicago, Illinois 60637 (United States); Computation Institute, University of Chicago, Chicago, Illinois 60637 (United States); Freed, K. F. [Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States); James Franck Institute, University of Chicago, Chicago, Illinois 60637 (United States); Computation Institute, University of Chicago, Chicago, Illinois 60637 (United States)

2014-12-14

Electrostatic forces enormously impact the structure, interactions, and function of biomolecules. We perform all-atom molecular dynamics simulations for 5 proteins and 5 RNAs to determine the dependence on ionic strength of the ion and water charge distributions surrounding the biomolecules, as well as the contributions of ions to the electrostatic free energy of interaction between the biomolecule and the surrounding salt solution (for a total of 40 different biomolecule/solvent combinations). Although water provides the dominant contribution to the charge density distribution and to the electrostatic potential even in 1M NaCl solutions, the contributions of water molecules and of ions to the total electrostatic interaction free energy with the solvated biomolecule are comparable. The electrostatic biomolecule/solvent interaction energies and the total charge distribution exhibit a remarkable insensitivity to salt concentrations over a huge range of salt concentrations (20 mM to 1M NaCl). The electrostatic potentials near the biomolecule's surface obtained from the MD simulations differ markedly, as expected, from the potentials predicted by continuum dielectric models, even though the total electrostatic interaction free energies are within 11% of each other.

Ionic strength independence of charge distributions in solvation of biomolecules

International Nuclear Information System (INIS)

Virtanen, J. J.; Sosnick, T. R.; Freed, K. F.

2014-01-01

Electrostatic forces enormously impact the structure, interactions, and function of biomolecules. We perform all-atom molecular dynamics simulations for 5 proteins and 5 RNAs to determine the dependence on ionic strength of the ion and water charge distributions surrounding the biomolecules, as well as the contributions of ions to the electrostatic free energy of interaction between the biomolecule and the surrounding salt solution (for a total of 40 different biomolecule/solvent combinations). Although water provides the dominant contribution to the charge density distribution and to the electrostatic potential even in 1M NaCl solutions, the contributions of water molecules and of ions to the total electrostatic interaction free energy with the solvated biomolecule are comparable. The electrostatic biomolecule/solvent interaction energies and the total charge distribution exhibit a remarkable insensitivity to salt concentrations over a huge range of salt concentrations (20 mM to 1M NaCl). The electrostatic potentials near the biomolecule's surface obtained from the MD simulations differ markedly, as expected, from the potentials predicted by continuum dielectric models, even though the total electrostatic interaction free energies are within 11% of each other

Standard electrode potential, Tafel equation, and the solvation thermodynamics.

Science.gov (United States)

Matyushov, Dmitry V

2009-06-21

Equilibrium in the electronic subsystem across the solution-metal interface is considered to connect the standard electrode potential to the statistics of localized electronic states in solution. We argue that a correct derivation of the Nernst equation for the electrode potential requires a careful separation of the relevant time scales. An equation for the standard metal potential is derived linking it to the thermodynamics of solvation. The Anderson-Newns model for electronic delocalization between the solution and the electrode is combined with a bilinear model of solute-solvent coupling introducing nonlinear solvation into the theory of heterogeneous electron transfer. We therefore are capable of addressing the question of how nonlinear solvation affects electrochemical observables. The transfer coefficient of electrode kinetics is shown to be equal to the derivative of the free energy, or generalized force, required to shift the unoccupied electronic level in the bulk. The transfer coefficient thus directly quantifies the extent of nonlinear solvation of the redox couple. The current model allows the transfer coefficient to deviate from the value of 0.5 of the linear solvation models at zero electrode overpotential. The electrode current curves become asymmetric in respect to the change in the sign of the electrode overpotential.

Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

International Nuclear Information System (INIS)

Wishart, J.F.

2011-01-01

Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs generally have low volatilities and are combustion-resistant, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of primary radiation chemistry, charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of reactions and product distributions. We study these issues by characterization of primary radiolysis products and measurements of their yields and reactivity, quantification of electron solvation dynamics and scavenging of electrons in different states of solvation. From this knowledge we wish to learn how to predict radiolytic mechanisms and control them or mitigate their effects on the properties of materials used in nuclear fuel processing, for example, and to apply IL radiation chemistry to answer questions about general chemical reactivity in ionic liquids that will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that the slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increase the importance of pre-solvated electron reactivity and consequently alter product distributions and subsequent chemistry. This difference from conventional solvents has profound effects on predicting and controlling radiolytic yields

A self-consistent phase-field approach to implicit solvation of charged molecules with Poisson–Boltzmann electrostatics

Science.gov (United States)

Sun, Hui; Wen, Jiayi; Zhao, Yanxiang; Li, Bo; McCammon, J. Andrew

2015-01-01

Dielectric boundary based implicit-solvent models provide efficient descriptions of coarse-grained effects, particularly the electrostatic effect, of aqueous solvent. Recent years have seen the initial success of a new such model, variational implicit-solvent model (VISM) [Dzubiella, Swanson, and McCammon Phys. Rev. Lett. 96, 087802 (2006) and J. Chem. Phys. 124, 084905 (2006)], in capturing multiple dry and wet hydration states, describing the subtle electrostatic effect in hydrophobic interactions, and providing qualitatively good estimates of solvation free energies. Here, we develop a phase-field VISM to the solvation of charged molecules in aqueous solvent to include more flexibility. In this approach, a stable equilibrium molecular system is described by a phase field that takes one constant value in the solute region and a different constant value in the solvent region, and smoothly changes its value on a thin transition layer representing a smeared solute-solvent interface or dielectric boundary. Such a phase field minimizes an effective solvation free-energy functional that consists of the solute-solvent interfacial energy, solute-solvent van der Waals interaction energy, and electrostatic free energy described by the Poisson–Boltzmann theory. We apply our model and methods to the solvation of single ions, two parallel plates, and protein complexes BphC and p53/MDM2 to demonstrate the capability and efficiency of our approach at different levels. With a diffuse dielectric boundary, our new approach can describe the dielectric asymmetry in the solute-solvent interfacial region. Our theory is developed based on rigorous mathematical studies and is also connected to the Lum–Chandler–Weeks theory (1999). We discuss these connections and possible extensions of our theory and methods. PMID:26723595

A self-consistent phase-field approach to implicit solvation of charged molecules with Poisson-Boltzmann electrostatics.

Science.gov (United States)

Sun, Hui; Wen, Jiayi; Zhao, Yanxiang; Li, Bo; McCammon, J Andrew

2015-12-28

Dielectric boundary based implicit-solvent models provide efficient descriptions of coarse-grained effects, particularly the electrostatic effect, of aqueous solvent. Recent years have seen the initial success of a new such model, variational implicit-solvent model (VISM) [Dzubiella, Swanson, and McCammon Phys. Rev. Lett. 96, 087802 (2006) and J. Chem. Phys. 124, 084905 (2006)], in capturing multiple dry and wet hydration states, describing the subtle electrostatic effect in hydrophobic interactions, and providing qualitatively good estimates of solvation free energies. Here, we develop a phase-field VISM to the solvation of charged molecules in aqueous solvent to include more flexibility. In this approach, a stable equilibrium molecular system is described by a phase field that takes one constant value in the solute region and a different constant value in the solvent region, and smoothly changes its value on a thin transition layer representing a smeared solute-solvent interface or dielectric boundary. Such a phase field minimizes an effective solvation free-energy functional that consists of the solute-solvent interfacial energy, solute-solvent van der Waals interaction energy, and electrostatic free energy described by the Poisson-Boltzmann theory. We apply our model and methods to the solvation of single ions, two parallel plates, and protein complexes BphC and p53/MDM2 to demonstrate the capability and efficiency of our approach at different levels. With a diffuse dielectric boundary, our new approach can describe the dielectric asymmetry in the solute-solvent interfacial region. Our theory is developed based on rigorous mathematical studies and is also connected to the Lum-Chandler-Weeks theory (1999). We discuss these connections and possible extensions of our theory and methods.

Order and correlation contributions to the entropy of hydrophobic solvation

Energy Technology Data Exchange (ETDEWEB)

Liu, Maoyuan; Besford, Quinn Alexander; Mulvaney, Thomas; Gray-Weale, Angus, E-mail: gusgw@gusgw.net [School of Chemistry, The University of Melbourne, Victoria 3010 (Australia)

2015-03-21

The entropy of hydrophobic solvation has been explained as the result of ordered solvation structures, of hydrogen bonds, of the small size of the water molecule, of dispersion forces, and of solvent density fluctuations. We report a new approach to the calculation of the entropy of hydrophobic solvation, along with tests of and comparisons to several other methods. The methods are assessed in the light of the available thermodynamic and spectroscopic information on the effects of temperature on hydrophobic solvation. Five model hydrophobes in SPC/E water give benchmark solvation entropies via Widom’s test-particle insertion method, and other methods and models are tested against these particle-insertion results. Entropies associated with distributions of tetrahedral order, of electric field, and of solvent dipole orientations are examined. We find these contributions are small compared to the benchmark particle-insertion entropy. Competitive with or better than other theories in accuracy, but with no free parameters, is the new estimate of the entropy contributed by correlations between dipole moments. Dipole correlations account for most of the hydrophobic solvation entropy for all models studied and capture the distinctive temperature dependence seen in thermodynamic and spectroscopic experiments. Entropies based on pair and many-body correlations in number density approach the correct magnitudes but fail to describe temperature and size dependences, respectively. Hydrogen-bond definitions and free energies that best reproduce entropies from simulations are reported, but it is difficult to choose one hydrogen bond model that fits a variety of experiments. The use of information theory, scaled-particle theory, and related methods is discussed briefly. Our results provide a test of the Frank-Evans hypothesis that the negative solvation entropy is due to structured water near the solute, complement the spectroscopic detection of that solvation structure by

Microscopic solvation of a lithium atom in water-ammonia mixed clusters: solvent coordination and electron localization in presence of a counterion.

Science.gov (United States)

Pratihar, Subha; Chandra, Amalendu

2008-07-14

The microsolvation structures and energetics of water-ammonia mixed clusters containing a lithium atom, i.e., Li(H(2)O)(n)(NH(3)), n = 1-5, are investigated by means of ab initio theoretical calculations. Several structural aspects such as the solvent coordination to the metal ion and binding motifs of the free valence electron of the metal are investigated. We also study the energetics aspects such as the dependence of vertical ionization energies on the cluster size, and all these structural and energetics aspects are compared to the corresponding results of previously studied anionic water-ammonia clusters without a metal ion. It is found that the Li-O and Li-N interactions play a very important role in stabilizing the lithium-water-ammonia clusters, and the presence of these metal ion-solvent interactions also affect the characteristics of electron solvation in these clusters. This is seen from the spatial distribution of the singly occupied molecular orbital (SOMO) which holds the ejected valence electron of the Li atom. For very small clusters, SOMO electron density is found to exist mainly at the vicinity of the Li atom, whereas for larger clusters, it is distributed outside the first solvation shell. The free dangling hydrogens of water and ammonia molecules are involved in capturing the SOMO electron density. In some of the conformers, OH{e}HO and OH{e}HN types of interactions are found to be present. The presence of the metal ion at the center of the cluster ensures that the ejected electron is solvated at a surface state only, whereas both surface and interiorlike states were found for the free electron in the corresponding anionic clusters without a metal ion. The vertical ionization energies of the present clusters are found to be higher than the vertical detachment energies of the corresponding anionic clusters which signify a relatively stronger binding of the free electron in the presence of the positive metal counterion. The shifts in different

Solvation of graphite oxide in water-methanol binary polar solvents

Energy Technology Data Exchange (ETDEWEB)

You, Shujie; Yu, Junchun; Sundqvist, Bertil; Talyzin, Alexandr V. [Department of Physics, Umeaa University, SE-901 87 Umeaa (Sweden)

2012-12-15

The phase transition between two solvated phases was studied by DSC for graphite oxide (GO) powders immersed in water-methanol mixtures of various compositions. GO forms solid solvates with two different compositions when immersed in methanol. Reversible phase transition between two solvate states due to insertion/desertion of methanol monolayer occurs upon temperature variations. The temperature point and the enthalpy ({Delta}H) of the phase transition are maximal for pure methanol and decrease linearly with increase of water fraction up to 30%. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Ion-Molecule Reaction Dynamics.

Science.gov (United States)

Meyer, Jennifer; Wester, Roland

2017-05-05

We review the recent advances in the investigation of the dynamics of ion-molecule reactions. During the past decade, the combination of single-collision experiments in crossed ion and neutral beams with the velocity map ion imaging detection technique has enabled a wealth of studies on ion-molecule reactions. These methods, in combination with chemical dynamics simulations, have uncovered new and unexpected reaction mechanisms, such as the roundabout mechanism and the subtle influence of the leaving group in anion-molecule nucleophilic substitution reactions. For this important class of reactions, as well as for many fundamental cation-molecule reactions, the information obtained with crossed-beam imaging is discussed. The first steps toward understanding micro-solvation of ion-molecule reaction dynamics are presented. We conclude with the presentation of several interesting directions for future research.

Rate theory of solvent exchange and kinetics of Li(+) - BF4 (-)/PF6 (-) ion pairs in acetonitrile.

Science.gov (United States)

Dang, Liem X; Chang, Tsun-Mei

2016-09-07

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li(+) and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li(+) in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li(+)-[BF4] and Li(+)-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li(+). We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li(+)-[BF4] and Li(+)-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

Recent results on solvation dynamics of electron and spur reactions of solvated electron in polar solvents studied by femtosecond laser spectroscopy and picosecond pulse radiolysis

International Nuclear Information System (INIS)

Mostafavi, M.

2006-01-01

Here, we report several studies done recently at ELYSE laboratory on the solvation dynamics of electron and on the kinetics of solvated electron in the spur reactions, performed by femtosecond laser spectroscopy and picosecond pulse radiolysis, respectively. Solvated electrons have been produced in polyol (1,2-Etanediol, 1,2-Propanediol and 1,3-Propanediol) by two-photon ionization of the solvent with 263 nm femtosecond laser pulses at room temperature. The two-photon absorption coefficient of these solvents at 263 nm has been determined. The dynamics of electron solvation in polyols has been studied by pump-probe transient absorption spectroscopy. So, time resolved absorption spectra ranging from 430 to 720 nm have been measured (Figure 1). A blue shift of the spectra is observed for the first tens of picoseconds. Using Bayesian data analysis method, the observed solvation dynamics are reconstructed with different models: stepwise mechanisms, continuous relaxation models or combinations of stepwise and continuous relaxation. That analysis clearly indicates that it is not obvious to select a unique model to describe the solvation dynamics of electron in diols. We showed that several models are able to reproduce correctly the data: a two-step model, a heterogeneous or bi-exponential continuous relaxation model and even a hybrid model with a stepwise transition and homogeneous continuous relaxation. Nevertheless, the best fits are given by the continuous spectral relaxation models. The fact that the time-evolution of the absorption spectrum of the solvated electron in diols can be accurately described by the temperature dependent absorption spectrum of the ground state solvated electron suggests that the spectral blue shift is mostly caused by the continuous relaxation of the electron trapped in a large distribution of solvent cages. Similar trends on electron solvation dynamics are observed in the cases of 1,2-ethanediol, 1,3-propanediol and 1,2 propanediol

Solvation of the electron in alcohols studied using the Argonne picosecond pulse radiolysis system

International Nuclear Information System (INIS)

Jonah, C.D.; Kenney-Wallace, G.A.

1979-01-01

With a stroboscopic pulse radiolysis system, it is possible to measure the reactions of solvated electrons and dry electrons and the solvation time of electrons in alcohols from 20 psec to 350 psec. The solvation in alcohol and alcohol-alkane solutions is a complex process which depends on the microscopic structure of the fluid, so that the studies of solvation in alcohols as a function of temperature or as a function of the concentration of the alcohols must take into account the structure of the fluid being studied. The relaxation processes may not be dominant at low temperature. However, in room temperature alcohols, pre-existing traps are the dominant means of electron trapping. The extrapolation to water may be reasonable since water and alcohols both give similar final species. To obtain such idea of the solvation process in alcohols, the change of the absorption of electrons at 500 nm was measured. At very low concentration of alcohols in alkanes, electrons form a complex with a cluster of alcohol molecules, and the most probable size of this cluster is two alcohols (C 4 , C 10 ). The species formed is not solvated electrons, since the characteristic spectrum of solvated electrons is absent, and the conductivity of the species is far above that of solvated electrons. (Yamashita, S.)

Determination of membrane hydration numbers of alkali metal ions by insertion in a conducting polymer

DEFF Research Database (Denmark)

Skaarup, Steen; Junaid Mohamed Jafeen, Mohamed; Careem, M.A.

2010-01-01

, and a secondary (or outer) solvation shell, consisting of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior...... may depend on the details of ion hydration. Although the solvation of alkali metal ions in aqueous solution has been discussed for many years, there is still no clear consensus. Part of the discrepancy is simply that different methods measure over different time scales, and therefore do...... not necessarily define the same hydration shell. This work presents a systematic study of one special variant of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS-). The technique...

Solvation pressure as real pressure: I. Ethanol and starch under negative pressure

CERN Document Server

Uden, N W A V; Faux, D A; Tanczos, A C; Howlin, B; Dunstan, D J

2003-01-01

The reality of the solvation pressure generated by the cohesive energy density of liquids is demonstrated by three methods. Firstly, the Raman spectrum of ethanol as a function of cohesive energy density (solvation pressure) in ethanol-water and ethanol-chloroform mixtures is compared with the Raman spectrum of pure ethanol under external hydrostatic pressure and the solvation pressure and hydrostatic pressure are found to be equivalent for some transitions. Secondly, the bond lengths of ethanol are calculated by molecular dynamics modelling for liquid ethanol under pressure and for ethanol vapour. The difference in bond lengths between vapour and liquid are found to be equivalent to the solvation pressure for the C-H sub 3 , C-H sub 2 and O-H bond lengths, with discrepancies for the C-C and C-O bond lengths. Thirdly, the pressure-induced gelation of potato starch is measured in pure water and in mixtures of water and ethanol. The phase transition pressure varies in accordance with the change in solvation pre...

Influence of GTP/GDP and magnesium ion on the solvated structure of the protein FtsZ: a molecular dynamics study.

Science.gov (United States)

Jamous, Carla; Basdevant, Nathalie; Ha-Duong, Tap

2014-01-01

We present here a structural analysis of ten extensive all-atom molecular dynamics simulations of the monomeric protein FtsZ in various binding states. Since the polymerization and GTPase activities of FtsZ depend on the nature of a bound nucleotide as well as on the presence of a magnesium ion, we studied the structural differences between the average conformations of the following five systems: FtsZ-Apo, FtsZ-GTP, FtsZ-GDP, FtsZ-GTP-Mg, and FtsZ-GDP-Mg. The in silico solvated average structure of FtsZ-Apo significantly differs from the crystallographic structure 1W59 of FtsZ which was crystallized in a dimeric form without nucleotide and magnesium. The simulated Apo form of the protein also clearly differs from the FtsZ structures when it is bound to its ligand, the most important discrepancies being located in the loops surrounding the nucleotide binding pocket. The three average structures of FtsZ-GTP, FtsZ-GDP, and FtsZ-GTP-Mg are overall similar, except for the loop T7 located at the opposite side of the binding pocket and whose conformation in FtsZ-GDP notably differs from the one in FtsZ-GTP and FtsZ-GTP-Mg. The presence of a magnesium ion in the binding pocket has no impact on the FtsZ conformation when it is bound to GTP. In contrast, when the protein is bound to GDP, the divalent cation causes a translation of the nucleotide outwards the pocket, inducing a significant conformational change of the loop H6-H7 and the top of helix H7.

Quantum calculations on water in the KcsA channel cavity with permeant and non-permeant ions

International Nuclear Information System (INIS)

Kariev, Alisher M.; Green, Michael E.

2009-01-01

Different ions in the pore of the KcsA channel behave differently, and we relate this to their solvation. We show that the selectivity is dependent, in part, on the solvation in the cavity (sometimes referred to as the vestibule, it is the region containing water molecules between the intracellular gate and the selectivity filter at the extracellular end of the pore). We have shown earlier that potassium is more dependent at the upper end of the cavity region on solvation by the threonines there, while sodium ion has more water molecules as ligands. In addition, sodium ion is placed asymmetrically, while potassium is nearly exactly symmetric with respect to the four-fold symmetry of the channel. We have now extended these calculations to rubidium and cesium ions, and find that rubidium solvation resembles that of potassium (and both are permeant ions), while cesium resembles sodium (and both are non-permeant), in terms of the geometry of up to eight hydrating, and four non-hydrating, water molecules. In each case, a maximum of 12 water molecules are relevant to the calculation. The placement of the water molecules in the two cases is essentially the same as found from the electron density in the X-ray structure of Zhou and MacKinnon. For Na + and K + , we show that energy decreases from bulk to the cavity to the lowest position in the selectivity filter (accurate energy could not be calculated for the heavier ions). A separate calculation shows that fixing the Na + ion at the position of the K + minimum, followed by re-optimization produced a significantly modified system, not something that could be produced by thermal fluctuations. Moving the K + into the Na + position in the upper cavity led to a small increase in energy, ∼ 3 k B T, but was accompanied by large shifts in the positions of hydrating waters, which would create a major kinetic barrier. Therefore, thermal fluctuations could not invalidate the conclusions of the main calculations.

Hydrophilic Solvation Dominates the Terahertz Fingerprint of Amino Acids in Water.

Science.gov (United States)

Esser, Alexander; Forbert, Harald; Sebastiani, Federico; Schwaab, Gerhard; Havenith, Martina; Marx, Dominik

2018-02-01

Spectroscopy in the terahertz frequency regime is a sensitive tool to probe solvation-induced effects in aqueous solutions. Yet, a systematic understanding of spectral lineshapes as a result of distinct solvation contributions remains terra incognita. We demonstrate that modularization of amino acids in terms of functional groups allows us to compute their distinct contributions to the total terahertz response. Introducing the molecular cross-correlation analysis method provides unique access to these site-specific contributions. Equivalent groups in different amino acids lead to look-alike spectral contributions, whereas side chains cause characteristic but additive complexities. Specifically, hydrophilic solvation of the zwitterionic groups in valine and glycine leads to similar terahertz responses which are fully decoupled from the side chain. The terahertz response due to H-bonding within the large hydrophobic solvation shell of valine turns out to be nearly indistinguishable from that in bulk water in direct comparison to the changes imposed by the charged functional groups that form strong H-bonds with their hydration shells. Thus, the hydrophilic groups and their solvation shells dominate the terahertz absorption difference, while on the same intensity scale, the influence of hydrophobic water can be neglected.

Pulse radiolysis study on solvated electrons in ionic liquid with controlling water content

International Nuclear Information System (INIS)

Yang Jinfeng; Kondoh, T.; Yoshida, Y.; Nagaishi, R.

2006-01-01

content of 0 to 1.4 wt% in ionic liquid, i.e., changing the ionic liquid from the dehydrated state to the water-saturated state. It indicates that the solvation structure of electrons solvated with DEMMA cations was changed to be that hydrated with water molecules, as shown in Fig. 1. In the experiment, several solutes, including acetone, trivalent ion of europium (III), pyrene, and biphenyl, were used to study the reactions of the solvated electrons in ionic liquid. (authors)

Ultrafast transient-absorption of the solvated electron in water

International Nuclear Information System (INIS)

Kimura, Y.; Alfano, J.C.; Walhout, P.K.; Barbara, P.F.

1994-01-01

Ultrafast near infrared (NIR)-pump/variable wavelength probe transient-absorption spectroscopy has been performed on the aqueous solvated electron. The photodynamics of the solvated electron excited to its p-state are qualitatively similar to previous measurements of the dynamics of photoinjected electrons at high energy. This result confirms the previous interpretation of photoinjected electron dynamics as having a rate-limiting bottleneck at low energies presumably involving the p-state

Dynamics of solvation and desolvation of rubidium attached to He nanodroplets

International Nuclear Information System (INIS)

Vangerow, J. von; John, O.; Stienkemeier, F.; Mudrich, M.

2015-01-01

The real-time dynamics of photoexcited and photoionized rubidium (Rb) atoms attached to helium (He) nanodroplets is studied by femtosecond pump-probe mass spectrometry. While excited Rb atoms in the perturbed 6p-state (Rb * ) desorb off the He droplets, Rb + photoions tend to sink into the droplet interior when created near the droplet surface. The transition from Rb + solvation to full Rb * desorption is found to occur at a delay time τ ∼ 600 fs for Rb * in the 6pΣ-state and τ ∼ 1200 fs for the 6pΠ-state. Rb + He ions are found to be created by directly exciting bound Rb * He exciplex states as well as by populating bound Rb + He-states in a photoassociative ionization process

Dynamics of solvation and desolvation of rubidium attached to He nanodroplets

Science.gov (United States)

von Vangerow, J.; John, O.; Stienkemeier, F.; Mudrich, M.

2015-07-01

The real-time dynamics of photoexcited and photoionized rubidium (Rb) atoms attached to helium (He) nanodroplets is studied by femtosecond pump-probe mass spectrometry. While excited Rb atoms in the perturbed 6p-state (Rb*) desorb off the He droplets, Rb+ photoions tend to sink into the droplet interior when created near the droplet surface. The transition from Rb+ solvation to full Rb* desorption is found to occur at a delay time τ ˜ 600 fs for Rb* in the 6pΣ-state and τ ˜ 1200 fs for the 6pΠ-state. Rb+He ions are found to be created by directly exciting bound Rb*He exciplex states as well as by populating bound Rb+He-states in a photoassociative ionization process.

The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model

Energy Technology Data Exchange (ETDEWEB)

Sundararaman, Ravishankar; Goddard, William A. [Joint Center for Artificial Photosynthesis, Pasadena, California 91125 (United States)

2015-02-14

Many important applications of electronic structure methods involve molecules or solid surfaces in a solvent medium. Since explicit treatment of the solvent in such methods is usually not practical, calculations often employ continuum solvation models to approximate the effect of the solvent. Previous solvation models either involve a parametrization based on atomic radii, which limits the class of applicable solutes, or based on solute electron density, which is more general but less accurate, especially for charged systems. We develop an accurate and general solvation model that includes a cavity that is a nonlocal functional of both solute electron density and potential, local dielectric response on this nonlocally determined cavity, and nonlocal approximations to the cavity-formation and dispersion energies. The dependence of the cavity on the solute potential enables an explicit treatment of the solvent charge asymmetry. With four parameters per solvent, this “CANDLE” model simultaneously reproduces solvation energies of large datasets of neutral molecules, cations, and anions with a mean absolute error of 1.8 kcal/mol in water and 3.0 kcal/mol in acetonitrile.

Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

Energy Technology Data Exchange (ETDEWEB)

Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.; Gates, B.C. [Univ. of California, Davis, CA (United States)

1995-12-31

The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.

Theory of optical spectra of solvated electrons

International Nuclear Information System (INIS)

Kestner, N.R.

1975-01-01

During the last few years better theoretical models of solvated electron have been developed. These models allow one to calculate a priori the observable properties of the trapped electron. One of the most important and most widely determined properties is the optical spectrum. In this paper we consider the predictions of the theories not only as to the band maximum but line shape and width. In addition we will review how the theories predict these will depend on the solvent, pressure, temperature, and solvent density. In all cases extensive comparisons will be made with experimental work. In addition four new areas will be explored and recent results will be presented. These concern electrons in dense polar gases, the time development of the solvated electron spectrum, solvated electrons in mixed solvents, and photoelectron emission spectra (PEE) as it relates to higher excited states. This paper will review all recent theoretical calculations and present a critical review of the present status and future developments which are anticipated. The best theories are quite successful in predicting trends, and qualitative agreement concerning band maximum. The theory is still weak in predicting line shape and line width

Ionic association and solvation of the ionic liquid 1-hexyl-3-methylimidazolium chloride in molecular solvents revealed by vapor pressure osmometry, conductometry, volumetry, and acoustic measurements.

Science.gov (United States)

Sadeghi, Rahmat; Ebrahimi, Nosaibah

2011-11-17

A systematic study of osmotic coefficient, conductivity, volumetric and acoustic properties of solutions of ionic liquid 1-hexyl-3-methylimidazolium chloride ([C(6)mim][Cl]) in various molecular solvents has been made at different temperatures in order to study of ionic association and solvation behavior of [C(6)mim][Cl] in different solutions. Precise measurements on electrical conductances of solutions of [C(6)mim][Cl] in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and acetonitrile at 293.15, 298.15, and 303.15 K are reported and analyzed with Barthel's low-concentration chemical model (lcCM) to obtain the limiting molar conductivities and association constants of this ionic liquid in the investigated solvents. Strong ion pairing was found for the ionic liquid in 2-propanol, 1-butanol, and 1-propanol, whereas ion association in acetonitrile, methanol and ethanol is rather weak and in water the ionic liquid is fully dissociated. In the second part of this work, the apparent molar volumes and isentropic compressibilities of [C(6)mim][Cl] in water, methanol, ethanol, acetonitrile, 1-propanol, 2-propanol, and 1-butanol are obtained at the 288.15-313.15 K temperature range at 5 K intervals at atmospheric pressure from the precise measurements of density and sound velocity. The infinite dilution apparent molar volume and isentropic compressibility values of the free ions and ion pairs of [C(6)mim][Cl] in the investigated solvents as well as the excess molar volume of the investigated solutions are determined and their variations with temperature and type of solvents are also studied. Finally, the experimental measurements of osmotic coefficient at 318.15 K for binary solutions of [C(6)mim][Cl] in water, methanol, ethanol, 2-propanol, and acetonitrile are taken using the vapor pressure osmometry (VPO) method and from which the values of the solvent activity, vapor pressure, activity coefficients, and Gibbs free energies are calculated. The results are

Femtosecond spectroscopic study of the solvation of amphiphilic molecules by water

NARCIS (Netherlands)

Rezus, Y.L.A.; Bakker, H.J.

2008-01-01

We use polarization-resolved mid-infrared pump-probe spectroscopy to study the aqueous solvation of proline and N-methylacetamide. These molecules serve as models to study the solvation of proteins. We monitor the orientational dynamics of partly deuterated water molecules (HDO) that are present at

Thermodynamics of solvation and solvophobic effect in formamide

International Nuclear Information System (INIS)

Sedov, I.A.; Stolov, M.A.; Solomonov, B.N.

2013-01-01

Highlights: • Enthalpies of solution of apolar organic compounds in formamide were measured. • Gibbs free energies of solution were experimentally determined. • Influence of the solvophobic effect on solvation thermodynamics was studied. • Thermodynamic features of solutions in formamide resemble those of aqueous solutions. -- Abstract: Using semi-adiabatic calorimetry, we measured the enthalpies of solution for various low-polar compounds including alkanes, aromatic hydrocarbons and their halogenated derivatives in formamide at temperature of 298 K. For the same compounds, the values of limiting activity coefficients in formamide were determined using GC headspace analysis at 298 K, and Gibbs free energies of solution and solvation were calculated. Based on these data and the available literature values of the Gibbs free energy of solvation in formamide for a number of other low-polar solutes, a study of the solvophobic effect in this solvent is performed, and its resemblance to the hydrophobic effect in aqueous solutions is demonstrated. It is shown that the contribution of the solvophobic effect into the solvation Gibbs free energy in formamide is much higher than that in aliphatic alcohols, but lower than that in water. Like in water, the magnitude of this contribution for different solutes linearly increases with the solute molecular volume. Solvophobic effect also significantly affects the enthalpies of dissolution in formamide, causing them to be more negative in the case of alkanes and more positive in the case of arenes

Difference rule-a new thermodynamic principle: prediction of standard thermodynamic data for inorganic solvates.

Science.gov (United States)

Jenkins, H Donald Brooke; Glasser, Leslie

2004-12-08

We present a quite general thermodynamic "difference" rule, derived from thermochemical first principles, quantifying the difference between the standard thermodynamic properties, P, of a solid n-solvate (or n-hydrate), n-S, containing n molecules of solvate, S (water or other) and the corresponding solid parent (unsolvated) salt: [P[n-solvate] - P[parent

Dipole moments of molecules solvated in helium nanodroplets

International Nuclear Information System (INIS)

Stiles, Paul L.; Nauta, Klaas; Miller, Roger E.

2003-01-01

Stark spectra are reported for hydrogen cyanide and cyanoacetylene solvated in helium nanodroplets. The goal of this study is to understand the influence of the helium solvent on measurements of the permanent electric dipole moment of a molecule. We find that the dipole moments of the helium solvated molecules, calculated assuming the electric field is the same as in vacuum, are slightly smaller than the well-known gas-phase dipole moments of HCN and HCCCN. A simple elliptical cavity model quantitatively accounts for this difference, which arises from the dipole-induced polarization of the helium

Ionic liquids: radiation chemistry, solvation dynamics and reactivity patterns

International Nuclear Information System (INIS)

Wishart, J.F.; Funston, A.M.; Szreder, T.

2006-01-01

Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of energy production, chemical industry and environmental applications. Pulse radiolysis of [R 4 N][NTf 2 ] [R 4 N][N(CN) 2 ], and [R 4 P][N(CN) 2 ] ionic liquids produces solvated electrons that absorb over a broad range in the near infrared and persisting for hundreds of nanoseconds. Systematic cation variation shows that solvated electron's spectroscopic properties depend strongly on the lattice structure of the ionic liquid. Very early in our radiolysis studies it became evident that

Unusual solvation through both p-orbital lobes of a carbene carbon

Energy Technology Data Exchange (ETDEWEB)

Hadad, C. Z., E-mail: cacier.hadad@udea.edu.co [Grupo de Química-Física Teórica, Instituto de Química, Universidad de Antioquia, A. A. 1226 Medellín (Colombia); Jenkins, Samantha [College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Flórez, Elizabeth [Departamento de Ciencias Básicas, Universidad de Medellín, Carrera 87 N° 30-65, Medellín (Colombia)

2015-03-07

As a result of a configurational space search done to explain the experimental evidence of transient specific solvation of singlet fluorocarbene amide with tetrahydrofuran, we found that the most stable structures consist in a group in which each oxygen of two tetrahydrofuran molecules act as electron donor to its respective empty p-orbital lobe of the carbene carbon atom, located at each side of the carbene molecular plane. This kind of species, which to our knowledge has not been reported before, explains very well the particular experimental characteristics observed for the transient solvation of this system. We postulate that the simultaneous interaction to both p-orbital lobes seems to confer a special stability to the solvation complexes, because this situation moves away the systems from the proximity of the corresponding transition states for the ylide products. Additionally, we present an analysis of other solvation complexes and a study of the nature of the involved interactions.

Why are ionic liquid ions mainly associated in water? A Car-Parrinello study of 1-ethyl-3-methyl-imidazolium chloride water mixture

Science.gov (United States)

Spickermann, C.; Thar, J.; Lehmann, S. B. C.; Zahn, S.; Hunger, J.; Buchner, R.; Hunt, P. A.; Welton, T.; Kirchner, B.

2008-09-01

In this study we present the results of a first principles molecular dynamics simulation of a single 1-ethyl-3-methyl-imidazolium chloride [C2C1im][Cl] ion pair dissolved in 60 water molecules. We observe a preference of the in plane chloride coordination with respect to the cation ring plane as compared to the energetic slightly more demanding on top coordination. Evaluation of the different radial distribution functions demonstrates that the structure of the hydration shell around the ion pair differs significantly from bulk water and that no true ion pair dissociation in terms of completely autonomous solvation shells takes place on the timescale of the simulation. In addition, dipole moment distributions of the solvent in distinct solvation shells around different functional parts of the [C2C1im][Cl] ion pair are calculated from maximally localized Wannier functions. The analysis of these distributions gives evidence for a depolarization of water molecules close to the hydrophobic parts of the cation as well as close to the anion. Examination of the angular distribution of different OH(H2O )-X angles in turn shows a linear coordination of chloride accompanied by a tangential orientation of water molecules around the hydrophobic groups, being a typical feature of hydrophobic hydration. Based on these orientational aspects, a structural model for the obvious preference of ion pair association is developed, which justifies the associating behavior of solvated [C2C1im][Cl] ions in terms of an energetically favorable interface between the solvation shells of the anion and the hydrophobic parts of the cation.

Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

International Nuclear Information System (INIS)

Wishart, J.F.

2008-01-01

Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate

IONIC LIQUIDS: RADIATION CHEMISTRY, SOLVATION DYNAMICS AND REACTIVITY PATTERNS

International Nuclear Information System (INIS)

WISHART, J.F.

2007-01-01

energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate the influence of ILs on charge transport processes. Methods. Picosecond pulse radiolysis studies at BNL

Rate theory of solvent exchange and kinetics of Li+ − BF4−/PF6− ion pairs in acetonitrile

International Nuclear Information System (INIS)

Dang, Liem X.; Chang, Tsun-Mei

2016-01-01

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li + and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li + in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li + -[BF 4 ] and Li + -[PF 6 ] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li + . We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li + -[BF 4 ] and Li + -[PF 6 ] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

Influence of electrolyte ion-solvent interactions on the performances of supercapacitors porous carbon electrodes

Science.gov (United States)

Decaux, C.; Matei Ghimbeu, C.; Dahbi, M.; Anouti, M.; Lemordant, D.; Béguin, F.; Vix-Guterl, C.; Raymundo-Piñero, E.

2014-10-01

The development of advanced and safe electrochemical supercapacitors or hybrid supercapacitors combining a battery electrode material such as graphite and a porous carbon electrode implies the use of new electrolytes containing a tetra-alkylammonium or lithium salt dissolved preferentially in a safe and environmentally friendly solvent such as alkylcarbonates. In those systems, the carbon porosity of the activated carbon electrode controls the electrochemical behavior of the whole device. In this work, it is demonstrated that electrolytes containing highly polarizing ions such as Li+ dissolved in polar solvents such as alkylcarbonates do not completely loss their solvation shell at the opposite of what is observed for poorly solvated cations like TEABF4. As a consequence, the optimal carbon pore size for obtaining the largest energy density, while keeping a high power density, is wider when strongly solvated cations, like Li+ are used than for conventional organic electrolytes using acetonitrile as solvent and TEA+ as salt cations. TEA+ cations are easily desolvated and hence are able to penetrate in small pores matching the dimensions of bare ions. The dissimilarity of behavior of alkylcarbonates and acetonitrile based electrolytes highlights the importance of ion-solvent interactions when searching the optimal porous texture for the electrode material.

1 SUPPLEMENTARY INFORMATION Nonpolar Solvation Dynamics ...

Indian Academy of Sciences (India)

IITP

. S. NP. ( t. ) ( )t. SNeqm. NP. (a). (b). Figure S2. (a) Nonequilibrium solvation response functions calculated after averaging over different number of nonequilibrium trajectories. The response function converges after averaging over more than ...

Analysis of biomolecular solvation sites by 3D-RISM theory.

Science.gov (United States)

Sindhikara, Daniel J; Hirata, Fumio

2013-06-06

We derive, implement, and apply equilibrium solvation site analysis for biomolecules. Our method utilizes 3D-RISM calculations to quickly obtain equilibrium solvent distributions without either necessity of simulation or limits of solvent sampling. Our analysis of these distributions extracts highest likelihood poses of solvent as well as localized entropies, enthalpies, and solvation free energies. We demonstrate our method on a structure of HIV-1 protease where excellent structural and thermodynamic data are available for comparison. Our results, obtained within minutes, show systematic agreement with available experimental data. Further, our results are in good agreement with established simulation-based solvent analysis methods. This method can be used not only for visual analysis of active site solvation but also for virtual screening methods and experimental refinement.

Investigation of the lithium ion mobility in cyclic model compounds and their ion conduction properties

Energy Technology Data Exchange (ETDEWEB)

Thielen, Joerg

2011-07-27

In view of both, energy density and energy drain, rechargeable lithium ion batteries outperform other present accumulator systems. However, despite great efforts over the last decades, the ideal electrolyte in terms of key characteristics such as capacity, cycle life, and most important reliable safety, has not yet been identified. Steps ahead in lithium ion battery technology require a fundamental understanding of lithium ion transport, salt association, and ion solvation within the electrolyte. Indeed, well defined model compounds allow for systematic studies of molecular ion transport. Thus, in the present work, based on the concept of immobilizing ion solvents, three main series with a cyclotriphosphazene (CTP), hexaphenylbenzene (HBP), and tetramethylcyclotetrasiloxane (TMS) scaffold were prepared. Lithium ion solvents, among others ethylene carbonate (EC), which has proven to fulfill together with propylene carbonate safety and market concerns in commercial lithium ion batteries, were attached to the different cores via alkyl spacers of variable length. All model compounds were fully characterized, pure and thermally stable up to at least 235 C, covering the requested broad range of glass transition temperatures from -78.1 C up to +6.2 C. While the CTP models tend to rearrange at elevated temperatures over time, which questions the general stability of alkoxide related (poly)phosphazenes, both, the HPB and CTP based models show no evidence of core stacking. In particular the CTP derivatives represent good solvents for various lithium salts, exhibiting no significant differences in the ionic conductivity {sigma}{sub dc} and thus indicating comparable salt dissociation and rather independent motion of cations and ions. In general, temperature-dependent bulk ionic conductivities investigated via impedance spectroscopy follow a William-Landel-Ferry (WLF) type behavior. Modifications of the alkyl spacer length were shown to influence ionic conductivities only in

Improvements to the APBS biomolecular solvation software suite.

Science.gov (United States)

Jurrus, Elizabeth; Engel, Dave; Star, Keith; Monson, Kyle; Brandi, Juan; Felberg, Lisa E; Brookes, David H; Wilson, Leighton; Chen, Jiahui; Liles, Karina; Chun, Minju; Li, Peter; Gohara, David W; Dolinsky, Todd; Konecny, Robert; Koes, David R; Nielsen, Jens Erik; Head-Gordon, Teresa; Geng, Weihua; Krasny, Robert; Wei, Guo-Wei; Holst, Michael J; McCammon, J Andrew; Baker, Nathan A

2018-01-01

The Adaptive Poisson-Boltzmann Solver (APBS) software was developed to solve the equations of continuum electrostatics for large biomolecular assemblages that have provided impact in the study of a broad range of chemical, biological, and biomedical applications. APBS addresses the three key technology challenges for understanding solvation and electrostatics in biomedical applications: accurate and efficient models for biomolecular solvation and electrostatics, robust and scalable software for applying those theories to biomolecular systems, and mechanisms for sharing and analyzing biomolecular electrostatics data in the scientific community. To address new research applications and advancing computational capabilities, we have continually updated APBS and its suite of accompanying software since its release in 2001. In this article, we discuss the models and capabilities that have recently been implemented within the APBS software package including a Poisson-Boltzmann analytical and a semi-analytical solver, an optimized boundary element solver, a geometry-based geometric flow solvation model, a graph theory-based algorithm for determining pK a values, and an improved web-based visualization tool for viewing electrostatics. © 2017 The Protein Society.

Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

Science.gov (United States)

Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

2018-04-01

Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

Li ⁺ solvation and kinetics of Li⁺–BF₄^-/PF ₆ ^- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

Energy Technology Data Exchange (ETDEWEB)

Chang, Tsun-Mei [Department of Chemistry, University of Wisconsin–Parkside, Kenosha, Wisconsin 53141, USA; Dang, Liem X. [Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 93352, USA

2017-10-28

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+-[BF4] and Li+-[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux; Impey, Madden, and McDonald approaches; and Grote-Hynes theory. We found the residence times of EC around Li+ ions varied from 70 to 450 ps, depending on the correction method used. We found the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influence the dissociation kinetics of ion pairing. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

Science.gov (United States)

Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

2011-12-01

The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.

The state of uranyl ions in water-dioxane solvent mixtures

International Nuclear Information System (INIS)

Geipel, G.; Nebel, D.; Baraniak, L.

1985-01-01

A comparison of the spectra of uranyl ions in HCl and dioxane solutions leads to the conclusion that dioxane promotes complex formation. The investigation of spectra showed that taking into account the hydrolysis of uranyl ions in dioxane containing solutions, two successive equilibrium reactions take place. The formation constants were determined. Conductivity measurements confirmed the spectrophotometrically determined equilibria. In solutions containing up to 60 % dioxane there is no incorporation of dioxane in the solvating envelope of the uranyl ion. (author)

Dynamics of solvation and desolvation of rubidium attached to He nanodroplets

Energy Technology Data Exchange (ETDEWEB)

Vangerow, J. von; John, O.; Stienkemeier, F.; Mudrich, M., E-mail: mudrich@physik.uni-freiburg.de [Physikalisches Institut, Universität Freiburg, 79104 Freiburg (Germany)

2015-07-21

The real-time dynamics of photoexcited and photoionized rubidium (Rb) atoms attached to helium (He) nanodroplets is studied by femtosecond pump-probe mass spectrometry. While excited Rb atoms in the perturbed 6p-state (Rb{sup *}) desorb off the He droplets, Rb{sup +} photoions tend to sink into the droplet interior when created near the droplet surface. The transition from Rb{sup +} solvation to full Rb{sup *} desorption is found to occur at a delay time τ ∼ 600 fs for Rb{sup *} in the 6pΣ-state and τ ∼ 1200 fs for the 6pΠ-state. Rb{sup +}He ions are found to be created by directly exciting bound Rb{sup *}He exciplex states as well as by populating bound Rb{sup +}He-states in a photoassociative ionization process.

Understanding the scale of the single ion free energy: A critical test of the tetra-phenyl arsonium and tetra-phenyl borate assumption

Science.gov (United States)

Duignan, Timothy T.; Baer, Marcel D.; Mundy, Christopher J.

2018-06-01

The tetra-phenyl arsonium and tetra-phenyl borate (TATB) assumption is a commonly used extra-thermodynamic assumption that allows single ion free energies to be split into cationic and anionic contributions. The assumption is that the values for the TATB salt can be divided equally. This is justified by arguing that these large hydrophobic ions will cause a symmetric response in water. Experimental and classical simulation work has raised potential flaws with this assumption, indicating that hydrogen bonding with the phenyl ring may favor the solvation of the TB- anion. Here, we perform ab initio molecular dynamics simulations of these ions in bulk water demonstrating that there are significant structural differences. We quantify our findings by reproducing the experimentally observed vibrational shift for the TB- anion and confirm that this is associated with hydrogen bonding with the phenyl rings. Finally, we demonstrate that this results in a substantial energetic preference of the water to solvate the anion. Our results suggest that the validity of the TATB assumption, which is still widely used today, should be reconsidered experimentally in order to properly reference single ion solvation free energy, enthalpy, and entropy.

Febuxostat-Minoxidil Salt Solvates: Crystal Structures, Characterization, Interconversion and Solubility Performance

Directory of Open Access Journals (Sweden)

Li-Yang Li

2018-02-01

Full Text Available Three febuxostat-minoxidil salt solvates with acetone (ACE, tetrahydrofuran (THF and isopropanol (IPA are synthesized by solvent-assisted grinding and characterized by infrared (IR, nuclear magnetic resonance (1H-NMR, single crystal and powder X-ray diffraction (PXRD, thermogravimetry (TG and differential scanning calorimetry (DSC. These febuxostat-minoxidil salt solvates feature isostructural with the same stoichiometries (1:1:1 molecule ratio. The proton transfers from the carboxylic group of febuxostat (FEB to imino N atom of minoxidil (MIN, which forms the motif with combined R 2 2 (9 R 4 2 (8 R 2 2 (9 graph set in the three solvates. The solvents occupy the different positions related to the motif, which results in the apparent differences in PXRD patterns before/after desolvation although they are isostructures. The FEB-MIN·THF was more thermostable than FEB-MIN·ACE and FEB-MIN·IPA relative to solvent removal from DSC patterns, which is different from the results from the solvent-exchange experiments in chemical kinetics. All three salt solvates exhibit increased equilibrium solubility compared to FEB in aqueous medium.

Predicting the stability constants of metal-ion complexes from first principles

Czech Academy of Sciences Publication Activity Database

Gutten, Ondrej; Rulíšek, Lubomír

2013-01-01

Roč. 52, č. 18 (2013), s. 10347-10355 ISSN 0020-1669 Institutional support: RVO:61388963 Keywords : stability constants * solvation energy * metal-ion complexation * theoretical calculations * DFT methods Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.794, year: 2013

Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer

Science.gov (United States)

Chen, Mohan; Zheng, Lixin; Santra, Biswajit; Ko, Hsin-Yu; DiStasio, Robert A., Jr.; Klein, Michael L.; Car, Roberto; Wu, Xifan

2018-03-01

Proton transfer via hydronium and hydroxide ions in water is ubiquitous. It underlies acid-base chemistry, certain enzyme reactions, and even infection by the flu. Despite two centuries of investigation, the mechanism underlying why hydroxide diffuses slower than hydronium in water is still not well understood. Herein, we employ state-of-the-art density-functional-theory-based molecular dynamics—with corrections for non-local van der Waals interactions, and self-interaction in the electronic ground state—to model water and hydrated water ions. At this level of theory, we show that structural diffusion of hydronium preserves the previously recognized concerted behaviour. However, by contrast, proton transfer via hydroxide is less temporally correlated, due to a stabilized hypercoordination solvation structure that discourages proton transfer. Specifically, the latter exhibits non-planar geometry, which agrees with neutron-scattering results. Asymmetry in the temporal correlation of proton transfer leads to hydroxide diffusing slower than hydronium.

Water Evaporation and Conformational Changes from Partially Solvated Ubiquitin

Directory of Open Access Journals (Sweden)

Saravana Prakash Thirumuruganandham

2010-01-01

Full Text Available Using molecular dynamics simulation, we study the evaporation of water molecules off partially solvated ubiquitin. The evaporation and cooling rates are determined for a molecule at the initial temperature of 300 K. The cooling rate is found to be around 3 K/ns, and decreases with water temperature in the course of the evaporation. The conformation changes are monitored by studying a variety of intermediate partially solvated ubiquitin structures. We find that ubiquitin shrinks with decreasing hydration shell and exposes more of its hydrophilic surface area to the surrounding.

Are mixed explicit/implicit solvation models reliable for studying phosphate hydrolysis? A comparative study of continuum, explicit and mixed solvation models.

Energy Technology Data Exchange (ETDEWEB)

Kamerlin, Shina C. L.; Haranczyk, Maciej; Warshel, Arieh

2009-05-01

Phosphate hydrolysis is ubiquitous in biology. However, despite intensive research on this class of reactions, the precise nature of the reaction mechanism remains controversial. In this work, we have examined the hydrolysis of three homologous phosphate diesters. The solvation free energy was simulated by means of either an implicit solvation model (COSMO), hybrid quantum mechanical / molecular mechanical free energy perturbation (QM/MM-FEP) or a mixed solvation model in which N water molecules were explicitly included in the ab initio description of the reacting system (where N=1-3), with the remainder of the solvent being implicitly modelled as a continuum. Here, both COSMO and QM/MM-FEP reproduce Delta Gobs within an error of about 2kcal/mol. However, we demonstrate that in order to obtain any form of reliable results from a mixed model, it is essential to carefully select the explicit water molecules from short QM/MM runs that act as a model for the true infinite system. Additionally, the mixed models tend to be increasingly inaccurate the more explicit water molecules are placed into the system. Thus, our analysis indicates that this approach provides an unreliable way for modelling phosphate hydrolysis in solution.

Solvated protein-DNA docking using HADDOCK

NARCIS (Netherlands)

van Dijk, Marc; Visscher, Koen M; Bonvin, Alexandre M.J.J; Kastritis, Panagiotis L.

2013-01-01

Interfacial water molecules play an important role in many aspects of protein-DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the

Solvation numbers and hydration constant for thorium(IV) in ethanol-water medium

International Nuclear Information System (INIS)

Sedaira, H.; Idriss, K.A.; Hashem, E.Y.

1996-01-01

The solvation number and hydration constant of Th 4+ in ethanol-water medium were determined at 25 degrees C using UV-spectral and electrochemical measurements. A solvate formation equilibrium is demonstrated and characterized. Three molecules of ethanol (S) can bond to the metal cation with strengths comparable to that for H 2 O to form ThS 3 (H 2 O) 3 4+ . Formation of thorium monochelate with lawsone (2-hydroxy-1.4-naphthoquinone) eliminates bonding with alcohol molecules. The dissociation constant of the chelating agent s K a and the formation contant of the monochelated metal ion s K f * that are essentially independent of the solution composition are evaluated. Hydration titrations involving thorium-lawsone monochlate are performed and the data obtained from the changes of pH with solvent composition are analyzed. The solution independent constant, s K f * for thorium-lawsone complex formation in mixed aqueous ethanol is given by log x K f * =vpK a + log s K h - log [LH] - vpH + 3 log v where vpK a is the dissociation constant of the chelating agent LH in the solvent system of v volume fraction of water and s K h is the solution-independent hydration constant of thorium (IV) in the solvent system. Log-values for the constants s K h , s K f * and s K z * are found to be 7.8 ±0.02, 11.38±0.04 and -0.753, respectively

Ion exchange in ultramarine blue. Studies using radioactive tracers (1963); Echanges d'ion dans le bleu d'outremer, etudies au moyen des traceurs radioactifs (1963)

Energy Technology Data Exchange (ETDEWEB)

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

1963-05-15

A study has been made of the exchange reaction between the constituent sodium in ultramarine blue, and silver in the form of a silver nitrate solution; an attempt hat been made to define the influence of the solvent of the silver nitrate on the kinetics of the exchange reaction. Five solvents have been used: water, methanol, ethanol, n-propanol and acetone. The reaction rates are controlled by a diffusion process inside the ultramarine grains, whatever the solvent used. It seems that the solvated ionic radius of the diffusing ion is one of the factors influencing the rate of reaction. Furthermore, the solvated ionic radius varies with temperature; this variation is different for each solvent and should explain the differences observed in the activation energies. (author) [French] Nous avons etudie la reaction d'echange entre le sodium de constitution du bleu d'outremer et l'argent sous forme de nitrate d'argent en solution; nous avons essaye de definir l'influence du solvant du nitrate d'argent sur la cinetique de la reaction d'echange. Nous avons utilise cinq solvant: l'eau, le methanol, l'ethanol, le n-propanol et l'acetone. Les vitesses de reaction sont controlees par un processus de diffusion a l'interieur des grains d'outremer quel que soit le solvant. Il semble que le rayon ionique solvate de l'ion diffusant est l'un des facteurs qui influencent la vitesse de reaction. D'autre part, le rayon ionique solvate varie avec la temperature, cette variation est differente pour chaque solvant et doit pouvoir expliquer les differences d'energie d'activation constatees. (auteur)

Influence of temperature and molecular structure on ionic liquid solvation layers.

Science.gov (United States)

Wakeham, Deborah; Hayes, Robert; Warr, Gregory G; Atkin, Rob

2009-04-30

Atomic force microscopy (AFM) force profiling is used to investigate the structure of adsorbed and solvation layers formed on a mica surface by various room temperature ionic liquids (ILs) ethylammonium nitrate (EAN), ethanolammonium nitrate (EtAN), ethylammonium formate (EAF), propylammonium formate (PAF), ethylmethylammonium formate (EMAF), and dimethylethylammonium formate (DMEAF). At least seven layers are observed for EAN at 14 degrees C (melting point 13 degrees C), decreasing as the temperature is increased to 30 degrees C due to thermal energy disrupting solvophobic forces that lead to segregation of cation alkyl tails from the charged ammonium and nitrate moieties. The number and properties of the solvation layers can also be controlled by introducing an alcohol moiety to the cation's alkyl tail (EtAN), or by replacing the nitrate anion with formate (EAF and PAF), even leading to the detection of distinct cation and anion sublayers. Substitution of primary by secondary or tertiary ammonium cations reduces the number of solvation layers formed, and also weakens the cation layer adsorbed onto mica. The observed solvation and adsorbed layer structures are discussed in terms of the intermolecular cohesive forces within the ILs.

Relaxation dynamics following transition of solvated electrons

International Nuclear Information System (INIS)

Barnett, R.B.; Landman, U.; Nitzan, A.

1989-01-01

Relaxation dynamics following an electronic transition of an excess solvated electron in clusters and in bulk water is studied using an adiabatic simulation method. In this method the solvent evolves classically and the electron is constrained to a specified state. The coupling between the solvent and the excess electron is evaluated via the quantum expectation value of the electron--water molecule interaction potential. The relaxation following excitation (or deexcitation) is characterized by two time scales: (i) a very fast (/similar to/20--30 fs) one associated with molecular rotations in the first solvation shell about the electron, and (ii) a slower stage (/similar to/200 fs), which is of the order of the longitudinal dielectric relaxation time. The fast relaxation stage exhibits an isotope effect. The spectroscopical consequences of the relaxation dynamics are discussed

Solvent effect on Rb+ to K+ ion mutation: Monte Carlo simulation study

International Nuclear Information System (INIS)

Kim, Hag Sung

2000-01-01

The solvent effects on the relative free energies of solvation and the difference in partition coefficients (log P) for Rb + to K + mutation in several solvents have been investigated using Monte Carlo simulation (MCS) of statistical perturbation theory (SPT). In comparing the relative free energies for interconversion of one ion pair, Rb + to K + , in H 2 O (TIP4P) in this study with the relative free energies of the computer simulations and the experimental, we found that the figure in this study is -5.00 ± 0.11 kcal/mol. There is good agreement among various studies, taking into account both methods used to obtain the hydration free energies and standard deviations. There is also good agreement between the calculated structural properties of this study and the simulations, ab initio and the experimental results. We have explained the deviation of the relationship between the free energy difference and the Onsager dielectric function of solvents by the electron pair donor properties of the solvents. For the Rb + and K + ion pair, the Onsager dielectric function of solvents (or solvent permittivity), donor number of solvent and the differences in solvation dominate the differences in the relative free energies of solvation and partition coefficients

Strong Stretching of Poly(ethylene glycol) Brushes Mediated by Ionic Liquid Solvation.

Science.gov (United States)

Han, Mengwei; Espinosa-Marzal, Rosa M

2017-09-07

We have measured forces between mica surfaces coated with a poly(ethylene glycol) (PEG) brush solvated by a vacuum-dry ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide, with a surface forces apparatus. At high grafting density, the solvation mediated by the ionic liquid causes the brush to stretch twice as much as in water. Modeling of the steric repulsion indicates that PEG behaves as a polyelectrolyte; the hydrogen bonding between ethylene glycol and the imidazolium cation seems to effectively charge the polymer brush, which justifies the strong stretching. Importantly, under strong polymer compression, solvation layers are squeezed out at a higher rate than for the neat ionic liquid. We propose that the thermal fluctuations of the PEG chains, larger in the brush than in the mushroom configuration, maintain the fluidity of the ionic liquid under strong compression, in contrast to the solid-like squeezing-out behavior of the neat ionic liquid. This is the first experimental study of the behavior of a polymer brush solvated by an ionic liquid under nanoconfinement.

Role of Dispersive Fluorous Interaction in the Solvation Dynamics of the Perfluoro Group Containing Molecules.

Science.gov (United States)

Mondal, Saptarsi; Chaterjee, Soumit; Halder, Ritaban; Jana, Biman; Singh, Prashant Chandra

2017-08-17

Perfluoro group containing molecules possess an important self-aggregation property through the fluorous (F···F) interaction which makes them useful for diverse applications such as medicinal chemistry, separation techniques, polymer technology, and biology. In this article, we have investigated the solvation dynamics of coumarin-153 (C153) and coumarin-6H (C6H) in ethanol (ETH), 2-fluoroethanol (MFE), and 2,2,2-trifluoroethanol (TFE) using the femtosecond upconversion technique and molecular dynamics (MD) simulation to understand the role of fluorous interaction between the solute and solvent molecules in the solvation dynamics of perfluoro group containing molecules. The femtosecond upconversion data show that the time scales of solvation dynamics of C6H in ETH, MFE, and TFE are approximately the same whereas the solvation dynamics of C153 in TFE is slow as compared to that of ETH and MFE. It has also been observed that the time scale of solvation dynamics of C6H in ETH and MFE is higher than that of C153 in the same solvents. MD simulation results show a qualitative agreement with the experimental data in terms of the time scale of the slow components of the solvation for all the systems. The experimental and simulation studies combined lead to the conclusion that the solvation dynamics of C6H in all solvents as well as C153 in ETH and MFE is mostly governed by the charge distribution of ester moieties (C═O and O) of dye molecules whereas the solvation of C153 in TFE is predominantly due to the dispersive fluorous interaction (F···F) between the perfluoro groups of the C153 and solvent molecules.

Solvation and complexation study by fluorescence spectroscopy of Eu(III) and Cm(III) ions in octanol solution and at the interface with water

International Nuclear Information System (INIS)

Vu, T.H.

2008-01-01

Polydentate N-donors ligands like bis-triazine-pyridine (BTP) and bis-triazine-bis-pyridine (BTBP) can selectively extract minor actinides (III) from lanthanides (III) ions and therefore have been studied in the field of nuclear waste reprocessing. The aim of the researches carried out during this thesis is a better description of this family in biphasic systems: speciation in the organic phase and around the interfacial area. After an exhaustive description of the solvation of europium(III) cation in mixed solutions n-octanol water with TRLIF spectrometry, the complexation with nitrogen ligands iPr-BTP, C5-BTBP and CyMe4-BTBP has been studied by TRLIF and ESI-MS techniques. For each compound, the inner sphere of europium has been described and the conditional stability constants determined. The composition of the organic medium, and particularly the hydration degree of n-octanol, has an impact on the nature and the ratio of species 'cation - counter ion - ligand - water'. With high water content (representative of extraction systems), the complexes observed with Cm(III) and Eu(III) have the same stoichiometry but the affinity towards the curium cation is higher and consistent to separation factors measured with biphasic systems. The method TIRF (total internal reflection fluorescence) was retained to study the behaviour of europium(III) inside the interfacial area. Fluorescence spectra of europium have been obtained but side signals and the high depth resolution of detection lead to difficulty in obtaining the signal of interfacial europium alone. The selected technique remains promising but some improvements need to be implemented for forthcoming measurement at liquid/liquid interface. (author) [fr

Entropic solvation force between surfaces modified by grafted chains: a density functional approach

Directory of Open Access Journals (Sweden)

O. Pizio

2010-01-01

Full Text Available The behavior of a hard sphere fluid in slit-like pores with walls modified by grafted chain molecules composed of hard sphere segments is studied using density functional theory. The chains are grafted to opposite walls via terminating segments forming pillars. The effects of confinement and of "chemical" modification of pore walls on the entropic solvation force are investigated in detail. We observe that in the absence of adsorbed fluid the solvation force is strongly repulsive for narrow pores and attractive for wide pores. In the presence of adsorbed fluid both parts of the curve of the solvation force may develop oscillatory behavior dependent on the density of pillars, the number of segments and adsorption conditions. Also, the size ratio between adsorbed fluid species and chain segments is of importance for the development of oscillations. The choice of these parameters is crucial for efficient manipulation of the solvation force as desired for pores of different width.

Comparative assessment of computational methods for the determination of solvation free energies in alcohol-based molecules.

Science.gov (United States)

Martins, Silvia A; Sousa, Sergio F

2013-06-05

The determination of differences in solvation free energies between related drug molecules remains an important challenge in computational drug optimization, when fast and accurate calculation of differences in binding free energy are required. In this study, we have evaluated the performance of five commonly used polarized continuum model (PCM) methodologies in the determination of solvation free energies for 53 typical alcohol and alkane small molecules. In addition, the performance of these PCM methods, of a thermodynamic integration (TI) protocol and of the Poisson-Boltzmann (PB) and generalized Born (GB) methods, were tested in the determination of solvation free energies changes for 28 common alkane-alcohol transformations, by the substitution of an hydrogen atom for a hydroxyl substituent. The results show that the solvation model D (SMD) performs better among the PCM-based approaches in estimating solvation free energies for alcohol molecules, and solvation free energy changes for alkane-alcohol transformations, with an average error below 1 kcal/mol for both quantities. However, for the determination of solvation free energy changes on alkane-alcohol transformation, PB and TI yielded better results. TI was particularly accurate in the treatment of hydroxyl groups additions to aromatic rings (0.53 kcal/mol), a common transformation when optimizing drug-binding in computer-aided drug design. Copyright © 2013 Wiley Periodicals, Inc.

Estimation of abraham solvation equation coefficients for hydrogen bond formation from abraham solvation parameters for solute activity and basicity

NARCIS (Netherlands)

Noort, van P.C.M.

2013-01-01

Abraham solvation equations find widespread use in environmental chemistry and pharmaco-chemistry. The coefficients in these equations, which are solvent (system) descriptors, are usually determined by fitting experimental data. To simplify the determination of these coefficients in Abraham

Ion association thermodynamics of alkali metal tetraphenylborates in the mixed solvent propylenecarbonate-1,2-dimethoxyethane

International Nuclear Information System (INIS)

Fialkov, Yu.Ya.; Gorbachev, V.Yu.

1997-01-01

Polythermal dependences of constants of ion association of (Li + -Cs + )BPh 4 salts in mixed solvent differ significantly in permittivity. Thermodynamic characteristics of this process are calculated and their relation with solvation processes is analyzed. (author)

Generalized Born Models of Macromolecular Solvation Effects

Science.gov (United States)

Bashford, Donald; Case, David A.

2000-10-01

It would often be useful in computer simulations to use a simple description of solvation effects, instead of explicitly representing the individual solvent molecules. Continuum dielectric models often work well in describing the thermodynamic aspects of aqueous solvation, and approximations to such models that avoid the need to solve the Poisson equation are attractive because of their computational efficiency. Here we give an overview of one such approximation, the generalized Born model, which is simple and fast enough to be used for molecular dynamics simulations of proteins and nucleic acids. We discuss its strengths and weaknesses, both for its fidelity to the underlying continuum model and for its ability to replace explicit consideration of solvent molecules in macromolecular simulations. We focus particularly on versions of the generalized Born model that have a pair-wise analytical form, and therefore fit most naturally into conventional molecular mechanics calculations.

Ion Transport and Structure in Polymer Electrolytes with Applications in Lithium Batteries

Science.gov (United States)

Chintapalli, Mahati

When mixed with lithium salts, polymers that contain more than one chemical group, such as block copolymers and endgroup-functionalized polymers, are promising electrolyte materials for next-generation lithium batteries. One chemical group can provide good ion solvation and transport properties, while the other chemical group can provide secondary properties that improve the performance characteristics of the battery. Secondary properties of interest include non-flammability for safer lithium ion batteries and high mechanical modulus for dendrite resistance in high energy density lithium metal batteries. Block copolymers and other materials with multiple chemical groups tend to exhibit nanoscale heterogeneity and can undergo microphase separation, which impacts the ion transport properties. In block copolymers that microphase separate, ordered self-assembled structures occur on longer length scales. Understanding the interplay between structure at different length scales, salt concentration, and ion transport is important for improving the performance of multifunctional polymer electrolytes. In this dissertation, two electrolyte materials are characterized: mixtures of endgroup-functionalized, short chain perfluoropolyethers (PFPEs) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, and mixtures of polystyrene-block-poly(ethylene oxide) (PS- b-PEO; SEO) and LiTFSI. The PFPE/LiTFSI electrolytes are liquids in which the PFPE backbone provides non-flammability, and the endgroups resemble small molecules that solvate ions. In these electrolytes, the ion transport properties and nanoscale heterogeneity (length scale 1 nm) are characterized as a function of endgroup using electrochemical techniques, nuclear magnetic resonance spectroscopy, and wide angle X-ray scattering. Endgroups, especially those containing PEO segments, have a large impact on ionic conductivity, in part because the salt distribution is not homogenous; we find that salt partitions

Enthalpy-entropy compensation: the role of solvation.

Science.gov (United States)

Dragan, Anatoliy I; Read, Christopher M; Crane-Robinson, Colyn

2017-05-01

Structural modifications to interacting systems frequently lead to changes in both the enthalpy (heat) and entropy of the process that compensate each other, so that the Gibbs free energy is little changed: a major barrier to the development of lead compounds in drug discovery. The conventional explanation for such enthalpy-entropy compensation (EEC) is that tighter contacts lead to a more negative enthalpy but increased molecular constraints, i.e., a compensating conformational entropy reduction. Changes in solvation can also contribute to EEC but this contribution is infrequently discussed. We review long-established and recent cases of EEC and conclude that the large fluctuations in enthalpy and entropy observed are too great to be a result of only conformational changes and must result, to a considerable degree, from variations in the amounts of water immobilized or released on forming complexes. Two systems exhibiting EEC show a correlation between calorimetric entropies and local mobilities, interpreted to mean conformational control of the binding entropy/free energy. However, a substantial contribution from solvation gives the same effect, as a consequence of a structural link between the amount of bound water and the protein flexibility. Only by assuming substantial changes in solvation-an intrinsically compensatory process-can a more complete understanding of EEC be obtained. Faced with such large, and compensating, changes in the enthalpies and entropies of binding, the best approach to engineering elevated affinities must be through the addition of ionic links, as they generate increased entropy without affecting the enthalpy.

Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yanyan; Su, Mao; Yu, Xiaofei; Zhou, Yufan; Wang, Jungang; Cao, Ruiguo; Xu, Wu; Wang, Chongmin; Baer, Donald R.; Borodin, Oleg; Xu, Kang; Wang, Yanting; Wang, Xue-Lin; Xu, Zhijie; Wang, Fuyi; Zhu, Zihua

2018-02-06

Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC, which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.

Quantitative measurement of solvation shells using frequency modulated atomic force microscopy

Science.gov (United States)

Uchihashi, T.; Higgins, M.; Nakayama, Y.; Sader, J. E.; Jarvis, S. P.

2005-03-01

The nanoscale specificity of interaction measurements and additional imaging capability of the atomic force microscope make it an ideal technique for measuring solvation shells in a variety of liquids next to a range of materials. Unfortunately, the widespread use of atomic force microscopy for the measurement of solvation shells has been limited by uncertainties over the dimensions, composition and durability of the tip during the measurements, and problems associated with quantitative force calibration of the most sensitive dynamic measurement techniques. We address both these issues by the combined use of carbon nanotube high aspect ratio probes and quantifying the highly sensitive frequency modulation (FM) detection technique using a recently developed analytical method. Due to the excellent reproducibility of the measurement technique, additional information regarding solvation shell size as a function of proximity to the surface has been obtained for two very different liquids. Further, it has been possible to identify differences between chemical and geometrical effects in the chosen systems.

Spectral luminescence studies of eosin solvation in water-alcohol mixtures

Energy Technology Data Exchange (ETDEWEB)

Ketsle, G.A.; Levshin, L.V.; Mel' nikov, G.V.; Saletskii, A.M.

1987-11-01

The authors investigate the effects of solvation of eosin molecules in binary water-propanol mixtures with the goal of assessing eosin as a candidate dye laser material. The fluorescence was measured with a Hitachi spectrofluorimeter and the absorption spectra were taken on a Specord spectrophotometer. Absorption and fluorescence were measured for different amounts of propanol in the solvent. Data are also given on excitation and de-excitation kinetics between ground and excited states. Values for quantum yields of fluorescence and phosphorescence, average excited state lifetime, and molecular volume of the dye with the solvated shell are tabulated.

Refined Dummy Atom Model of Mg(2+) by Simple Parameter Screening Strategy with Revised Experimental Solvation Free Energy.

Science.gov (United States)

Jiang, Yang; Zhang, Haiyang; Feng, Wei; Tan, Tianwei

2015-12-28

Metal ions play an important role in the catalysis of metalloenzymes. To investigate metalloenzymes via molecular modeling, a set of accurate force field parameters for metal ions is highly imperative. To extend its application range and improve the performance, the dummy atom model of metal ions was refined through a simple parameter screening strategy using the Mg(2+) ion as an example. Using the AMBER ff03 force field with the TIP3P model, the refined model accurately reproduced the experimental geometric and thermodynamic properties of Mg(2+). Compared with point charge models and previous dummy atom models, the refined dummy atom model yields an enhanced performance for producing reliable ATP/GTP-Mg(2+)-protein conformations in three metalloenzyme systems with single or double metal centers. Similar to other unbounded models, the refined model failed to reproduce the Mg-Mg distance and favored a monodentate binding of carboxylate groups, and these drawbacks needed to be considered with care. The outperformance of the refined model is mainly attributed to the use of a revised (more accurate) experimental solvation free energy and a suitable free energy correction protocol. This work provides a parameter screening strategy that can be readily applied to refine the dummy atom models for metal ions.

Molecular dynamics study of the solvation of an alpha-helical transmembrane peptide by DMSO

NARCIS (Netherlands)

Duarte, A.M.; Mierlo, van C.P.M.; Hemminga, M.A.

2008-01-01

10-ns molecular dynamics study of the solvation of a hydrophobic transmembrane helical peptide in dimethyl sulfoxide (DMSO) is presented. The objective is to analyze how this aprotic polar solvent is able to solvate three groups of amino acid residues (i.e., polar, apolar, and charged) that are

Solvation effect on decomposition rate of 10-methyl-10-phenylphenoxarsonium iodide in some alcohols and ketones

International Nuclear Information System (INIS)

Gavrilov, V.I.; Gumerov, N.S.; Rakhmatullin, R.R.

1989-01-01

By the method of conductometry decomposition kinetics of 10-methyl-10phenylphenoxarsonium iodide in methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and methyl ethyl ketone at initial concentration of the salt 0.00024-0.003 mol/l, is studied. It is shown that at the temperatures up to 80-95 deg C practically no decomposition of arsonium salt in methanol and ethanol is observed. With an increase in the length of alcohol alkyl radical the decomposition rate increases. The values of activation enrgy both for alcohols and ketone are approximately the same. At the same time, decomposition rate in alcohol proved much slower than in ketone, which is related to iodide-ion solvation in protic solvents

Solvation effect on decomposition rate of 10-methyl-10-phenylphenoxarsonium iodide in some alcohols and ketones

Energy Technology Data Exchange (ETDEWEB)

Gavrilov, V I; Gumerov, N S; Rakhmatullin, R R [Kazanskij Khimiko-Tekhnologicheskij Inst., Kazan (USSR)

1989-03-01

By the method of conductometry decomposition kinetics of 10-methyl-10phenylphenoxarsonium iodide in methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and methyl ethyl ketone at initial concentration of the salt 0.00024-0.003 mol/l, is studied. It is shown that at the temperatures up to 80-95 deg C practically no decomposition of arsonium salt in methanol and ethanol is observed. With an increase in the length of alcohol alkyl radical the decomposition rate increases. The values of activation enrgy both for alcohols and ketone are approximately the same. At the same time, decomposition rate in alcohol proved much slower than in ketone, which is related to iodide-ion solvation in protic solvents.

Ion exchange in ultramarine blue. Studies using radioactive tracers (1963)

International Nuclear Information System (INIS)

Goenvec, H.

1963-05-01

A study has been made of the exchange reaction between the constituent sodium in ultramarine blue, and silver in the form of a silver nitrate solution; an attempt hat been made to define the influence of the solvent of the silver nitrate on the kinetics of the exchange reaction. Five solvents have been used: water, methanol, ethanol, n-propanol and acetone. The reaction rates are controlled by a diffusion process inside the ultramarine grains, whatever the solvent used. It seems that the solvated ionic radius of the diffusing ion is one of the factors influencing the rate of reaction. Furthermore, the solvated ionic radius varies with temperature; this variation is different for each solvent and should explain the differences observed in the activation energies. (author) [fr

Pulse radiolysis study in ethanol and N-propanol of the solvated electron formation and reactivity at low temperatures

International Nuclear Information System (INIS)

Bono Merino, M.R.

1978-01-01

The electron solvation process in polar media has been studied in liquid ethanol and n-propanol at temperatures near their melting points. The results show that using the change of absorption at a given wavelength to determine the solvation time leads to a value which varies with the wavelength considered. Furthermore, for n-propanol it appears that the process occurs without a definite order. Studies of the spectral shifts show that the passage from the initial to the final spectrum (solvated electron spectrum) involves intermediate transient spectra which probably correspond to partly solvated states of the electron. The interpretation of these various results points out the ambiguity of the kinetic measurements: the simultaneous existence of several partly solvated states of the electron is not consistent with the hypothesis previously admitted that the molar extinction coefficient at a given wavelength is unique and does not vary with time. The reaction of the solvated electron with acetone has been studied in ethanol in the temperature range from +25 to -105 0 C: this reaction is diffusion controlled [fr

Solvation in atomic liquids: connection between Gaussian field theory and density functional theory

Directory of Open Access Journals (Sweden)

V. Sergiievskyi

2017-12-01

Full Text Available For the problem of molecular solvation, formulated as a liquid submitted to the external potential field created by a molecular solute of arbitrary shape dissolved in that solvent, we draw a connection between the Gaussian field theory derived by David Chandler [Phys. Rev. E, 1993, 48, 2898] and classical density functional theory. We show that Chandler's results concerning the solvation of a hard core of arbitrary shape can be recovered by either minimising a linearised HNC functional using an auxiliary Lagrange multiplier field to impose a vanishing density inside the core, or by minimising this functional directly outside the core — indeed a simpler procedure. Those equivalent approaches are compared to two other variants of DFT, either in the HNC, or partially linearised HNC approximation, for the solvation of a Lennard-Jones solute of increasing size in a Lennard-Jones solvent. Compared to Monte-Carlo simulations, all those theories give acceptable results for the inhomogeneous solvent structure, but are completely out-of-range for the solvation free-energies. This can be fixed in DFT by adding a hard-sphere bridge correction to the HNC functional.

Influence of a Counterion on the Ion Atmosphere of an Anion: A Molecular Dynamics Study of LiX and CsX (X = F(-), Cl(-), I(-)) in Methanol.

Science.gov (United States)

Kumar, Parveen; Kulkarni, Anant D; Yashonath, S

2015-08-27

We report molecular dynamics (MD) simulations to explore the influence of a counterion on the structure and dynamics of cationic and anionic solvation shells for various ions in methanol at 298 K. We show that the variation in ionic size of either the cation or the anion in an ion pair influences the solvation structure of the other ion as well as the diffusivity in an electrolyte solution of methanol. The extent of ionic association between the cation and its counteranion of different ionic sizes has been investigated by analyzing the radial distribution functions (RDFs) and the orientation of methanol molecules in the first solvation shell (FSS) of ions. It is shown that the methanol in the FSS of the anion as well the cation exhibit quite different radial and orientational structures as compared to methanol which lie in the FSS of either the anion or the cation but not both. We find that the coordination number (CN) of F(-), Cl(-), and I(-) ions decreases with increasing size of the anion which is contrary to the trend reported for the anions in H2O. The mean residence time (MRT) of methanol molecules in the FSS of ions has been calculated using the stable states picture (SSP) approach. It is seen that the ion-counterion interaction has a considerable influence on the MRT of methanol molecules in the FSS of ions. We also discuss the stability order of the ion-counterion using the potentials of mean force (PMFs) for ion pairs with ions of different sizes. The PMF plots reveal that the Li(+)-F(-) pair (small-small) is highly stable and the Li(+)-I(-) pair is least stable (small-large) in electrolyte solutions.

Modelos contínuos do solvente: fundamentos Continuum solvation models: fundamentals

Directory of Open Access Journals (Sweden)

Josefredo R. Pliego Jr

2006-06-01

Full Text Available Continuum solvation models are nowadays widely used in the modeling of solvent effects and the range of applications goes from the calculation of partition coefficients to chemical reactions in solution. The present work presents a detailed explanation of the physical foundations of continuum models. We discuss the polarization of a dielectric and its representation through the volume and surface polarization charges. The Poisson equation for a dielectric was obtained and we have also derived and discuss the apparent surface charge method and its application for free energy of solvation calculations.

Solvation of monovalent anions in formamide and methanol: Parameterization of the IEF-PCM model

International Nuclear Information System (INIS)

Boees, Elvis S.; Bernardi, Edson; Stassen, Hubert; Goncalves, Paulo F.B.

2008-01-01

The thermodynamics of solvation for a series of monovalent anions in formamide and methanol has been studied using the polarizable continuum model (PCM). The parameterization of this continuum model was guided by molecular dynamics simulations. The parameterized PCM model predicts the Gibbs free energies of solvation for 13 anions in formamide and 16 anions in methanol in very good agreement with experimental data. Two sets of atomic radii were tested in the definition of the solute cavities in the PCM and their performances are evaluated and discussed. Mean absolute deviations of the calculated free energies of solvation from the experimental values are in the range of 1.3-2.1 kcal/mol

Comparison of solvation dynamics of electrons in four polyols

Energy Technology Data Exchange (ETDEWEB)

Lampre, I.; Pernot, P.; Bonin, J. [Laboratoire de Chimie Physique/ELYSE, Universite Paris-Sud 11, UMR 8000, Bat. 349, Orsay F-91405 (France); CNRS, Orsay F-91405 (France); Mostafavi, M. [Laboratoire de Chimie Physique/ELYSE, Universite Paris-Sud 11, UMR 8000, Bat. 349, Orsay F-91405 (France); CNRS, Orsay F-91405 (France)], E-mail: mehran.mostafavi@lcp.u-psud.fr

2008-10-15

Using pump-probe transient absorption spectroscopy, we studied the solvation dynamics of the electron in liquid polyalcohols: ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol and propane-1,2,3-triol. Time-resolved absorption spectra ranging from 440 to 720 nm were measured. Our study shows that the excess electron in the diols presents an intense and wide absorption band in the visible and near-IR spectral domain at early time after two-photon ionization of the neat solvent. Then, for the first tens of picoseconds, the electron spectrum shifts toward the blue domain and its bandwidth decreases as the red part of the initial spectrum rapidly drops, while the blue part hardly evolves. In contrast, in the triol, the absorption spectrum of the electron is early situated in the visible range after the pump pulse and then solely evolves in the red part. The Bayesian data analysis of the observed picosecond solvation dynamics with different models is in favor of a heterogeneous continuous relaxation. That is corroborated by the analogy between the change in the absorption band with increasing time or decreasing temperature. That tends to indicate a similar organization disorder of the solvent. Moreover, the electron solvation dynamics is very fast in propane-1,2,3-triol despite its high viscosity and highlight the role of the OH-group in that process.

Certain regularities of the radiolytic reduction of lead ions in various systems

International Nuclear Information System (INIS)

Chikvaidze, N.M.; Nanobashvili, H.M.; Gabisonya, L.V.

1983-01-01

The radiolysis of the aqueous solutions of the lead salts, chloride, acetate and nitrate, depending on the nature of the acceptor and various factors was studied. The radical and transient products of the radiolysis-solvated electron, ion radicals of the attendant anions, the univalent lead ion were identified and their yields determined by EPR and optical spectroscopy. The decay kinetics of the reducing particles and the kinetics of the formation of anomalous valent lead(I) with its following transformation to metal were studied. The mechanism of the radiation chemical reduction of lead(II) ions is suggested. (author)

Halide anion solvation and recognition by a macro tri-cyclic tetra-ammonium host in an ionic liquid: a molecular dynamics stud

International Nuclear Information System (INIS)

Chaumont, A.; Wipff, G.

2006-01-01

We report a molecular dynamics study of halide anions X - and their inclusion complexes X - - L 4+ with a macro-tri-cyclic tetrahedral host L 4+ built from four quaternary ammonium sites, in an ionic liquid (IL) based on the 1-butyl-3-methyl-imidazolium (BMI + ) cation and the PF 6 - anion. The 'dry' and 'humid' forms of the [BMI][PF 6 ] IL are compared, showing the importance of IL ions in the 'dry' IL and, in some cases, of water molecules in the 'humid' IL. In the 'dry' IL the F - , Cl - , Br - and I - un-complexed halides are surrounded by 4-5 BMI + cations whose binding mode evolves from hydrogen bonding to facial coordination along this series. Solvent humidity has the largest impact on the solvation of F - whose first shell BMI + cations are all displaced by H 2 O molecules, while the first solvation shell of Cl - , Br - and I - comprises 3-4 BMI + cations plus ca. 4 H 2 O molecules. The solvation of the L 4+ host and of its X - - L 4+ complex mainly involves PF 6 - anions in the 'dry' IL, and additional H 2 O molecules in the 'humid' IL. The question of anion binding selectivity is addressed by free energy perturbation calculations which predict that, in the 'dry' liquid, F - is preferred over Cl - , Br - and I - , which contrasts with the aqueous solution where L 4+ is selective for Cl - . In the 'humid' liquid however, there is no F - /Cl - discrimination, showing the importance of small amounts of water on the complexation selectivity. (authors)

Transport of secondary electrons and reactive species in ion tracks

Science.gov (United States)

Surdutovich, Eugene; Solov'yov, Andrey V.

2015-08-01

The transport of reactive species brought about by ions traversing tissue-like medium is analysed analytically. Secondary electrons ejected by ions are capable of ionizing other molecules; the transport of these generations of electrons is studied using the random walk approximation until these electrons remain ballistic. Then, the distribution of solvated electrons produced as a result of interaction of low-energy electrons with water molecules is obtained. The radial distribution of energy loss by ions and secondary electrons to the medium yields the initial radial dose distribution, which can be used as initial conditions for the predicted shock waves. The formation, diffusion, and chemical evolution of hydroxyl radicals in liquid water are studied as well. COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy.

Sink or Swim: Ions and Organics at the Ice-Air Interface.

Science.gov (United States)

Hudait, Arpa; Allen, Michael T; Molinero, Valeria

2017-07-26

The ice-air interface is an important locus of environmental chemical reactions. The structure and dynamics of the ice surface impact the uptake of trace gases and kinetics of reactions in the atmosphere and snowpack. At tropospheric temperatures, the ice surface is partially premelted. Experiments indicate that ions increase the liquidity of the ice surface but hydrophilic organics do not. However, it is not yet known the extent of the perturbation solutes induce at the ice surface and what is the role of the disordered liquid-like layer in modulating the interaction between solutes and their mobility and aggregation at the ice surface. Here we use large-scale molecular simulations to investigate the effect of ions and glyoxal, one of the most abundant oxygenated volatile organic compounds in the atmosphere, on the structure, dynamics, and solvation properties of the ice surface. We find that the premelted surface of ice has unique solvation properties, different from those of liquid water. The increase in surface liquidity resulting from the hydration of ions leads to a water-mediated attraction of ions at the ice surface. Glyoxal molecules, on the other hand, perturb only slightly the surface of ice and do not experience water-driven attraction. They nonetheless accumulate as dry agglomerates at the ice surface, driven by direct interactions between the organic molecules. The enhanced attraction and clustering of ions and organics at the ice surface may play a significant role in modulating the mechanism and rate of heterogeneous chemical reactions occurring at the surface of atmospheric ice particles.

Significance of solvated electrons (e(aq)-) as promoters of life on earth.

Science.gov (United States)

Getoff, Nikola

2014-01-01

Based on the present state of knowledge a new hypothesis concerning the origin of life on Earth is presented, and emphasizes the particular significance of solvated electrons (e(aq)(-)). Solvated electrons are produced in seawater, mainly by (40)K radiation and in atmospheric moisture by VUV light, electrical discharges and cosmic ray. Solvated electrons are involved in primary chemical processes and in biological processes. The conversion of aqueous CO2 and CO into simple organic substances, the generation of ammonia from N2 and water, the formation of amines, amino acids and simple proteins under the action of e(aq)(-) has been experimentally proven. Furthermore, it is supposed that the generation of the primitive cell and equilibria of primitive enzymes are also realized due to the strong reducing property of e(aq)(-). The presented hypothesis is mainly founded on recently obtained experimental results. The involvement of e(aq)(-) in such mechanisms, as well as their action as an initiator of life is also briefly discussed.

Polarizability and Aqueous Solvation of the Sulfate Dianion

Czech Academy of Sciences Publication Activity Database

Jungwirth, Pavel; Curtis, J. E.; Tobias, D. J.

2003-01-01

Roč. 367, - (2003), s. 704-710 ISSN 0009-2614 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : polarizability * aqueous solvation * dianion Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.438, year: 2003

Selective nonspecific solvation under dielectric saturation and fluorescence spectra of dye solutions in binary solvents.

Science.gov (United States)

Bakhshiev, N G; Kiselev, M B

1991-09-01

The influence of selective nonspecific solvation on the fluorescence spectra of three substitutedN-methylphthalimides in a binary solvent system consisting of a nonpolar (n-heptane) and a polar (pyridine) component has been studied under conditions close to dielectric saturation. The substantially nonlinearity of the effect is confirmation that the spectral shifts of fluorescence bands depend on the number of polar solvent molecules involved in solvating the dye molecule. The measured fluorescence spectral shifts determined by substituting one nonpolar solvent molecula with a polar one in the proximity of the dye molecule agree quantitatively with the forecasts of the previously proposed semiempirical theory which describes this nonlinear solvation phenomenon.

On the microscopic fluctuations driving the NMR relaxation of quadrupolar ions in water

Energy Technology Data Exchange (ETDEWEB)

Carof, Antoine; Salanne, Mathieu; Rotenberg, Benjamin, E-mail: benjamin.rotenberg@upmc.fr [Sorbonne Universités, UPMC Univ. Paris 06, CNRS, Laboratoire PHENIX, Case 51, 4 Place Jussieu, F-75005 Paris (France); Charpentier, Thibault [CEA, IRAMIS, NIMBE, LSDRM, UMR CEA-CNRS 3685, F-91191 Gif-sur-Yvette Cedex (France)

2015-11-21

Nuclear Magnetic Resonance (NMR) relaxation is sensitive to the local structure and dynamics around the probed nuclei. The Electric Field Gradient (EFG) is the key microscopic quantity to understand the NMR relaxation of quadrupolar ions, such as {sup 7}Li{sup +}, {sup 23}Na{sup +}, {sup 25}Mg{sup 2+}, {sup 35}Cl{sup −}, {sup 39}K{sup +}, or {sup 133}Cs{sup +}. Using molecular dynamics simulations, we investigate the statistical and dynamical properties of the EFG experienced by alkaline, alkaline Earth, and chloride ions at infinite dilution in water. Specifically, we analyze the effect of the ionic charge and size on the distribution of the EFG tensor and on the multi-step decay of its auto-correlation function. The main contribution to the NMR relaxation time arises from the slowest mode, with a characteristic time on the picosecond time scale. The first solvation shell of the ion plays a dominant role in the fluctuations of the EFG, all the more that the ion radius is small and its charge is large. We propose an analysis based on a simplified charge distribution around the ion, which demonstrates that the auto-correlation of the EFG, hence the NMR relaxation time, reflects primarily the collective translational motion of water molecules in the first solvation shell of the cations. Our findings provide a microscopic route to the quantitative interpretation of NMR relaxation measurements and open the way to the design of improved analytical theories for NMR relaxation for small ionic solutes, which should focus on water density fluctuations around the ion.

Fluorescent probe studies of polarity and solvation within room temperature ionic liquids: a review.

Science.gov (United States)

Pandey, Shubha; Baker, Sheila N; Pandey, Siddharth; Baker, Gary A

2012-09-01

Ionic liquids display an array of useful and sometimes unconventional, solvent features and have attracted considerable interest in the field of green chemistry for the potential they hold to significantly reduce environmental emissions. Some of these points have a bearing on the chemical reactivity of these systems and have also generated interest in the physical and theoretical aspects of solvation in ionic liquids. This review presents an introduction to the field of ionic liquids, followed by discussion of investigations into the solvation properties of neat ionic liquids or mixed systems including ionic liquids as a major or minor component. The ionic liquid based multicomponent systems discussed are composed of other solvents, other ionic liquids, carbon dioxide, surfactants or surfactant solutions. Although we clearly focus on fluorescence spectroscopy as a tool to illuminate ionic liquid systems, the issues discussed herein are of general relevance to discussions of polarity and solvent effects in ionic liquids. Transient solvation measurements carried out by means of time-resolved fluorescence measurements are particularly powerful for their ability to parameterize the kinetics of the solvation process in ionic liquids and are discussed as well.

Mutagenicity of Tween 80-solvated mild gasification products in the Ames salmonella microsomal assay system

Energy Technology Data Exchange (ETDEWEB)

1992-01-13

The results of the Tween 80-solvated Ames testing of six mild gasification samples indicate significant mutagenic activity only in the composite materials (MG-119 and MG-120), previously suspected from the DMSO-solvated assays, which had shown some variable but ultimately insignificant mutagenic responses. The activity of these samples from the Tween 80-solvated assays was quite low when compared to either the positive controls or the SRC-II HD coal-liquefaction reference material. The class of mutagenic activity expressed by these samples solvated in Tween 80 was that of an indirect-acting, frameshift mutagen(s) since significant activity was found only on tester strain TA98 in the presence of the metabolic activation fraction (S9). Because DMSO and other solvents have been shown to affect the mutagenic activity of certain pure chemicals, the possibility of solvent/mutagen interactions in complex mixtures such as coal-derived liquids exists. Thus, the testing of the genotoxic activity of undefined, chemically complex compounds may require the use of at least two solvent systems to reduce the possibility of artifactual findings. 10 refs., 4 tabs.

A sensitive fluorescent probe for the polar solvation dynamics at protein-surfactant interfaces.

Science.gov (United States)

Singh, Priya; Choudhury, Susobhan; Singha, Subhankar; Jun, Yongwoong; Chakraborty, Sandipan; Sengupta, Jhimli; Das, Ranjan; Ahn, Kyo-Han; Pal, Samir Kumar

2017-05-17

Relaxation dynamics at the surface of biologically important macromolecules is important taking into account their functionality in molecular recognition. Over the years it has been shown that the solvation dynamics of a fluorescent probe at biomolecular surfaces and interfaces account for the relaxation dynamics of polar residues and associated water molecules. However, the sensitivity of the dynamics depends largely on the localization and exposure of the probe. For noncovalent fluorescent probes, localization at the region of interest in addition to surface exposure is an added challenge compared to the covalently attached probes at the biological interfaces. Here we have used a synthesized donor-acceptor type dipolar fluorophore, 6-acetyl-(2-((4-hydroxycyclohexyl)(methyl)amino)naphthalene) (ACYMAN), for the investigation of the solvation dynamics of a model protein-surfactant interface. A significant structural rearrangement of a model histone protein (H1) upon interaction with anionic surfactant sodium dodecyl sulphate (SDS) as revealed from the circular dichroism (CD) studies is nicely corroborated in the solvation dynamics of the probe at the interface. The polarization gated fluorescence anisotropy of the probe compared to that at the SDS micellar surface clearly reveals the localization of the probe at the protein-surfactant interface. We have also compared the sensitivity of ACYMAN with other solvation probes including coumarin 500 (C500) and 4-(dicyanomethylene)-2-methyl-6-(p-dimethylamino-styryl)-4H-pyran (DCM). In comparison to ACYMAN, both C500 and DCM fail to probe the interfacial solvation dynamics of a model protein-surfactant interface. While C500 is found to be delocalized from the protein-surfactant interface, DCM becomes destabilized upon the formation of the interface (protein-surfactant complex). The timescales obtained from this novel probe have also been compared with other femtosecond resolved studies and molecular dynamics simulations.

Multiheteromacrocycles that complex metal ions. Third progress report, 1 May 1976--30 April 1977

International Nuclear Information System (INIS)

Cram, D.J.

1977-01-01

The overall objective of this research is to design, synthesize and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes and clusters. Host organic compounds consist of strategically placed solvating, coordinating and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The specific compounds synthesized and their complexing and lipophilizing properties are summarized

Comparison between implicit and hybrid solvation methods for the ...

Indian Academy of Sciences (India)

Administrator

Both implicit solvation method (dielectric polarizable continuum model, DPCM) and hybrid ... the free energy change (ΔGsol) as per the PCM ... Here the gas phase change is written as ΔGg = ΔEelec + ..... bution to the field of electrochemistry.

Crystal structures of two solvates of (18-crown-6potassium acetate

Directory of Open Access Journals (Sweden)

Phil Liebing

2016-12-01

Full Text Available The crystal and molecular strutures of two solvated forms of [K(18c6]OAc (18c6 = 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane and OAc = acetate were determined by single-crystal X-ray diffraction, namely (acetato-κ2O,O′(1,4,7,10,13,16-hexaoxacyclooctadecane-κ6Opotassium dihydrate, [K(CH3COO(C12H24O6]·2H2O (1 and (acetato-κ2O,O′aqua(1,4,7,10,13,16-hexaoxacyclooctadecane-κ6Opotassium acetic acid monosolvate [K(CH3COO(C12H24O6(H2O]·CH3COOH (2. In both compounds, the acetate anion is bonded to the potassium ion in a chelating fashion and the metal atom is consequently slightly displaced from the O6 plane of the crown ether. In the crystals, O—H...O hydrogen bonds lead to a polymeric ladder structure in the dihydrate 1, while the acetic acid hydrate 2 features inversion dimers.

Synthesis and characterization of ion containing polymers

Science.gov (United States)

Dou, Shichen

Two types of ion-containing polymers are included in this dissertation. The first was focused on the rheology, solvation, and correlation length of polyelectrolyte solutions in terms of charge density, solvent dielectric constant, and solvent quality. The second was focused on the PEO-based polyester ionomers as single ion conductors. A series of polyelectrolytes with varied charge density (0.03 residual salt significantly reduces the viscosity of polyelectrolyte solutions at concentrations c salt, with low residual salt, and with high residual salt concentration. PEO-based polyester ionomers were synthesized by melt polycondensation. Mn was determined using the 1H NMR of ionomers. No ion-cluster was observed from the DSC, SAXS, and rheology measurements. Ionic conductivity greatly depends on the Tg, T-T g and ion content of the ionomers. PEG600-PTMO650 (z)-Li copolyester ionomers show microphase separation and much lower ionic conductivity, compared to that of PE600-Li. PTMO650-Li shows nonconductor behavior.

Sensitivity of Electron Transfer Mediated Decay to Ion Pairing.

Science.gov (United States)

Pohl, Marvin N; Richter, Clemens; Lugovoy, Evgeny; Seidel, Robert; Slavíček, Petr; Aziz, Emad F; Abel, Bernd; Winter, Bernd; Hergenhahn, Uwe

2017-08-17

Ion pairing in electrolyte solutions remains a topic of discussion despite a long history of research. Very recently, nearest-neighbor mediated electronic de-excitation processes of core hole vacancies (electron transfer mediated decay, ETMD) were proposed to carry a spectral fingerprint of local solvation structure and in particular of contact ion pairs. Here, for the first time, we apply electron-electron coincidence detection to a liquid microjet, and record ETMD spectra of Li 1s vacancies in aqueous solutions of lithium chloride (LiCl) in direct comparison to lithium acetate (LiOAc). A change in the ETMD spectrum dependent on the electrolyte anion identity is observed for 4.5 M salt concentration. We discuss these findings within the framework of the formation and presence of contact ion pairs and the unique sensitivity of ETMD spectroscopy to ion pairing.

Photoinduced electron transfer and solvation in iodide-doped acetonitrile clusters.

Science.gov (United States)

Ehrler, Oli T; Griffin, Graham B; Young, Ryan M; Neumark, Daniel M

2009-04-02

We have used ultrafast time-resolved photoelectron imaging to measure charge transfer dynamics in iodide-doped acetonitrile clusters I(-)(CH(3)CN)(n) with n = 5-10. Strong modulations of vertical detachment energies were observed following charge transfer from the halide, allowing interpretation of the ongoing dynamics. We observe a sharp drop in the vertical detachment energy (VDE) within 300-400 fs, followed by a biexponential increase that is complete by approximately 10 ps. Comparison to theory suggests that the iodide is internally solvated and that photodetachment results in formation of a diffuse electron cloud in a confined cavity. We interpret the initial drop in VDE as a combination of expansion of the cavity and localization of the excess electron on one or two solvent molecules. The subsequent increase in VDE is attributed to a combination of the I atom leaving the cavity and rearrangement of the acetonitrile molecules to solvate the electron. The n = 5-8 clusters then show a drop in VDE of around 50 meV on a much longer time scale. The long-time VDEs are consistent with those of (CH(3)CN)(n)(-) clusters with internally solvated electrons. Although the excited-state created by the pump pulse decays by emission of a slow electron, no such decay is seen by 200 ps.

Solvation of decane and benzene in mixtures of 1-octanol and N, N-dimethylformamide

Science.gov (United States)

Kustov, A. V.; Smirnova, N. L.

2016-09-01

The heats of dissolution of decane and benzene in a model system of octanol-1 (OctOH) and N, N-dimethylformamide (DMF) at 308 K are measured using a variable temperature calorimeter equipped with an isothermal shell. Standard enthalpies are determined and standard heat capacities of dissolution in the temperature range of 298-318 K are calculated using data obtained in [1, 2]. The state of hydrocarbon molecules in a binary mixture is studied in terms of the enhanced coordination model (ECM). Benzene is shown to be preferentially solvated by DMF over the range of physiological temperatures. The solvation shell of decane is found to be strongly enriched with 1-octanol. It is obvious that although both hydrocarbons are nonpolar, the presence of the aromatic π-system in benzene leads to drastic differences in their solvation in a lipid-protein medium.

Solution thermodynamics and preferential solvation of sulfamethazine in (methanol + water) mixtures

International Nuclear Information System (INIS)

Delgado, Daniel R.; Almanza, Ovidio A.; Martínez, Fleming; Peña, María A.; Jouyban, Abolghasem; Acree, William E.

2016-01-01

Highlights: • Solubility of sulfamethazine (SMT) was measured in (methanol + water) mixtures. • SMT solubility was correlated with Jouyban–Acree model. • Gibbs energy, enthalpy, and entropy of dissolution of SMT were calculated. • Non-linear enthalpy–entropy relationship was observed for SMT. • Preferential solvation of SMT by methanol was analyzed by using the IKBI method. - Abstract: The solubility of sulfamethazine (SMT) in {methanol (1) + water (2)} co-solvent mixtures was determined at five different temperatures from (293.15 to 313.15) K. The sulfonamide exhibited its highest mole fraction solubility in pure methanol (δ 1 = 29.6 MPa 1/2 ) and its lowest mole fraction solubility in water (δ 2 = 47.8 MPa 1/2 ) at each of the five temperatures studied. The Jouyban–Acree model was used to correlate/predict the solubility values. The respective apparent thermodynamic functions Gibbs energy, enthalpy, and entropy of solution were obtained from the solubility data through the van’t Hoff and Gibbs equations. Apparent thermodynamic quantities of mixing were also calculated for this drug using values of the ideal solubility reported in the literature. A non-linear enthalpy–entropy relationship was noted for SMT in plots of both the enthalpy vs. Gibbs energy of mixing and the enthalpy vs. entropy of mixing. These plots suggest two different trends according to the slopes obtained when the composition of the mixtures changes. Accordingly, the mechanism for SMT transfer processes in water-rich mixtures from water to the mixture with 0.70 in mass fraction of methanol is entropy driven. Conversely, the mechanism is enthalpy driven in mixtures whenever the methanol composition exceeds 0.70 mol fraction. An inverse Kirkwood–Buff integral analysis of the preferential solvation of SMT indicated that the drug is preferentially solvated by water in water-rich mixtures but is preferentially solvated by methanol in methanol-rich mixtures.

Solvation phenomena in association theories with applications to oil & gas and chemical industries

DEFF Research Database (Denmark)

Kontogeorgis, Georgios; Folas, Georgios; Muro Sunè, Nuria

2008-01-01

Association theories e.g. those belonging to the SAFT family account explicitly for self- and cross-association (solvation) phenomena. Such phenomena are of great practical importance as they affect, often dramatically, the phase behaviour of many mixtures of industrial relevance. From the scient......Association theories e.g. those belonging to the SAFT family account explicitly for self- and cross-association (solvation) phenomena. Such phenomena are of great practical importance as they affect, often dramatically, the phase behaviour of many mixtures of industrial relevance. From...

Abacavir methanol 2.5-solvate

Directory of Open Access Journals (Sweden)

Phuong-Truc T. Pham

2009-08-01

Full Text Available The structure of abacavir (systematic name: {(1S,4R-4-[2-amino-6-(cyclopropylamino-9H-purin-9-yl]cyclopent-2-en-1-yl}methanol, C14H18N6O·2.5CH3OH, consists of hydrogen-bonded ribbons which are further held together by additional hydrogen bonds involving the hydroxyl group and two N atoms on an adjacent purine. The asymmetric unit also contains 2.5 molecules of methanol solvate which were grossly disordered and were excluded using SQUEEZE subroutine in PLATON [Spek, (2009. Acta Cryst. D65, 148–155].

Continuous registration of optical absorption spectra of periodically produced solvated electrons

International Nuclear Information System (INIS)

Krebs, P.

1975-01-01

Absorption spectra of unstable intermediates, such as solvated electrons, were usually taken point by point, recording the time-dependent light absorption after their production by a flash. The experimental arrangement for continuous recording of the spectra consists of a conventional one beam spectral photometer with a stabilized white light source, a monochromator, and a light detector. By periodic production of light absorbing intermediates such as solvated electrons, e.g., by ac uv light, a small ac signal is modulated on the light detector output which after amplification can be continuously recorded as a function of wavelength. This method allows the detection of absorption spectra when disturbances from the outside provide a signal-to-noise ratio smaller than 1

Microscopic picture of the aqueous solvation of glutamic acid

NARCIS (Netherlands)

Leenders, E.J.M.; Bolhuis, P.G.; Meijer, E.J.

2008-01-01

We present molecular dynamics simulations of glutamic acid and glutamate solvated in water, using both density functional theory (DFT) and the Gromos96 force field. We focus on the microscopic aspects of the solvation−particularly on the hydrogen bond structures and dynamics−and investigate the

Structure and dynamics of aqueous solution of uranyl ions

International Nuclear Information System (INIS)

Chopra, Manish; Choudhury, Niharendu

2014-01-01

The present work describes a molecular dynamics simulation study of structure and dynamics of aqueous solution of uranyl ions in water. Structural properties of the system in terms of radial distribution functions and dynamical characteristics as obtained through velocity autocorrelation function and mean square displacements have been analyzed. The results for radial distribution functions show the oxygen of water to form the first solvation shell at 2.4 Å around the uranium atom, whereas the hydrogen atoms of water are distributed around the uranium atom with the major peak at around 3.0 Å. Analyses of transport behaviors of ions and water through MSD indicates that the diffusion of the uranyl ion is much less as compared to that of the water molecules. It is also observed that the dynamical behavior of water molecules gets modified due to the presence of uranyl ion. The effect of increase in concentration of uranyl ions on the structure and dynamics of water molecules is also studied

Incorporation of Hydrogen Bond Angle Dependency into the Generalized Solvation Free Energy Density Model.

Science.gov (United States)

Ma, Songling; Hwang, Sungbo; Lee, Sehan; Acree, William E; No, Kyoung Tai

2018-04-23

To describe the physically realistic solvation free energy surface of a molecule in a solvent, a generalized version of the solvation free energy density (G-SFED) calculation method has been developed. In the G-SFED model, the contribution from the hydrogen bond (HB) between a solute and a solvent to the solvation free energy was calculated as the product of the acidity of the donor and the basicity of the acceptor of an HB pair. The acidity and basicity parameters of a solute were derived using the summation of acidities and basicities of the respective acidic and basic functional groups of the solute, and that of the solvent was experimentally determined. Although the contribution of HBs to the solvation free energy could be evenly distributed to grid points on the surface of a molecule, the G-SFED model was still inadequate to describe the angle dependency of the HB of a solute with a polarizable continuum solvent. To overcome this shortcoming of the G-SFED model, the contribution of HBs was formulated using the geometric parameters of the grid points described in the HB coordinate system of the solute. We propose an HB angle dependency incorporated into the G-SFED model, i.e., the G-SFED-HB model, where the angular-dependent acidity and basicity densities are defined and parametrized with experimental data. The G-SFED-HB model was then applied to calculate the solvation free energies of organic molecules in water, various alcohols and ethers, and the log P values of diverse organic molecules, including peptides and a protein. Both the G-SFED model and the G-SFED-HB model reproduced the experimental solvation free energies with similar accuracy, whereas the distributions of the SFED on the molecular surface calculated by the G-SFED and G-SFED-HB models were quite different, especially for molecules having HB donors or acceptors. Since the angle dependency of HBs was included in the G-SFED-HB model, the SFED distribution of the G-SFED-HB model is well described

Solvation dynamics of lithium salts in wet nitrobenzene

Czech Academy of Sciences Publication Activity Database

Moakes, G.; Gelbaum, L. T.; Leisen, J.; Janata, J.; Mareček, Vladimír

2006-01-01

Roč. 593, 1-2 (2006), s. 111-118 ISSN 0022-0728 R&D Projects: GA ČR GA203/03/0822 Grant - others:Georgia Research Alliance(US) GRA.CG06.D Institutional research plan: CEZ:AV0Z40400503 Keywords : solvation * NMR * FTIR * nitrobenzene/water * solvatomers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.339, year: 2006

Solvated electrons at elevated temperatures in different alcohols: Temperature and molecular structure effects

Energy Technology Data Exchange (ETDEWEB)

Yan, Yu [Department of Nuclear Engineering and Management, Graduate School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Lin, Mingzhang [Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, 2-4 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1195 (Japan); Katsumura, Yosuke, E-mail: katsu@n.t.u-tokyo.ac.j [Department of Nuclear Engineering and Management, Graduate School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656 (Japan); Nuclear Professional School, Graduate School of Engineering, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan); Fu, Haiying; Muroya, Yusa [Nuclear Professional School, Graduate School of Engineering, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan)

2010-12-15

The absorption spectra of solvated electrons in pentanol, hexanol and octanol are measured from 22 to 200, 22 to 175 and 50 to150 {sup o}C, respectively, at a fixed pressure of 15 MPa, using nanosecond pulse radiolysis technique. The results show that the peak positions of the absorption spectra have a red-shift (shift to longer wavelengths) as temperature increases, similar to water and other alcohols. Including the above mentioned data, a compilation of currently available experimental data on the energy of absorption maximum (E{sub max}) of solvated electrons changed with temperature in monohydric alcohols, diols and triol is presented. E{sub max} of solvated electron is larger in those alcohols that have more OH groups at all the temperatures. The molecular structure effect, including OH numbers, OH position and carbon chain length, is investigated. For the primary alcohols with same OH group number and position, the temperature coefficient increases with increase in chain length. For the alcohols with same chain length and OH numbers, temperature coefficient is larger for the symmetric alcohols than the asymmetric ones.

Spectroscopic and quantum-chemical investigation of association of ions in acetonitrile - LiX (X=I, ClO4, NCS) systems

International Nuclear Information System (INIS)

Semenov, S.G.; Solov'eva, L.A.; Akopyan, S.Kh.

1995-01-01

Data on association constants of ions in acetonitrile-salt binary systems, obtained from the data on intensity of IR absorption bands of acetonitrile (Acn) molecules contained in solvate shells of Li + cations, have been analyzed. Using the CCP MO LCAO semiempirical method in the PPDP approximation, electronic structure of acetonitrile molecule and Acn k Li + and Acn m Li + X - complexes has been studied. It is ascertained that relative stability of ionic pairs Acn 3 Li + X - , estimated by the squares of their dipole momenta (characterizing solvation energy) increases in the series X=I, ClO 4 , NCS in agreement with data of spectroscopic experiment, according to which the constant of ion association for LiNCS solution in acetonitrile is much higher than for the systems CH 3 CN-LiI and CH 3 CN-LiClO 4 . 13 refs.,2 figs., 2 tabs.64

Solvent density inhomogeneities and solvation free energies in supercritical diatomic fluids: a density functional approach.

Science.gov (United States)

Husowitz, B; Talanquer, V

2007-02-07

Density functional theory is used to explore the solvation properties of a spherical solute immersed in a supercritical diatomic fluid. The solute is modeled as a hard core Yukawa particle surrounded by a diatomic Lennard-Jones fluid represented by two fused tangent spheres using an interaction site approximation. The authors' approach is particularly suitable for thoroughly exploring the effect of different interaction parameters, such as solute-solvent interaction strength and range, solvent-solvent long-range interactions, and particle size, on the local solvent structure and the solvation free energy under supercritical conditions. Their results indicate that the behavior of the local coordination number in homonuclear diatomic fluids follows trends similar to those reported in previous studies for monatomic fluids. The local density augmentation is particularly sensitive to changes in solute size and is affected to a lesser degree by variations in the solute-solvent interaction strength and range. The associated solvation free energies exhibit a nonmonotonous behavior as a function of density for systems with weak solute-solvent interactions. The authors' results suggest that solute-solvent interaction anisotropies have a major influence on the nature and extent of local solvent density inhomogeneities and on the value of the solvation free energies in supercritical solutions of heteronuclear molecules.

Solvation quantities from a COSMO-RS equation of state

International Nuclear Information System (INIS)

Panayiotou, C.; Tsivintzelis, I.; Aslanidou, D.; Hatzimanikatis, V.

2015-01-01

Highlights: • Extension of the successful COSMO-RS model to an equation-of-state model. • Two scaling constants, obtained from atom-specific contributions. • Overall estimation of the solvation quantities and contributions. - Abstract: This work focuses on the extension of the successful COSMO-RS model of mixtures into an equation-of-state model of fluids and its application for the estimation of solvation/hydration quantities of a variety of chemical substances. These quantities include free-energies, enthalpies and entropies of hydration as well as the separate contributions to each of them. Emphasis is given on the estimation of contributions from the conformational changes of solutes upon solvation and the associated restructuring of solvent in its immediate neighborhood. COSMO-RS is a quantum-mechanics based group/segment contribution model in which the Quasi-Chemical (QC) approach is used for the description of the non-random distribution of interacting segments in the system. Thus, the equation-of-state development is done through such a QC framework. The new model will not need any adjustable parameters for the strong specific interactions, such as hydrogen bonds, since they will be provided by the quantum-mechanics based cosmo-files – a key feature of COSMO-RS model. It will need, however, one volumetric and one energy parameter per fluid, which are scaling constants or molecular descriptors of the fluid and are obtained from rather easily available data such as densities, boiling points, vapor pressures, heats of vaporization or second virial coefficients. The performance and the potential of the new equation-of-state model to become a fully predictive model are critically discussed

Jahn Teller effect of cations in water: The cupric ion in water

Energy Technology Data Exchange (ETDEWEB)

Halley, J.W. [Minnesota Univ., Minneapolis, MN (United States). School of Physics and Astronomy; Wang, X.R. [Hong Kong Univ. of Science and Technology, Kowlon (Hong Kong). Dept. of Physics; Curtiss, L.A. [Argonne National Lab., IL (United States)

1993-02-01

We report a molecular dynamics model for the Jahn Teller effect in the solvation shell of a cation in solution in an aqueous liquid. We apply the model to the cupric ion and compare results with results of neutron scattering experiments on copper chlorate solutions. We conclude that the original interpretation of the experiments in terms of a Jan Teller effect may require modification.

The solvation of carbohydrates in dimethylsulfoxide and water

International Nuclear Information System (INIS)

Berger, S.; Diaz, M.D.; Horwat, Ch.

1999-01-01

The solvation of sucrose and other carbohydrates in DMSO and water is probed by intermolecular NOE measurements. The NOE effects are interpreted in terms of specific binding of the solvent to certain sites of the molecules. It is shown that DMSO attaches to specific sites of the sucrose molecule, whereas for water such a clear differentiation cannot be proven. (author)

XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Summary of reports

International Nuclear Information System (INIS)

2011-01-01

The collection contains materials of plenary, sectional and poster sessions, presented at the XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Theoretical questions and new experimental methods of chemistry of solutions, structure and dynamics of molecular and ion-molecular systems in solution and at the phase boundary; modern aspects of applied chemistry of solutions are discussed [ru

Proton-bound cluster ions in ion mobility spectrometry

Science.gov (United States)

Ewing, R. G.; Eiceman, G. A.; Stone, J. A.

1999-01-01

Gaseous oxygen and nitrogen bases, both singly and as binary mixtures, have been introduced into ion mobility spectrometers to study the appearance of protonated molecules, and proton-bound dimers and trimers. At ambient temperature it was possible to simultaneously observe, following the introduction of molecule A, comparable intensities of peaks ascribable to the reactant ion (H2O)nH+, the protonated molecule AH+ and AH+ H2O, and the symmetrical proton bound dimer A2H+. Mass spectral identification confirmed the identifications and also showed that the majority of the protonated molecules were hydrated and that the proton-bound dimers were hydrated to a much lesser extent. No significant peaks ascribable to proton-bound trimers were obtained no matter how high the sample concentration. Binary mixtures containing molecules A and B, in some cases gave not only the peaks unique to the individual compounds but also peaks due to asymmetrical proton bound dimers AHB+. Such ions were always present in the spectra of mixtures of oxygen bases but were not observed for several mixtures of oxygen and nitrogen bases. The dimers, which were not observable, notable for their low hydrogen bond strengths, must have decomposed in their passage from the ion source to the detector, i.e. in a time less than approximately 5 ms. When the temperature was lowered to -20 degrees C, trimers, both homogeneous and mixed, were observed with mixtures of alcohols. The importance of hydrogen bond energy, and hence operating temperature, in determining the degree of solvation of the ions that will be observed in an ion mobility spectrometer is stressed. The possibility is discussed that a displacement reaction involving ambient water plays a role in the dissociation.

Thermodynamics of sublimation and solvation for bicyclo-derivatives of 1,3-thiazine

International Nuclear Information System (INIS)

Ol’khovich, Marina V.; Blokhina, Svetlana V.; Sharapova, Angelica V.; Perlovich, German L.; Proshin, Alexey N.

2013-01-01

Highlights: • Temperature dependencies of saturated vapor pressure of new bicyclo-derivatives were obtained. • Thermodynamic functions of sublimation and solvation were calculated. • The correlations between thermodynamic functions and molecular descriptors are discussed. - Abstract: Temperature dependencies of saturated vapor pressure of novel bicyclo-derivatives of 1,3-thiazine with methoxy- and carbonyl-substituents have been obtained by method of transference by means of an inert gas carrier. Thermodynamic functions of sublimation have been calculated. Correlations between thermodynamic functions of sublimation and thermophysical properties of the substances and molecular descriptors have been established. The enthalpies of solvation of compounds were calculated using the measured values of enthalpies of sublimation and of standard enthalpies of solution in hexane and buffer

Solvation of excess electrons trapped in charge pockets on molecular surfaces

Science.gov (United States)

Jalbout, Abraham F.

This work considers the ability of hydrogen fluoride (HF) to solvate excess electrons located on cyclic hydrocarbon surfaces. The principle applied involves the formation of systems in which excess electrons can be stabilized not only on concentrated molecular surface charge pockets but also by HF. Recent studies have shown that OH groups can form stable hydrogen-bonded networks on one side of a hydrocarbon surface (i.e. cyclohexane sheets), at the same time, the hydrogen atoms on the opposite side of this surface form a pocket of positive charge can attract the excess electron. This density can be further stabilized by the addition of an HF molecule that can form an 'anion with an internally solvated electron' (AISE) state. These systems are shown to be stable with respect to vertical electron detachment (VDE).

Infrared spectroscopy of model electrochemical interfaces in ultrahigh vacuum: some implications for ionic and chemisorbate solvation at electrode surfaces

Science.gov (United States)

Villegas, Ignacio; Kizhakevariam, Naushad; Weaver, Michael J.

1995-07-01

The utility of infrared reflection-absorption spectroscopy (IRAS) for examining structure and bonding for model electrochemical interfaces in ultrahigh vacuum (UHV) is illustrated, focusing specifically on the solvation of cations and chemisorbed carbon monoxide on Pt(111). These systems were chosen partly in view of the availability of IRAS data (albeit limited to chemisorbate vibrations) for the corresponding in-situ metal-solution interfaces, enabling direct spectral comparisons to be made with the "UHV electrochemical model" systems. Kelvin probe measurements of the metal-UHV surface potential changes (ΔΦ) attending alterations in the interfacial composition are also described: these provide the required link to the in-situ electrode potentials as well as yielding additional insight into surface solvation. Variations in the negative electronic charge density and, correspondingly, in the cation surface concentration (thereby mimicking charge-induced alterations in the electrode potential below the potential of zero charge) are achieved by potassium atom dosage onto Pt(111). Of the solvents selected for discussion here — deuterated water, methanol, and acetonitrile — the first two exhibit readily detectable vibrational bands which provide information on the ionic solvation structure. Progressively dosing these solvents onto Pt(111) in the presence of low potassium coverages yields marked alterations in the solvent vibrational bands which can be understood in terms of sequential cation solvation. Comparison between these spectra for methanol with analogous data for sequential methanol solvation of gas-phase alkali cations enables the influence of the interfacial environment to be assessed. The effects of solvating chemisorbed CO are illustrated for acetonitrile; the markedly larger shifts in CO frequencies and binding sites for dilute CO adlayers can be accounted for in terms of short-range coadsorbate interactions in addition to longer-range Stark effects

Modifying Poisson equation for near-solute dielectric polarization and solvation free energy

Energy Technology Data Exchange (ETDEWEB)

Yang, Pei-Kun, E-mail: peikun@isu.edu.tw

2016-06-15

Highlights: • We modify the Poisson equation. • The dielectric polarization was calculated from the modified Poisson equation. • The solvation free energies of the solutes were calculated from the dielectric polarization. • The calculated solvation free energies were similar to those obtained from MD simulations. - Abstract: The dielectric polarization P is important for calculating the stability of protein conformation and the binding affinity of protein–protein/ligand interactions and for exploring the nonthermal effect of an external electric field on biomolecules. P was decomposed into the product of the electric dipole moment per molecule p; bulk solvent density N{sub bulk}; and relative solvent molecular density g. For a molecular solute, 4πr{sup 2}p(r) oscillates with the distance r to the solute, and g(r) has a large peak in the near-solute region, as observed in molecular dynamics (MD) simulations. Herein, the Poisson equation was modified for computing p based on the modified Gauss’s law of Maxwell’s equations, and the potential of the mean force was used for computing g. For one or two charged atoms in a water cluster, the solvation free energies of the solutes obtained by these equations were similar to those obtained from MD simulations.

Ultrafast dynamics of solvation and charge transfer in a DNA-based biomaterial.

Science.gov (United States)

Choudhury, Susobhan; Batabyal, Subrata; Mondol, Tanumoy; Sao, Dilip; Lemmens, Peter; Pal, Samir Kumar

2014-05-01

Charge migration along DNA molecules is a key factor for DNA-based devices in optoelectronics and biotechnology. The association of a significant amount of water molecules in DNA-based materials for the intactness of the DNA structure and their dynamic role in the charge-transfer (CT) dynamics is less documented in contemporary literature. In the present study, we have used a genomic DNA-cetyltrimethyl ammonium chloride (CTMA) complex, a technological important biomaterial, and Hoechest 33258 (H258), a well-known DNA minor groove binder, as fluorogenic probe for the dynamic solvation studies. The CT dynamics of CdSe/ZnS quantum dots (QDs; 5.2 nm) embedded in the as-prepared and swollen biomaterial have also been studied and correlated with that of the timescale of solvation. We have extended our studies on the temperature-dependent CT dynamics of QDs in a nanoenvironment of an anionic, sodium bis(2-ethylhexyl)sulfosuccinate reverse micelle (AOT RMs), whereby the number of water molecules and their dynamics can be tuned in a controlled manner. A direct correlation of the dynamics of solvation and that of the CT in the nanoenvironments clearly suggests that the hydration barrier within the Arrhenius framework essentially dictates the charge-transfer dynamics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvation thermodynamics of L-cystine, L-tyrosine, and L-leucine in aqueous-electrolyte media

Science.gov (United States)

Roy, Sanjay; Guin, Partha Sarathi; Mahali, Kalachand; Dolui, Bijoy Krishna

2017-12-01

Solubilities of L-cystine, L-tyrosine, and L-leucine in aqueous NaCl media at 298.15 K have been studied. Indispensable and related solvent parameters such as molar mass, molar volume, etc., were also determined. The results are used to evaluate the standard transfer Gibbs free energy, cavity forming enthalpy of transfer, cavity forming transfer Gibbs free energy and dipole-dipole interaction effects during the course of solvation. Various weak interactions involving solute-solvent or solvent-solvent molecules were characterized in order to find their role on the solvation of these amino acids.

Alkylation of nitriles with gaseous carbenium ions. The ritter reaction in the dilute gas state

International Nuclear Information System (INIS)

Cacace, F.; Ciranni, G.; Giacomello, P.

1982-01-01

Radiolytically formed carbenium ions, such as sec-C 3 H 7 + , sec-C 4 H 9 + , and t-C 4 H 9 + , react in the gas phase with model aliphatic and aromatic nitriles yielding the corresponding nitrilium ions. The latter undergo efficient condensation with water that eventually leads to the formation of the corresponding N-alkylamides. The mechanism is analogous to the Ritter reaction in solution. The reactivity and selectivity of the gas-phase electrophilic attack on nitriles has been deduced from competition experiments under conditions that largely exclude the effects of solvation, ion pairing, etc., which complicate the interpretation of solution-chemistry measurements. 1 table

Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies.

Science.gov (United States)

Bardhan, Jaydeep P; Jungwirth, Pavel; Makowski, Lee

2012-09-28

Two mechanisms have been proposed to drive asymmetric solvent response to a solute charge: a static potential contribution similar to the liquid-vapor potential, and a steric contribution associated with a water molecule's structure and charge distribution. In this work, we use free-energy perturbation molecular-dynamics calculations in explicit water to show that these mechanisms act in complementary regimes; the large static potential (∼44 kJ/mol/e) dominates asymmetric response for deeply buried charges, and the steric contribution dominates for charges near the solute-solvent interface. Therefore, both mechanisms must be included in order to fully account for asymmetric solvation in general. Our calculations suggest that the steric contribution leads to a remarkable deviation from the popular "linear response" model in which the reaction potential changes linearly as a function of charge. In fact, the potential varies in a piecewise-linear fashion, i.e., with different proportionality constants depending on the sign of the charge. This discrepancy is significant even when the charge is completely buried, and holds for solutes larger than single atoms. Together, these mechanisms suggest that implicit-solvent models can be improved using a combination of affine response (an offset due to the static potential) and piecewise-linear response (due to the steric contribution).

Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies

Science.gov (United States)

Bardhan, Jaydeep P.; Jungwirth, Pavel; Makowski, Lee

2012-01-01

Two mechanisms have been proposed to drive asymmetric solvent response to a solute charge: a static potential contribution similar to the liquid-vapor potential, and a steric contribution associated with a water molecule's structure and charge distribution. In this work, we use free-energy perturbation molecular-dynamics calculations in explicit water to show that these mechanisms act in complementary regimes; the large static potential (∼44 kJ/mol/e) dominates asymmetric response for deeply buried charges, and the steric contribution dominates for charges near the solute-solvent interface. Therefore, both mechanisms must be included in order to fully account for asymmetric solvation in general. Our calculations suggest that the steric contribution leads to a remarkable deviation from the popular “linear response” model in which the reaction potential changes linearly as a function of charge. In fact, the potential varies in a piecewise-linear fashion, i.e., with different proportionality constants depending on the sign of the charge. This discrepancy is significant even when the charge is completely buried, and holds for solutes larger than single atoms. Together, these mechanisms suggest that implicit-solvent models can be improved using a combination of affine response (an offset due to the static potential) and piecewise-linear response (due to the steric contribution). PMID:23020318

Additive scheme for calculation of solvation enthalpies of heterocyclic aromatic compounds. Sublimation/vaporization enthalpy at 298.15 K

International Nuclear Information System (INIS)

Solomonov, Boris N.; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.

2016-01-01

Highlights: • Additivity scheme for solvation enthalpies estimation of heteroaromatic compounds was proposed. • Method for determination of vaporization/sublimation enthalpies directly at 298.15 K was developed. • Solution enthalpies of 25 heteroaromatic compounds were measured. • Vaporization/sublimation enthalpies of 44 heteroaromatic compounds were determined. • Obtained values are in good agreement with the results of conventional methods. - Abstract: Hereby we propose a method for determination of vaporization and sublimation enthalpies of heterocyclic and carbonyl-containing aromatic compounds at 298.15 K. According to this method vaporization and sublimation enthalpies at 298.15 K are determined based on enthalpies of solvation and solution. Solvation enthalpies of heteroatomatic and carbonyl-containing compounds are calculated using an additive scheme from the solvation enthalpy of closest aromatic hydrocarbon and contributions related to the exchange of CH-groups of hydrocarbon with corresponding substituent atoms or groups. Measured solution enthalpies together with calculated solvation enthalpies allowed to calculate corresponding vaporization and sublimation enthalpies at 298.15 K for a large number of heterocyclic and carbonyl-containing compounds. We have also found that in a number of cases instead of solution enthalpy in benzene at 298.15 K fusion enthalpy at the melting temperature can be used. Comparison between literature data and calculated vaporization and sublimation enthalpies demonstrates satisfactory performance of the proposed method.

Additive scheme for calculation of solvation enthalpies of heterocyclic aromatic compounds. Sublimation/vaporization enthalpy at 298.15 K

Energy Technology Data Exchange (ETDEWEB)

Solomonov, Boris N., E-mail: boris.solomonov@kpfu.ru; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.

2016-06-10

Highlights: • Additivity scheme for solvation enthalpies estimation of heteroaromatic compounds was proposed. • Method for determination of vaporization/sublimation enthalpies directly at 298.15 K was developed. • Solution enthalpies of 25 heteroaromatic compounds were measured. • Vaporization/sublimation enthalpies of 44 heteroaromatic compounds were determined. • Obtained values are in good agreement with the results of conventional methods. - Abstract: Hereby we propose a method for determination of vaporization and sublimation enthalpies of heterocyclic and carbonyl-containing aromatic compounds at 298.15 K. According to this method vaporization and sublimation enthalpies at 298.15 K are determined based on enthalpies of solvation and solution. Solvation enthalpies of heteroatomatic and carbonyl-containing compounds are calculated using an additive scheme from the solvation enthalpy of closest aromatic hydrocarbon and contributions related to the exchange of CH-groups of hydrocarbon with corresponding substituent atoms or groups. Measured solution enthalpies together with calculated solvation enthalpies allowed to calculate corresponding vaporization and sublimation enthalpies at 298.15 K for a large number of heterocyclic and carbonyl-containing compounds. We have also found that in a number of cases instead of solution enthalpy in benzene at 298.15 K fusion enthalpy at the melting temperature can be used. Comparison between literature data and calculated vaporization and sublimation enthalpies demonstrates satisfactory performance of the proposed method.

Origin of parameter degeneracy and molecular shape relationships in geometric-flow calculations of solvation free energies

Energy Technology Data Exchange (ETDEWEB)

Daily, Michael D. [Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Chun, Jaehun [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Heredia-Langner, Alejandro [National Security Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Wei, Guowei [Department of Mathematics, Michigan State University, East Lansing, Michigan 48824 (United States); Baker, Nathan A. [Computational and Statistical Analytics Division, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States)

2013-11-28

Implicit solvent models are important tools for calculating solvation free energies for chemical and biophysical studies since they require fewer computational resources but can achieve accuracy comparable to that of explicit-solvent models. In past papers, geometric flow-based solvation models have been established for solvation analysis of small and large compounds. In the present work, the use of realistic experiment-based parameter choices for the geometric flow models is studied. We find that the experimental parameters of solvent internal pressure p = 172 MPa and surface tension γ = 72 mN/m produce solvation free energies within 1 RT of the global minimum root-mean-squared deviation from experimental data over the expanded set. Our results demonstrate that experimental values can be used for geometric flow solvent model parameters, thus eliminating the need for additional parameterization. We also examine the correlations between optimal values of p and γ which are strongly anti-correlated. Geometric analysis of the small molecule test set shows that these results are inter-connected with an approximately linear relationship between area and volume in the range of molecular sizes spanned by the data set. In spite of this considerable degeneracy between the surface tension and pressure terms in the model, both terms are important for the broader applicability of the model.

Improvements to the APBS biomolecular solvation software suite: Improvements to the APBS Software Suite

Energy Technology Data Exchange (ETDEWEB)

Jurrus, Elizabeth [Pacific Northwest National Laboratory, Richland Washington; Engel, Dave [Pacific Northwest National Laboratory, Richland Washington; Star, Keith [Pacific Northwest National Laboratory, Richland Washington; Monson, Kyle [Pacific Northwest National Laboratory, Richland Washington; Brandi, Juan [Pacific Northwest National Laboratory, Richland Washington; Felberg, Lisa E. [University of California, Berkeley California; Brookes, David H. [University of California, Berkeley California; Wilson, Leighton [University of Michigan, Ann Arbor Michigan; Chen, Jiahui [Southern Methodist University, Dallas Texas; Liles, Karina [Pacific Northwest National Laboratory, Richland Washington; Chun, Minju [Pacific Northwest National Laboratory, Richland Washington; Li, Peter [Pacific Northwest National Laboratory, Richland Washington; Gohara, David W. [St. Louis University, St. Louis Missouri; Dolinsky, Todd [FoodLogiQ, Durham North Carolina; Konecny, Robert [University of California San Diego, San Diego California; Koes, David R. [University of Pittsburgh, Pittsburgh Pennsylvania; Nielsen, Jens Erik [Protein Engineering, Novozymes A/S, Copenhagen Denmark; Head-Gordon, Teresa [University of California, Berkeley California; Geng, Weihua [Southern Methodist University, Dallas Texas; Krasny, Robert [University of Michigan, Ann Arbor Michigan; Wei, Guo-Wei [Michigan State University, East Lansing Michigan; Holst, Michael J. [University of California San Diego, San Diego California; McCammon, J. Andrew [University of California San Diego, San Diego California; Baker, Nathan A. [Pacific Northwest National Laboratory, Richland Washington; Brown University, Providence Rhode Island

2017-10-24

The Adaptive Poisson-Boltzmann Solver (APBS) software was developed to solve the equations of continuum electrostatics for large biomolecular assemblages that has provided impact in the study of a broad range of chemical, biological, and biomedical applications. APBS addresses three key technology challenges for understanding solvation and electrostatics in biomedical applications: accurate and efficient models for biomolecular solvation and electrostatics, robust and scalable software for applying those theories to biomolecular systems, and mechanisms for sharing and analyzing biomolecular electrostatics data in the scientific community. To address new research applications and advancing computational capabilities, we have continually updated APBS and its suite of accompanying software since its release in 2001. In this manuscript, we discuss the models and capabilities that have recently been implemented within the APBS software package including: a Poisson-Boltzmann analytical and a semi-analytical solver, an optimized boundary element solver, a geometry-based geometric flow solvation model, a graph theory based algorithm for determining pKa values, and an improved web-based visualization tool for viewing electrostatics.

Solvated protein-protein docking using Kyte-Doolittle-based water preferences

NARCIS (Netherlands)

Kastritis, P.; Visscher, K.M.; van Dijk, A.D.J.; Bonvin, A.M.J.J.

2013-01-01

HADDOCK is one of the few docking programs that can explicitly account for water molecules in the docking process. Its solvated docking protocol starts from hydrated molecules and a fraction of the resulting interfacial waters is subsequently removed in a biased Monte Carlo procedure based on

Solvated protein-protein docking using Kyte-Doolittle-based water preferences

NARCIS (Netherlands)

Kastritis, Panagiotis L.; Visscher, Koen M.; van Dijk, Aalt D.J.; Bonvin, Alexandre M.J.J.

HADDOCK is one of the few docking programs that can explicitly account for water molecules in the docking process. Its solvated docking protocol starts from hydrated molecules and a fraction of the resulting interfacial waters is subsequently removed in a biased Monte Carlo procedure based on

Molecular Studies of Complex Soil Organic Matter Interactions with Metal Ions and Mineral Surfaces using Classical Molecular Dynamics and Quantum Chemistry Methods

Science.gov (United States)

Andersen, A.; Govind, N.; Laskin, A.

2017-12-01

Mineral surfaces have been implicated as potential protectors of soil organic matter (SOM) against decomposition and ultimate mineralization to small molecules which can provide nutrients for plants and soil microbes and can also contribute to the Earth's elemental cycles. SOM is a complex mixture of organic molecules of biological origin at varying degrees of decomposition and can, itself, self-assemble in such a way as to expose some biomolecule types to biotic and abiotic attack while protecting other biomolecule types. The organization of SOM and SOM with mineral surfaces and solvated metal ions is driven by an interplay of van der Waals and electrostatic interactions leading to partitioning of hydrophilic (e.g. sugars) and hydrophobic (e.g., lipids) SOM components that can be bridged with amphiphilic molecules (e.g., proteins). Classical molecular dynamics simulations can shed light on assemblies of organic molecules alone or complexation with mineral surfaces. The role of chemical reactions is also an important consideration in potential chemical changes of the organic species such as oxidation/reduction, degradation, chemisorption to mineral surfaces, and complexation with solvated metal ions to form organometallic systems. For the study of chemical reactivity, quantum chemistry methods can be employed and combined with structural insight provided by classical MD simulations. Moreover, quantum chemistry can also simulate spectroscopic signatures based on chemical structure and is a valuable tool in interpreting spectra from, notably, x-ray absorption spectroscopy (XAS). In this presentation, we will discuss our classical MD and quantum chemistry findings on a model SOM system interacting with mineral surfaces and solvated metal ions.

Secondary deuterium isotope effects in the hydrolysis of some acetals

International Nuclear Information System (INIS)

Paterson, R.V.

Secondary α-deuterium kinetic isotope effects have been determined in the hydrolyses of some acetals. Benzaldehyde dimethyl acetal and 2-phenyl-1,3-dioxolan show isotope effects in agreement with an A1 mechanism. 2-Phenyl-4,4,5,5-tetramethyl-1,3-dioxolan, which has been shown to undergo hydrolysis by an A2 type mechanism, has an isotope effect in agreement with participation by water in the transition state. Hydrolysis of benzylidene norbornanediols, although complicated by isomerisation, has an isotope effect in agreement with an A2 mechanism. Kinetic isotope effects in acetals which have a neighbouring carboxyl group have also been determined. Hydrolysis of 2-carboxybenzaldehyde dimethyl acetal in aqueous and 82% w/w dioxan-water buffers has isotope effects in agreement with a large degree of carbonium ion character in the transition state. Anderson and Capon proposed nucleophilic participation in the hydrolysis of this acetal in 82% dioxan-water. The isotope effect determined in this study is not in agreement with this finding. Hydrolysis of 2-(2'-carboxyphenyl)-4,4,5,5-tetramethyl-1,3-dioxolan shows an isotope effect larger than the corresponding dioxolan without the carboxyl group in agreement with some carbonium ion character in the transition state. A new synthesis of a deuterated aldehyde is described which might be general for aldehydes which will not form benzoins readily. (author)

Effect of solvation on reactions of aluminium, gallium, indium, zinc and cadmium with azo compounds

International Nuclear Information System (INIS)

Savvin, S.B.

1985-01-01

Colour reactions have been examined between Al, Ga, In, Zn, Cd and reagents of a group of chromotropic acid 2.7-bisazo derivatives (Picramin B, Picramin M, Methanyl B, sulphonitrophenol M, sulphonitrophenol B) in organo-aqueous solutions containing acetone, propanol, DMFA, DMSO and acetic acid. Sensitive colour reactions occur in all the cases in aceton- or propanol-containing solutions: more sensitive than in water for Al, Ga, In; new reactions for Zn and Cd which are specific for organo-aqueous media and not observed in aqueous solutions. Sensitive reactions are observed only for Al and Ga in DMSO or DMFA solutions. Zn, Cd and In do not give colour reactions in such solutions. Differences in colour reactions for the elements in DMFA- and DMSO-containing media are connected with different solvation effects of the solvents on certain cations. Preferable solvation of some cations has been confirmed by infrared studies and is in agreement with the data reported on selective solvation

Modelling the Preferential Solvation of Ferulic Acid in {2-Propanol (1 + Water (2} Mixtures at 298.15 K

Directory of Open Access Journals (Sweden)

Abolghasem Jouyban 1,2, Fleming Martínez 3 *

2017-12-01

Full Text Available Background: Recently Haq et al. reported the equilibrium solubility in {2-propanol (1 + water (2} mixtures at several temperatures with some numerical correlation analysis. Nevertheless, no attempt was made to evaluate the preferential solvation of this compound by the solvents. Methods: Preferential solvation of ferulic acid in the saturated mixtures at 298.15 K was analyzed based on the inverse Kirkwood-Buff integrals as described in the literature. Results: Ferulic acid is preferentially solvated by water in water-rich mixtures (0.00 < x1 < 0.19 but preferentially solvated by 2-propanol in mixtures with composition 0.19 < x1 < 1.00. Conclusion: These results could be interpreted as a consequence of hydrophobic hydration around the non-polar groups of the solute in the former case (0.00 < x1 < 0.19. Moreover, in the last case (0.19 < x1 < 1.00, the observed trend could be a consequence of the acid behavior of ferulic acid in front to 2-propanol molecules because this cosolvent is more basic than water as described by the respective solvatochromic parameters.

6,6'-Dimethoxygossypol: molecular structure, crystal polymorphism, and solvate formation

Science.gov (United States)

6,6´-Dimethoxygossypol (DMG) is a naturally produced derivative of gossypol that is found in relatively high concentration in some Gossypium barbadense cotton varieties. Like gossypol, DMG forms an equimolar solvate with acetic acid, but it was not clear if, like gossypol, the compound would form c...

Octanol-Water Partition Coefficient from 3D-RISM-KH Molecular Theory of Solvation with Partial Molar Volume Correction.

Science.gov (United States)

Huang, WenJuan; Blinov, Nikolay; Kovalenko, Andriy

2015-04-30

The octanol-water partition coefficient is an important physical-chemical characteristic widely used to describe hydrophobic/hydrophilic properties of chemical compounds. The partition coefficient is related to the transfer free energy of a compound from water to octanol. Here, we introduce a new protocol for prediction of the partition coefficient based on the statistical-mechanical, 3D-RISM-KH molecular theory of solvation. It was shown recently that with the compound-solvent correlation functions obtained from the 3D-RISM-KH molecular theory of solvation, the free energy functional supplemented with the correction linearly related to the partial molar volume obtained from the Kirkwood-Buff/3D-RISM theory, also called the "universal correction" (UC), provides accurate prediction of the hydration free energy of small compounds, compared to explicit solvent molecular dynamics [ Palmer , D. S. ; J. Phys.: Condens. Matter 2010 , 22 , 492101 ]. Here we report that with the UC reparametrized accordingly this theory also provides an excellent agreement with the experimental data for the solvation free energy in nonpolar solvent (1-octanol) and so accurately predicts the octanol-water partition coefficient. The performance of the Kovalenko-Hirata (KH) and Gaussian fluctuation (GF) functionals of the solvation free energy, with and without UC, is tested on a large library of small compounds with diverse functional groups. The best agreement with the experimental data for octanol-water partition coefficients is obtained with the KH-UC solvation free energy functional.

Enthalpies of potassium iodide dissolution in dimethyl acetamide mixtures with water

International Nuclear Information System (INIS)

Privalova, N.M.; Gritsenko, S.I.; Vorob'ev, A.F.

1986-01-01

Enthalpies of potassium iodide dissolution in mixed dimethyl acetamide - water solvent at 298.15 K in the whole range of dimethyl acetamide compositions are measured by the calorimetric method. From the plots of KI dissolution enthalpy dependence and dependence of experimental ΔH p∞ 0 value deviations from calculational ones on solvent composition, as well as from the results of calculation of solvate shell composition of potassium iodide ions in the mixed solvent, it is obvious that in the region of 0-15 mol% concentrations of dimethyl acetamide insufficient enrichment of solvate ion shells by dimethyl acetamide (DMAA) occurs, in the region of 15-40 mol% DMAA compositions enrichment of solvate shells of ions by water occurs, in the region of 40-100 mol% DMAA enrichment of solvate ion shells by the organic component in comparison with mixture compostion occurs. Maximum enrichment of solvate ion shells by mixture components in three above mentioned regions of the mixed solvent occurs at 10, 30 and 80 mol% DMAA concentrations

Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.

Science.gov (United States)

Zhu, Di; Zhang, Linghong; Ruther, Rose E; Hamers, Robert J

2013-09-01

The photocatalytic reduction of N₂ to NH₃ is typically hampered by poor binding of N₂ to catalytic materials and by the very high energy of the intermediates involved in this reaction. Solvated electrons directly introduced into the reactant solution can provide an alternative pathway to overcome such limitations. Here we demonstrate that illuminated hydrogen-terminated diamond yields facile electron emission into water, thus inducing reduction of N₂ to NH₃ at ambient temperature and pressure. Transient absorption measurements at 632 nm reveal the presence of solvated electrons adjacent to the diamond after photoexcitation. Experiments using inexpensive synthetic diamond samples and diamond powder show that photocatalytic activity is strongly dependent on the surface termination and correlates with the production of solvated electrons. The use of diamond to eject electrons into a reactant liquid represents a new paradigm for photocatalytic reduction, bringing electrons directly to reactants without requiring molecular adsorption to the surface.

A solvated electron lithium electrode for secondary batteries

Science.gov (United States)

Sammells, A. F.; Semkow, K. W.

1986-09-01

Attention is given to a novel method for the achievement of high electro-chemical reversibility in Li-based nonaqueous cells, using a liquid negative electrode that consists of Li dissolved in liquid ammonia as a solvated electron Li electrode. The containment of this liquid negative active material from direct contact to a liquid nonaqueous electrolyte in the positive electrode compartment was realized through the use of a Li-intercalated, electronically conducting ceramic membrane.

Performance of the SMD and SM8 models for predicting solvation free energy of neutral solutes in methanol, dimethyl sulfoxide and acetonitrile

Science.gov (United States)

Zanith, Caroline C.; Pliego, Josefredo R.

2015-03-01

The continuum solvation models SMD and SM8 were developed using 2,346 solvation free energy values for 318 neutral molecules in 91 solvents as reference. However, no solvation data of neutral solutes in methanol was used in the parametrization, while only few solvation free energy values of solutes in dimethyl sulfoxide and acetonitrile were used. In this report, we have tested the performance of the models for these important solvents. Taking data from literature, we have generated solvation free energy, enthalpy and entropy values for 37 solutes in methanol, 21 solutes in dimethyl sulfoxide and 19 solutes in acetonitrile. Both SMD and SM8 models have presented a good performance in methanol and acetonitrile, with mean unsigned error equal or less than 0.66 and 0.55 kcal mol-1 in methanol and acetonitrile, respectively. However, the correlation is worse in dimethyl sulfoxide, where the SMD and SM8 methods present mean unsigned error of 1.02 and 0.95 kcal mol-1, respectively. Our results point out the SMx family of models need be improved for dimethyl sulfoxide solvent.

Ion pair and solvation dynamics of [Bmim][BF4 ] + water system.

Science.gov (United States)

Cascão, João; Silva, Wagner; Ferreira, Ana S D; Cabrita, Eurico J

2018-02-01

In this work, 1-butyl-3-methylimidazolium tetrafluoroborate/water mixtures were analysed over the whole water composition (x w ) in order to study the rotational and translational behaviour of the ions. We employed a multinuclear NMR approach to determine anion/cation/water diffusion coefficients and longitudinal relaxation rates at different water content. In neat ionic liquids (IL), the cation diffuses faster than the anion, and at low x w , anions and cations share almost the same diffusion coefficient, but above a critical water concentration, the anion begins to diffuse faster than the cation. We identified this composition as approximately 10% x w where the ions share the same diffusion coefficient. We found that the water at this composition seems to have a much more dramatic effect in the rotational diffusion of the anion that decreases substantially and approaches that of the anion in the diluted IL. Translational and rotational dynamics of the ions suggest that water is first incorporated in pockets in the nanostructure of the IL allowing the ions to maintain most of the cation/anion interactions present in neat IL but already disrupting some anion/cation interactions due to preferential interaction with the anion. HOESY and NOESY data show that water displays contacts both with the cation and the anion in a positive NOE regime in contrary to the negative regime found for the cation/anion and cation/cation cross-relaxation. This is in accordance with the high relative diffusion coefficient of water and suggests that water molecules can exchange between preferential location sites that allow water to maintain contacts both with the anion and cation. Copyright © 2017 John Wiley & Sons, Ltd.

Quantitative prediction of solvation free energy in octanol of organic compounds.

Science.gov (United States)

Delgado, Eduardo J; Jaña, Gonzalo A

2009-03-01

The free energy of solvation, DeltaGS0, in octanol of organic compounds is quantitatively predicted from the molecular structure. The model, involving only three molecular descriptors, is obtained by multiple linear regression analysis from a data set of 147 compounds containing diverse organic functions, namely, halogenated and non-halogenated alkanes, alkenes, alkynes, aromatics, alcohols, aldehydes, ketones, amines, ethers and esters; covering a DeltaGS0 range from about -50 to 0 kJ.mol(-1). The model predicts the free energy of solvation with a squared correlation coefficient of 0.93 and a standard deviation, 2.4 kJ.mol(-1), just marginally larger than the generally accepted value of experimental uncertainty. The involved molecular descriptors have definite physical meaning corresponding to the different intermolecular interactions occurring in the bulk liquid phase. The model is validated with an external set of 36 compounds not included in the training set.

Examination of hydrogen-bonding interactions between dissolved solutes and alkylbenzene solvents based on Abraham model correlations derived from measured enthalpies of solvation

Energy Technology Data Exchange (ETDEWEB)

Varfolomeev, Mikhail A.; Rakipov, Ilnaz T. [Chemical Institute, Kazan Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation); Acree, William E., E-mail: acree@unt.edu [Department of Chemistry, 1155 Union Circle # 305070, University of North Texas, Denton, TX 76203-5017 (United States); Brumfield, Michela [Department of Chemistry, 1155 Union Circle # 305070, University of North Texas, Denton, TX 76203-5017 (United States); Abraham, Michael H. [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)

2014-10-20

Highlights: • Enthalpies of solution measured for 48 solutes dissolved in mesitylene. • Enthalpies of solution measured for 81 solutes dissolved in p-xylene. • Abraham model correlations derived for enthalpies of solvation of solutes in mesitylene. • Abraham model correlations derived for enthalpies of solvation of solutes in p-xylene. • Hydrogen-bonding enthalpies reported for interactions of aromatic hydrocarbons with hydrogen-bond acidic solutes. - Abstract: Enthalpies of solution at infinite dilution of 48 organic solutes in mesitylene and 81 organic solutes in p-xylene were measured using isothermal solution calorimeter. Enthalpies of solvation for 92 organic vapors and gaseous solutes in mesitylene and for 130 gaseous compounds in p-xylene were determined from the experimental and literature data. Abraham model correlations are determined from the experimental enthalpy of solvation data. The derived correlations describe the experimental gas-to-mesitylene and gas-to-p-xylene solvation enthalpies to within average standard deviations of 1.87 kJ mol{sup −1} and 2.08 kJ mol{sup −1}, respectively. Enthalpies of X-H⋯π (X-O, N, and C) hydrogen bond formation of proton donor solutes (alcohols, amines, chlorinated hydrocarbons etc.) with mesitylene and p-xylene were calculated based on the Abraham solvation equation. Obtained values are in good agreement with the results determined using conventional methods.

Electrospray droplet exposure to organic vapors: metal ion removal from proteins and protein complexes.

Science.gov (United States)

DeMuth, J Corinne; McLuckey, Scott A

2015-01-20

The exposure of aqueous nanoelectrospray droplets to various organic vapors can dramatically reduce sodium adduction on protein ions in positive ion mass spectra. Volatile alcohols, such as methanol, ethanol, and isopropanol lead to a significant reduction in sodium ion adduction but are not as effective as acetonitrile, acetone, and ethyl acetate. Organic vapor exposure in the negative ion mode, on the other hand, has essentially no effect on alkali ion adduction. Evidence is presented to suggest that the mechanism by which organic vapor exposure reduces alkali ion adduction in the positive mode involves the depletion of alkali metal ions via ion evaporation of metal ions solvated with organic molecules. The early generation of metal/organic cluster ions during the droplet desolvation process results in fewer metal ions available to condense on the protein ions formed via the charged residue mechanism. These effects are demonstrated with holomyoglobin ions to illustrate that the metal ion reduction takes place without detectable protein denaturation, which might be revealed by heme loss or an increase in charge state distribution. No evidence is observed for denaturation with exposure to any of the organic vapors evaluated in this work.

Tris[2-(deuteriomethylsulfanylphenyl]phosphine deuteriochloroform 0.125-solvate

Directory of Open Access Journals (Sweden)

Seik Weng Ng

2008-05-01

Full Text Available The title deuterated tripodal phosphine, C21H12D9PS3·0.125CDCl3, crystallizes as two independent molecules, one of which lies on a general position and the other about a threefold rotation axis, and as a deuteriochloroform solvate. The solvent molecule is disordered about a site of symmetry 3, so that the ratio of phosphine to solvent is 8:1. The P atom adopts a pyramidal coordination geometry.

Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

Science.gov (United States)

Cram, D. J.

1980-01-15

Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

Interface of the polarizable continuum model of solvation with semi-empirical methods in the GAMESS program

DEFF Research Database (Denmark)

Svendsen, Casper Steinmann; Blædel, Kristoffer L.; Christensen, Anders Steen

2013-01-01

An interface between semi-empirical methods and the polarized continuum model (PCM) of solvation successfully implemented into GAMESS following the approach by Chudinov et al (Chem. Phys. 1992, 160, 41). The interface includes energy gradients and is parallelized. For large molecules such as ubiq......An interface between semi-empirical methods and the polarized continuum model (PCM) of solvation successfully implemented into GAMESS following the approach by Chudinov et al (Chem. Phys. 1992, 160, 41). The interface includes energy gradients and is parallelized. For large molecules...

Reactivity of the cadmium ion in concentrated phosphoric acid solutions.

Science.gov (United States)

De Gyves, J; Gonzales, J; Louis, C; Bessiere, J

1989-07-01

The solvation transfer coefficients which characterize the changes of ion reactivity with phosphoric acid concentration have been calculated for cadmium from the constants of the successive chloride complexes, and for silver and diethyldithiophosphate from potentiometric measurements. They evidence the strong desolvation of the cadmium species in concentrated phosphoric acid media, causing a remarkable increase of its reactivity. They allow the results of liquid-liquid extraction, precipitation and flotation reactions to be correctly interpreted and their changes to be foreseen when the reagents are modified.

Water-enhanced solvation of organics

Energy Technology Data Exchange (ETDEWEB)

Lee, Jane H. [Univ. of California, Berkeley, CA (United States)

1993-07-01

Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log γ_s vs x_w/x_s curve. From graph shape Δ(log γ_s) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid, propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement Δ(log γ_acid)/Δ(x_w/x_acid) = -0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was -0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol and 2,3-butanediol did not level off at large water/solute mole ratio. Solutes investigated by solid-liquid equilibrium were citric acid, gallic acid, phenol, xylenols, 2-naphthol. Saturation concentration of citric acid in anhydrous butyl acetate increased from 0.0009 to 0.087 mol/L after 1.3 % (g/g) water co-dissolved into organic phase. Effect of water-enhanced solvation for citric acid is very large but very small for phenol and its derivatives.

Solvation dynamics in triton-X-100 and triton-X-165 micelles: Effect of micellar size and hydration

Science.gov (United States)

Kumbhakar, Manoj; Nath, Sukhendu; Mukherjee, Tulsi; Pal, Haridas

2004-09-01

Dynamic Stokes' shift measurements using coumarin 153 as the fluorescence probe have been carried out to study solvation dynamics in two nonionic micelles, viz., triton-X-100 (TX-100) and triton-X-165 (TX-165). In both the micelles, the solvent relaxation dynamics is biexponential in nature. While the fast solvation time τs1 is seen to be almost similar for both the micelles, the slow solvation time τs2 is found to be appreciably smaller in TX-165 than in TX-100 micelle. Dynamic light scattering measurements indicate that the TX-165 micelles are substantially smaller in size than that of TX-100. Assuming similar core size for both the micelles, as expected from the similar chemical structures of the nonpolar ends for both the surfactants, the Palisade layer is also indicated to be substantially thinner for TX-165 micelles than that of TX-100. The aggregation number of TX-165 micelles is also found to be substantially smaller than that of TX-100 micelles. Fluorescence spectral studies of C153 dye in the two micelles indicate that the Palisade layer of TX-165 micelles is more polar than that of TX-100 micelles. Fluorescence anisotropy measurements indicate that the microviscosity in the Palisade layer of TX-165 micelles is also lower than that of TX-100 micelles. Based on these results it is inferred that the structure of the Palisade layer of TX-165 micelles is quite loose and have higher degree hydration in comparison to that of TX-100 micelles. Due to these structural differences in the Palisade layers of TX-165 and TX-100 micelles the solvation dynamics is faster in the former micelles than in the latter. It has been further inferred that in the present systems the collective response of the water molecules at somewhat away from the probes is responsible for the faster component of the solvation time, which does not reflect much of the structural changes of the micellar Palisade layer. On the contrary, the slower solvation time component, which is mainly due to

Preferential solvation of fluorenone and 4-hydroxyfluorenone in binary solvent mixtures

International Nuclear Information System (INIS)

Jozefowicz, Marek; Heldt, Janina R.

2003-01-01

Preferential solvation of fluorenone and 4-hydroxyfluorenone in binary solvent mixtures has been studied using steady-state spectroscopic measurements. This study concerns the solvent-induced shift of the absorption and fluorescence spectra of both molecules in two solvent mixtures, i.e., cyclohexane-tetrahydrofuran and cyclohexane-ethanol. The first system contains polar solute molecules, fluorenone and 4-hydroxyfluorenone, in a mixture of polar aprotic (tetrahydrofuran) and non-polar (cyclohexane) solvents. In the second solvents mixture, hydrogen bonding with solute molecules (ethanol) may occur. The results of spectroscopic measurements are analysed using theoretical models of Bakshiev, Mazurenko and Suppan which describe preferential solvation phenomena. In the case of cyclohexane-tetrahydrofuran mixtures, the deviation from linearity in the absorption and fluorescence solvatochromic shifts vs. the solution polarity is due to non-specific dipolar solvent-solute interactions. For cyclohexane-ethanol binary mixtures, both non-specific and specific (hydrogen bond and proton-relay tautomerization) interactions contribute to the observed solvatochromism

Quantitative Prediction of Solvation Free Energy in Octanol of Organic Compounds

Directory of Open Access Journals (Sweden)

Eduardo J. Delgado

2009-03-01

Full Text Available The free energy of solvation, ΔGS0 , in octanol of organic compunds is quantitatively predicted from the molecular structure. The model, involving only three molecular descriptors, is obtained by multiple linear regression analysis from a data set of 147 compounds containing diverse organic functions, namely, halogenated and non-halogenated alkanes, alkenes, alkynes, aromatics, alcohols, aldehydes, ketones, amines, ethers and esters; covering a ΔGS0 range from about –50 to 0 kJ·mol-1. The model predicts the free energy of solvation with a squared correlation coefficient of 0.93 and a standard deviation, 2.4 kJ·mol-1, just marginally larger than the generally accepted value of experimental uncertainty. The involved molecular descriptors have definite physical meaning corresponding to the different intermolecular interactions occurring in the bulk liquid phase. The model is validated with an external set of 36 compounds not included in the training set.

Hydration number of alkali metal ions determined by insertion in a conducting polymer

DEFF Research Database (Denmark)

Skaarup, Steen

2008-01-01

of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior may depend on the details of ion hydration....... The solvation of alkali metal ions has been discussed for many years without a clear consensus. This work presents a systematic study of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS...... direct calculation of the number of M+ ions entering the film, and therefore the inserted M+ mass. The mass of the water molecules is calculated as a difference. The results yield the following primary hydration numbers: Li+: 5.5-5.6; Na+: 4.0-4.1; K+: 2.0-2.5; Rb+: 0.6-1.2; Cs+: ~0. The most important...

Solvation of o-hydroxybenzoic acid in pure and modified supercritical carbon dioxide, according to numerical modeling data

Science.gov (United States)

Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.; Petrenko, V. E.

2015-08-01

The dissolution of an elementary fragment of crystal structure (an o-hydroxybenzoic acid ( o-HBA) dimer) in both pure and modified supercritical (SC) carbon dioxide by adding methanol (molar fraction, 0.035) at T = 318 K, ρ = 0.7 g/cm3 is simulated. Features of the solvation mechanism in each solvent are revealed. The solvation of o-HBA in pure SC CO2 is shown to occur via electron donor-acceptor interactions. o-HBA forms a solvate complex in modified SC CO2 through hydrogen bonds between the carboxyl group and methanol. The hydroxyl group of o-HBA participates in the formation of an intramolecular hydrogen bond, and not in interactions with the solvent. It is concluded that the o-HBA-methanol complex is a stable molecular structure, and its lifetime is one order of magnitude higher than those of other hydrogen bonds in fluids.

Interaction of d(10) metal ions with thioether ligands: a thermodynamic and theoretical study.

Science.gov (United States)

Melchior, Andrea; Peralta, Elena; Valiente, Manuel; Tavagnacco, Claudio; Endrizzi, Francesco; Tolazzi, Marilena

2013-05-07

Thermodynamic parameters of complex formation between d(10) metal ions, such as Zn(2+), Cd(2+), Hg(2+) and Ag(+), and the macrocyclic thioether 1,4,7-trithiacyclononane ([9]AneS3) or the monodentate diethylsulfide (Et(2)S), in acetonitrile (AN) at 298.15 K, were studied by a systematic methodology including potentiometry, calorimetry and polarography. [9]AneS3 is able to form complexes with all the target cations, Et(2)S only reacts with Hg(2+) and Ag(+). Mononuclear ML(j) (j = 1, 2) complexes are formed with all the metal ions investigated, where the affinity order is Hg(2+) > Ag(+) > Cd(2+) ≈ Zn(2+) when L = [9]AneS3 and Hg(2+) > Ag(+) when L = Et(2)S. Enthalpy and entropy values are generally negative, as a consequence of both metal ion interactions with neutral ligands, the reagents' loss of degrees of freedom and the release of solvating molecules. DFT calculations on the complexes formed with [9]AneS3 in vacuum and in AN are also carried out, to correlate experimental and theoretical thermodynamic values and to highlight the interplay between the direct metal-thioether interaction and the solvation effects. Trends obtained for the stability constants and enthalpies of the 1 : 1 and 1 : 2 complexes in solvent well reproduce the experimental ones for all the divalent metal ion complexes with [9]AneS3 and indicate the release of 3 AN molecules in the formation of each consecutive octahedral complex. In addition, calculated and experimental values for Ag(+) complex formation in solution suggest that in AgL(2) species [9]AneS3 ligands are not both tridentate.

Enthalpies of solution, enthalpies of fusion and enthalpies of solvation of polyaromatic hydrocarbons: Instruments for determination of sublimation enthalpy at 298.15 K

Energy Technology Data Exchange (ETDEWEB)

Solomonov, Boris N., E-mail: boris.solomonov@ksu.ru; Varfolomeev, Mikhail A.; Nagrimanov, Ruslan N.; Mukhametzyanov, Timur A.; Novikov, Vladimir B.

2015-12-20

Graphical abstract: - Highlights: • Solution enthalpies of aromatic hydrocarbons were measured at 298.15 K. • Solution enthalpy of aromatic hydrocarbons in benzene is equal to their fusion enthalpy. • Method for calculation of solvation enthalpy of aromatic hydrocarbons was proposed. • Approach for estimation of aromatic hydrocarbons sublimation enthalpy was developed. • Obtained sublimation enthalpies coincide well with the recommended literature data. - Abstract: In this work a simple method for calculation of solvation enthalpies of polyaromatic hydrocarbons (PAHs) in various solvents at 298.15 K was proposed. According to this method the enthalpy of solvation of any polyaromatic hydrocarbon in a particular solvent can be calculated on the basis of the general formula of the compound, the solvation enthalpy of benzene in the same solvent and parameter related to the contribution of hydrogen atom into solvation enthalpy. The validity of the proposed method was confirmed by the comparison of calculated and experimentally measured values of solvation enthalpies of PAHs in benzene, tetrahydrofuran and acetonitrile. This method was used for determination of the sublimation enthalpy of PAHs at 298.15 K based on the general relationship between the enthalpy of sublimation/vaporization of the compound of interest and its enthalpies of solution and solvation in the same solvent at 298.15 K. Enthalpies of solution at infinite dilution of several PAHs were measured in acetonitrile, benzene and tetrahydrofuran at 298.15 K. It was shown that solution enthalpies of PAHs in benzene at 298.15 K are approximately equal to their fusion enthalpies at the melting temperature. Solvation enthalpies of 15 PAHs at 298.15 K calculated according to the proposed method together with corresponding fusion enthalpy values (at the melting temperature) were used to calculate the sublimation enthalpy values at 298.15 K. Comparison of the obtained results with recommended values of

Computational Study of Geometry, Solvation Free Energy, Dipole Moment, Polarizability, Hyperpolarizability and Molecular Properties of 2-Methylimidazole

Directory of Open Access Journals (Sweden)

Mohammad Firoz Khan

2016-12-01

Full Text Available Ab initio calculations were carried out to study the geometry, solvation free energy, dipole moment, molecular electrostatic potential (MESP, Mulliken and Natural charge distribution, polarizability, hyperpolarizability, Natural Bond Orbital (NBO energetic and different molecular properties like global reactivity descriptors (chemical hardness, softness, chemical potential, electronegativity, electrophilicity index of 2-methylimidazole. B3LYP/6-31G(d,p level of theory was used to optimize the structure both in the gas phase and in solution. The solvation free energy, dipole moment and molecular properties were calculated by applying the Solvation Model on Density (SMD in four solvent systems, namely water, dimethylsulfoxide (DMSO, n-octanol and chloroform. The computed bond distances, bond angles and dihedral angles of 2-methylimidazole agreed reasonably well with the experimental data except for C(2-N(1, C(4-C(5 and N(1-H(7 bond lengths and N(1-C(5-C(4 bond angle. The solvation free energy, dipole moment, polarizability, first order hyperpolarizability, chemical potential, electronegativity and electrophilicity index of 2-methylimidazole increased on going from non-polar to polar solvents. Chemical hardness also increased with increasing polarity of the solvent and the opposite relation was found in the case of softness. These results provide better understanding of the stability and reactivity of 2-methylimidazole in different solvent systems.

Ion-pair and triple-ion formation of some tetraalkylammonium iodides in n-hexanol and its binary mixtures with o-toluidine

International Nuclear Information System (INIS)

Roy, Mahendra Nath; Sarkar, Lovely; Dewan, Rajani

2011-01-01

The electrolytic conductivity of the tetraalkylammonium iodides, R 4 NI (R = butyl to heptyl), has been studied in (0.00, 0.25, 0.50 and 0.75) mass fraction of o-toluidine (C 7 H 9 N) in n-hexanol (C 6 H 14 O) at T = 298.15 K. The limiting molar conductance Λ 0 , association constants K A and the co-sphere diameter R for ion-pair formation in 0.00 and 0.25 mass fraction of solvent mixture have been evaluated using the Fuoss-equation. However, the deviation of the conductometric curves (Λversusc 1/2 ) from linearity for the electrolytes at 0.50 and 0.75 mass fraction of o-toluidine (C 7 H 9 N) in n-hexanol (C 6 H 14 O) indicates triple ion formation, and therefore the corresponding conductance data have been analyzed by the Fuoss-Kraus theory of triple ions. The observed values of the molar conductivity are explained by the ion-pairs (M + + X - ↔ MX) and triple-ions (2M + +X - ↔M 2 X + ,M + +2X - ↔MX 2 - ) formation. From the investigations, the following trend in conductance of the solvated salts has been observed: Display Omitted

Mutagenicity of Tween 80-solvated mild gasification products in the Ames salmonella microsomal assay system. [Quarterly report, October--December 1991

Energy Technology Data Exchange (ETDEWEB)

1992-01-13

The results of the Tween 80-solvated Ames testing of six mild gasification samples indicate significant mutagenic activity only in the composite materials (MG-119 and MG-120), previously suspected from the DMSO-solvated assays, which had shown some variable but ultimately insignificant mutagenic responses. The activity of these samples from the Tween 80-solvated assays was quite low when compared to either the positive controls or the SRC-II HD coal-liquefaction reference material. The class of mutagenic activity expressed by these samples solvated in Tween 80 was that of an indirect-acting, frameshift mutagen(s) since significant activity was found only on tester strain TA98 in the presence of the metabolic activation fraction (S9). Because DMSO and other solvents have been shown to affect the mutagenic activity of certain pure chemicals, the possibility of solvent/mutagen interactions in complex mixtures such as coal-derived liquids exists. Thus, the testing of the genotoxic activity of undefined, chemically complex compounds may require the use of at least two solvent systems to reduce the possibility of artifactual findings. 10 refs., 4 tabs.

Solvation free energies and partition coefficients with the coarse-grained and hybrid all-atom/coarse-grained MARTINI models.

Science.gov (United States)

Genheden, Samuel

2017-10-01

We present the estimation of solvation free energies of small solutes in water, n-octanol and hexane using molecular dynamics simulations with two MARTINI models at different resolutions, viz. the coarse-grained (CG) and the hybrid all-atom/coarse-grained (AA/CG) models. From these estimates, we also calculate the water/hexane and water/octanol partition coefficients. More than 150 small, organic molecules were selected from the Minnesota solvation database and parameterized in a semi-automatic fashion. Using either the CG or hybrid AA/CG models, we find considerable deviations between the estimated and experimental solvation free energies in all solvents with mean absolute deviations larger than 10 kJ/mol, although the correlation coefficient is between 0.55 and 0.75 and significant. There is also no difference between the results when using the non-polarizable and polarizable water model, although we identify some improvements when using the polarizable model with the AA/CG solutes. In contrast to the estimated solvation energies, the estimated partition coefficients are generally excellent with both the CG and hybrid AA/CG models, giving mean absolute deviations between 0.67 and 0.90 log units and correlation coefficients larger than 0.85. We analyze the error distribution further and suggest avenues for improvements.

Solvation free energies and partition coefficients with the coarse-grained and hybrid all-atom/coarse-grained MARTINI models

Science.gov (United States)

Genheden, Samuel

2017-10-01

We present the estimation of solvation free energies of small solutes in water, n-octanol and hexane using molecular dynamics simulations with two MARTINI models at different resolutions, viz. the coarse-grained (CG) and the hybrid all-atom/coarse-grained (AA/CG) models. From these estimates, we also calculate the water/hexane and water/octanol partition coefficients. More than 150 small, organic molecules were selected from the Minnesota solvation database and parameterized in a semi-automatic fashion. Using either the CG or hybrid AA/CG models, we find considerable deviations between the estimated and experimental solvation free energies in all solvents with mean absolute deviations larger than 10 kJ/mol, although the correlation coefficient is between 0.55 and 0.75 and significant. There is also no difference between the results when using the non-polarizable and polarizable water model, although we identify some improvements when using the polarizable model with the AA/CG solutes. In contrast to the estimated solvation energies, the estimated partition coefficients are generally excellent with both the CG and hybrid AA/CG models, giving mean absolute deviations between 0.67 and 0.90 log units and correlation coefficients larger than 0.85. We analyze the error distribution further and suggest avenues for improvements.

Broadband Dielectric Spectroscopy and Quasi-Elastic Neutron Scattering on Single-Ion Polymer Conductors

Science.gov (United States)

Soles, Christopher; Peng, Hua-Gen; Page, Kirt; Snyder, Chad; Pandy, Ashoutosh; Jeong, Youmi; Runt, James; NIST Collaboration; Pennsylvania Collaboration

2011-03-01

The application of solid polymer electrolytes in rechargeable batteries has not been fully realized after decades of research due to its low conductivity. Dramatic increases of the ion conductivity are needed and this progress requires the understanding of conduction mechanism. We address this topic in two fronts, namely, the effect of plasticizer additives and geometric confinement on the charge transfer mechanism. To this end, we combine broadband dielectric spectroscopy (BDS) to characterize the ion mobility and quasi-elastic neutron scattering (QENS) to quantify segmental motion on a single-ion model polymer electrolyte. Deuterated small molecules were used as plasticizers so that the segmental motion of the polymer electrolyte could be monitored by QENS to understand the mechanism behind the increased conductivity. Anodic aluminum oxide (AAO) membranes with well defined channel sizes are used as the matrix to study the transport of ions solvated in a 1D polymer electrolyte.

Lieb-Liniger-like model of quantum solvation in CO-4HeN clusters

Science.gov (United States)

Farrelly, D.; Iñarrea, M.; Lanchares, V.; Salas, J. P.

2016-05-01

Small 4He clusters doped with various molecules allow for the study of "quantum solvation" as a function of cluster size. A peculiarity of quantum solvation is that, as the number of 4He atoms is increased from N = 1, the solvent appears to decouple from the molecule which, in turn, appears to undergo free rotation. This is generally taken to signify the onset of "microscopic superfluidity." Currently, little is known about the quantum mechanics of the decoupling mechanism, mainly because the system is a quantum (N + 1)-body problem in three dimensions which makes computations difficult. Here, a one-dimensional model is studied in which the 4He atoms are confined to revolve on a ring and encircle a rotating CO molecule. The Lanczos algorithm is used to investigate the eigenvalue spectrum as the number of 4He atoms is varied. Substantial solvent decoupling is observed for as few as N = 5 4He atoms. Examination of the Hamiltonian matrix, which has an almost block diagonal structure, reveals increasingly weak inter-block (solvent-molecule) coupling as the number of 4He atoms is increased. In the absence of a dopant molecule the system is similar to a Lieb-Liniger (LL) gas and we find a relatively rapid transition to the LL limit as N is increased. In essence, the molecule initially—for very small N—provides a central, if relatively weak, attraction to organize the cluster; as more 4He atoms are added, the repulsive interactions between the identical bosons start to dominate as the solvation ring (shell) becomes more crowded which causes the molecule to start to decouple. For low N, the molecule pins the atoms in place relative to itself; as N increases the atom-atom repulsion starts to dominate the Hamiltonian and the molecule decouples. We conclude that, while the notion of superfluidity is a useful and correct description of the decoupling process, a molecular viewpoint provides complementary insights into the quantum mechanism of the transition from a molecular

Geometric and energetic considerations of surface fluctuations during ion transfer across the water-immiscible organic liquid interface

Energy Technology Data Exchange (ETDEWEB)

Karnes, John J.; Benjamin, Ilan, E-mail: benjamin@chemistry.ucsc.edu [Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064 (United States)

2016-07-07

Molecular dynamics simulations and umbrella sampling free energy calculations are used to examine the thermodynamics, energetics, and structural fluctuations that accompany the transfer of a small hydrophilic ion (Cl{sup −}) across the water/nitrobenzene interface. By examining several constrained interface structures, we isolate the energetic costs of interfacial deformation and co-transfer of hydration waters during the ion transfer. The process is monitored using both energy-based solvation coordinates and a geometric coordinate recently introduced by Morita and co-workers to describe surface fluctuations. Our simulations show that these coordinates provide a complimentary description of the water surface fluctuations during the transfer and are necessary for elucidating the mechanism of the ion transfer.

SAMPL4, a blind challenge for computational solvation free energies: the compounds considered

Science.gov (United States)

Guthrie, J. Peter

2014-03-01

For the fifth time I have provided a set of solvation energies (1 M gas to 1 M aqueous) for a SAMPL challenge. In this set there are 23 blind compounds and 30 supplementary compounds of related structure to one of the blind sets, but for which the solvation energy is readily available. The best current values of each compound are presented along with complete documentation of the experimental origins of the solvation energies. The calculations needed to go from reported data to solvation energies are presented, with particular attention to aspects which are new to this set. For some compounds the vapor pressures (VP) were reported for the liquid compound, which is solid at room temperature. To correct from VPsubcooled liquid to VPsublimation requires ΔSfusion, which is only known for mannitol. Estimated values were used for the others, all but one of which were benzene derivatives and expected to have very similar values. The final compound for which ΔSfusion was estimated was menthol, which melts at 42 °C so that modest errors in ΔSfusion will have little effect. It was also necessary to look into the effects of including estimated values of ΔCp on this correction. The approximate sizes of the effects of inclusion of ΔCp in the correction from VPsubcooled liquid to VPsublimation were estimated and it was noted that inclusion of ΔCp invariably makes ΔGS more positive. To extend the set of compounds for which the solvation energy could be calculated we explored the use of boiling point (b.p.) data from Reaxys/Beilstein as a substitute for studies of the VP as a function of temperature. B.p. data are not always reliable so it was necessary to develop a criterion for rejecting outliers. For two compounds (chlorinated guaiacols) it became clear that inclusion represented overreach; for each there were only two independent pressure, temperature points, which is too little for a trustworthy extrapolation. For a number of compounds the extrapolation from lowest

Solvation-based vapour pressure model for (solvent + salt) systems in conjunction with the Antoine equation

International Nuclear Information System (INIS)

Senol, Aynur

2013-01-01

Highlights: • Vapour pressures of (solvent + salt) systems have been estimated through a solvation-based model. • Two structural forms of the generalized solvation model using the Antoine equation have been performed. • A simplified concentration-dependent vapour pressure model has been also processed. • The model reliability analysis has been performed in terms of a log-ratio objective function. • The reliability of the models has been interpreted in terms of the statistical design factors. -- Abstract: This study deals with modelling the vapour pressure of a (solvent + salt) system on the basis of the principles of LSER. The solvation model framework clarifies the simultaneous impact of several physical variables such as the vapour pressure of a pure solvent estimated by the Antoine equation, the solubility and solvatochromic parameters of the solvent and the physical properties of the ionic salt. It has been analyzed independently the performance of two structural forms of the generalized model, i.e., a relation depending on an integration of the properties of the solvent and the ionic salt and a relation on a reduced property-basis. A simplified concentration-dependent vapour pressure model has been also explored and implemented on the relevant systems. The vapour pressure data of sixteen (solvent + salt) systems have been processed to analyze statistically the reliability of existing models in terms of a log–ratio objective function. The proposed vapour pressure models match relatively well the observed performance, yielding the overall design factors of 1.066 and 1.073 for the solvation-based models with the integrated and reduced properties, and 1.008 for the concentration-based model, respectively

Characterization of solvated electrons in hydrogen cyanide clusters: (HCN)n- (n=3, 4)

Science.gov (United States)

Wu, Di; Li, Ying; Li, Zhuo; Chen, Wei; Li, Zhi-Ru; Sun, Chia-Chung

2006-02-01

Theoretical studies of the solvated electrons (HCN)n- (n =3, 4) reveal a variety of electron trapping possibilities in the (HCN)n (n =3, 4) clusters. Two isomers for (HCN)3- and four isomers for (HCN)4- are obtained at the MP2/aug -cc-pVDZ+dBF (diffusive bond functions) level of theory. In view of vertical electron detachment energies (VDEs) at the CCSD(T) level, the excess electron always "prefers" locating in the center of the system, i.e., the isomer with higher coordination number shows larger VDE value. However, the most stable isomers of the solvated electron state (HCN)3- and (HCN)4- are found to be the linear C∞ν and D∞h structures, respectively, but not the fullyl symmetric structures which have the largest VDE values.

Alkylation of amide linkages and cleavage of the C chain in the enzyme-activated-substrate inhibition of alpha-chymotrypsin with N-nitrosamides

International Nuclear Information System (INIS)

Donadio, S.; Perks, H.M.; Tsuchiya, K.; White, E.H.

1985-01-01

Active-site-directed N-nitrosamides inhibit alpha-chymotrypsin through an enzyme-activated-substrate mechanism. In this work, the activation results in the release--in the active site--of benzyl carbonium ions, which alkylate and inhibit the enzyme. The final ratio of benzyl groups to enzyme molecules is 1.0, but the alkyl groups are scattered over a number of sites. Reduction and alkylation of the inhibited enzyme generate peptides insoluble in most media. Guanidine hydrochloride at 6 M proved a good solvent, and its use as an eluant on G-75 Sephadex permitted separation of the peptides. In the case of 14 C-labeled enzyme, such an approach has shown that all of the alkylation occurs on the C chain of the enzyme, the chain of which the active site is constructed. Chemical modification of the peptides with ethylenediamine and N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide rendered them soluble in dilute acid, permitting high-performance liquid chromatographic separation. Model studies have shown that the benzyl carbonium ions are highly reactive, alkylating amide linkages at both oxygen and nitrogen. Chromatography of this mixture and also 13 C NMR spectroscopy of the intact inhibited enzyme have shown that three major N-alkylations have occurred. Tryptic digestion of the C chain of chymotrypsin, which contains all of the alkylation sites, provides evidence that the stable N sites are principally located between residue 216 and residue 230

Directly relating gas-phase cluster measurements to solution-phase hydrolysis, the absolute standard hydrogen electrode potential, and the absolute proton solvation energy.

Science.gov (United States)

Donald, William A; Leib, Ryan D; O'Brien, Jeremy T; Williams, Evan R

2009-06-08

Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M(H(2)O)(24)(2+)(g) + e(-)(g)-->M(H(2)O)(24)(+)(g) and 2) M(H(2)O)(24)(2+)(g) + e(-)(g)-->MOH(H(2)O)(23)(+)(g) + H(g) and the hydrogen atom affinities of MOH(H(2)O)(23)(+)(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e(-)(g) (standard deviation of 0.02 V) and a real proton solvation free energy of -265 kcal mol(-1) are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution.

Ni(salen): a system that forms many solvates with interacting Ni atoms

NARCIS (Netherlands)

Siegler, M.A.M.; Lutz, M.

2009-01-01

Recrystallization of [N,N’-Ethylene-bis(salicylideneiminato)]-nickel(II) [Ni(salen)] has been carried out from a large selection of solvents. Crystals can be either solvent free or solvates. This study is based on X-ray crystal structure determinations, which include the redetermination of Ni(salen)

Electrolytes and interphasial chemistry in Li ion devices

Energy Technology Data Exchange (ETDEWEB)

Xu, K. [Electrochemistry Branch, Sensors and Electron Devices Directorate, U. S. Army Research Laboratory, Adelphi, Maryland, 20783-1197 (United States)

2010-07-01

Since its appearance in 1991, the Li ion battery has been the major power source driving the rapid digitalisation of our daily life; however, much of the processes and mechanisms underpinning this newest battery chemistry remains poorly understood. As in any electrochemical device, the major challenge comes from the electrolyte/electrode interfaces, where the discontinuity in charge distribution and extreme disequality in electric forces induce diversified processes that eventually determine the kinetics of Li{sup +} intercalation chemistry. This article will summarize the most recent efforts on the fundamental understanding of the interphases in Li ion devices. Emphasis will be placed on the formation chemistry of the so-called 'SEI' on graphitic anode, the effect of solvation sheath structure of Li{sup +} on the intercalation energy barrier, and the feasibility of tailoring a desired interphase. Biologically inspired approaches to an ideal interphase will also be briefly discussed. (author)

Electrolytes and Interphasial Chemistry in Li Ion Devices

Directory of Open Access Journals (Sweden)

Kang Xu

2010-01-01

Full Text Available Since its appearance in 1991, the Li ion battery has been the major power source driving the rapid digitalization of our daily life; however, much of the processes and mechanisms underpinning this newest battery chemistry remains poorly understood. As in any electrochemical device, the major challenge comes from the electrolyte/electrode interfaces, where the discontinuity in charge distribution and extreme disequality in electric forces induce diversified processes that eventually determine the kinetics of Li+ intercalation chemistry. This article will summarize the most recent efforts on the fundamental understanding of the interphases in Li ion devices. Emphasis will be placed on the formation chemistry of the so-called “SEI” on graphitic anode, the effect of solvation sheath structure of Li+ on the intercalation energy barrier, and the feasibility of tailoring a desired interphase. Biologically inspired approaches to an ideal interphase will also be briefly discussed.

Nuclear chemical method for preparation of free carbenium ions and radiochemical investigation of reactions of these particles

International Nuclear Information System (INIS)

Nefedov, V.D.; Sinotova, E.N.; Toropova, M.A.

1980-01-01

Tritium nuclear transformation (β-decay) in the composition of the molecules of hydrocarbons, appearance of primary molecular ions and formation of free carbenium ion are the main items of nuclear-chemical method of preparation of free carbenium ions. The method permits to prepare carbenium ions present in free state, i.e. without counterion and without solvate sheath of variou nitial localization of the charge. The rate of carbenium ion generation is strictly definite and does not depend upon outer conditions. The method suggested permits to prepare carbenium ions in all phases, study their reactions with individual substances in gaseous, liquid and solid states. The study of ion-molecular reactions is carried out using radiochemical method. The analysis of the products is made using the method of gaseous radiochromatography. Development of preparation techniques of carbenium ions and their analogues, study of the reactions of these particles with different classes of compounds, investigation of the effect of different factors upon procedure of ion-molecular reactions are the main directions of the investigations

Solvatochromism and preferential solvation of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone by UV-vis absorption and laser-induced fluorescence measurements

Science.gov (United States)

Sasirekha, V.; Vanelle, P.; Terme, T.; Ramakrishnan, V.

2008-12-01

Solvation characteristics of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone ( 1) in pure and binary solvent mixtures have been studied by UV-vis absorption spectroscopy and laser-induced fluorescence techniques. The binary solvent mixtures used as CCl 4 (tetrachloromethane)-DMF ( N, N-dimethylformamide), AN (acetonitrile)-DMSO (dimethylsulfoxide), CHCl 3 (chloroform)-DMSO, CHCl 3-MeOH (methanol), and MeOH-DMSO. The longest wavelength band of 1 has been studied in pure solvents as well as in binary solvent mixtures as a function of the bulk mole fraction. The Vis absorption band maxima show an unusual blue shift with increasing solvent polarity. The emission maxima of 1 show changes with varying the pure solvents and the composition in the case of binary solvent mixtures. Non-ideal solvation characteristics are observed in all binary solvent mixtures. It has been observed that the quantity [ ν-(Xν+Xν)] serves as a measure of the extent of preferential solvation, where ν˜ and X are the position of band maximum in wavenumbers (cm -1) and the bulk mole fraction values, respectively. The preferential solvation parameters local mole fraction ( X2L), solvation index ( δs2), and exchange constant ( k12) are evaluated.

Cation-Size-Dependent Conformational Locking of Glutamic Acid by Alkali Ions: Infrared Photodissociation Spectroscopy of Cryogenic Ions.

Science.gov (United States)

Klyne, Johanna; Bouchet, Aude; Ishiuchi, Shun-Ichi; Fujii, Masaaki; Dopfer, Otto

2018-03-01

Consolidated knowledge of conformation and stability of amino acids and their clusters is required to understand their biochemical recognition. Often, alkali ions interact with amino acids and proteins. Herein, infrared photodissociation (IRPD) spectra of cryogenic metalated glutamic acid ions (GluM + , M = Li-Cs) are systematically analyzed in the isomer-specific fingerprint and XH stretch ranges (1100-1900, 2600-3600 cm -1 ) to provide a direct measure for cation-size-dependent conformational locking. GluM + ions are generated by electrospray ionization and cooled down to 15 K in a cryogenic quadrupole ion trap. The assignment of the IRPD spectra is supported by density functional theory calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level. In the global minimum of GluM + , the flexibility of Glu is strongly reduced by the formation of rigid ionic CO···M + ···OC metal bridges, corresponding to charge solvation. The M + binding energy decreases monotonically with increasing cation size from D 0 = 314 to 119 kJ/mol for Li-Cs. Whereas for Li and Na only the global minimum of GluM + is observed, for K-Cs at least three isomers exist at cryogenic temperature. The IRPD spectra of cold GluM + ions are compared to IR multiple-photon dissociation spectra measured at room temperature. Furthermore, we elucidate the differences of the impact of protonation and metalation on the structure and conformational locking of Glu.

Conduction Mechanisms and Structure of Ionomeric Single-Ion Conductors

Energy Technology Data Exchange (ETDEWEB)

Colby, Ralph H. [Pennsylvania State Univ., University Park, PA (United States); Maranas, Janna K. [Pennsylvania State Univ., University Park, PA (United States); Mueller, Karl T. [Pennsylvania State Univ., University Park, PA (United States); Runt, James [Pennsylvania State Univ., University Park, PA (United States); Winey, Karen I. [Univ. of Pennsylvania, Philadelphia, PA (United States)

2015-03-01

Our team has designed using DFT (Gaussian) and synthesized low glass transition temperature single-ion conductors that are either polyanions that conduct small cations Li⁺, Na⁺, Cs⁺ or polycations that conduct small anions F^-, OH^-, Br^-. We utilize a wide range of complimentary experimental materials characterization tools to understand ion transport; differential scanning calorimetry, dielectric relaxation spectroscopy, infrared spectroscopy, nuclear magnetic resonance spectroscopy, linear viscoelasticity, X-ray scattering and molecular dynamics simulations. The glass transition temperature T_g needs to be as low as possible to facilitate ion transport, so the nonionic parts of the polymer need to be polar, flexible and have strong solvation interactions with the ions. The lowest T_g we have managed for polyanions conducting Li⁺ is -60 °C. In contrast, polysiloxanes with PEO side chains and tetrabutylphosphonium cationic side groups have T_g ≈ -75 °C that barely increases with ion content, as anticipated by DFT. A survey of all polyanions in the literature suggests that T_g < -80 °C is needed to achieve the 10^-4 S/cm conductivity needed for battery separators.

Effective interactions between nanoparticles: Creating temperature-independent solvation environments for self-assembly

Energy Technology Data Exchange (ETDEWEB)

Yadav, Hari O. S., E-mail: cyz108802@chemistry.iitd.ac.in, E-mail: hariyadav.iitd@gmail.com; Shrivastav, Gourav; Agarwal, Manish; Chakravarty, Charusita [Department of Chemistry, Indian Institute of Technology-Delhi, New Delhi 110016 (India)

2016-06-28

The extent to which solvent-mediated effective interactions between nanoparticles can be predicted based on structure and associated thermodynamic estimators for bulk solvents and for solvation of single and pairs of nanoparticles is studied here. As a test of the approach, we analyse the strategy for creating temperature-independent solvent environments using a series of homologous chain fluids as solvents, as suggested by an experimental paper [M. I. Bodnarchuk et al., J. Am. Chem. Soc. 132, 11967 (2010)]. Our conclusions are based on molecular dynamics simulations of Au{sub 140}(SC{sub 10}H{sub 21}){sub 62} nanoparticles in n-alkane solvents, specifically hexane, octane, decane and dodecane, using the TraPPE-UA potential to model the alkanes and alkylthiols. The 140-atom gold core of the nanocrystal is held rigid in a truncated octahedral geometry and the gold-thiolate interaction is modeled using a Morse potential. The experimental observation was that the structural and rheological properties of n-alkane solvents are constant over a temperature range determined by equivalent solvent vapour pressures. We show that this is a consequence of the fact that long chain alkane liquids behave to a good approximation as simple liquids formed by packing of monomeric methyl/methylene units. Over the corresponding temperature range (233–361 K), the solvation environment is approximately constant at the single and pair nanoparticle levels under good solvent conditions. However, quantitative variations of the order of 10%–20% do exist in various quantities, such as molar volume of solute at infinite dilution, entropy of solvation, and onset distance for soft repulsions. In the opposite limit of a poor solvent, represented by vacuum in this study, the effective interactions between nanoparticles are no longer temperature-independent with attractive interactions increasing by up to 50% on decreasing the temperature from 361 K to 290 K, accompanied by an increase in

A post Gurney quantum mechanical perspective on the electrolysis of water: ion neutralization in solution

Science.gov (United States)

Guo, Enyi; McKenzie, David R.

2017-11-01

Electron fluxes crossing the interface between a metallic conductor and an aqueous environment are important in many fields; hydrogen production, environmental scanning tunnelling microscopy, scanning electrochemical microscopy being some of them. Gurney (Gurney 1931 Proc. R. Soc. Lond. 134, 137 (doi:10.1098/rspa.1931.0187)) provided in 1931 a scheme for tunnelling during electrolysis and outlined conditions for it to occur. We measure the low-voltage current flows between gold electrodes in pure water and use the time-dependent behaviour at voltage switch-on and switch-off to evaluate the relative contribution to the steady current arising from tunnelling of electrons between the electrodes and ions in solution and from the neutralization of ions adsorbed onto the electrode surface. We ascribe the larger current contribution to quantum tunnelling of electrons to and from ions in solution near the electrodes. We refine Gurney's barrier scheme to include solvated electron states and quantify energy differences using updated information. We show that Gurney's conditions would prevent the current flow at low voltages we observe but outline how the ideas of Marcus (Marcus 1956 J. Chem. Phys. 24, 966-978 (doi:10.1063/1.1742723)) concerning solvation fluctuations enable the condition to be relaxed. We derive an average barrier tunnelling model and a multiple pathways tunnelling model and compare predictions with measurements of the steady-state current-voltage relation. The tunnelling barrier was found to be wide and low in agreement with other experimental studies. Applications as a biosensing mechanism are discussed that exploit the fast tunnelling pathways along molecules in solution.

Solubility and preferential solvation of some n-alkyl-parabens in methanol + water mixtures at 298.15 K

International Nuclear Information System (INIS)

Cárdenas, Zaira J.; Jiménez, Daniel M.; Delgado, Daniel R.; Almanza, Ovidio A.; Jouyban, Abolghasem; Martínez, Fleming; Acree, William E.

2017-01-01

Highlights: • Parabens equilibrium solubility was determined in methanol + water binary mixtures at 298.15 K. • Solubility values were correlated with the Jouyban-Acree model. • Preferential solvation parameters were derived by using the IKBI method. • δx 1,3 values are negative in water-rich mixtures but positive in the other mixtures. - Abstract: Methyl, ethyl and propyl parabens equilibrium solubility was determined in (methanol + water) binary mixtures at 298.15 K. The mole fraction solubility of these compounds increased in 503 (from 2.40 × 10 −4 to 0.121), 1377 (from 9.86 × 10 −5 to 0.136) and 4597 (from 3.73 × 10 −5 to 0.171) times when passing from neat water to neat methanol, for methyl, ethyl and propyl parabens, respectively. All these solubility values were correlated with the Jouyban-Acree model. Preferential solvation parameters by methanol (δx 1,3 ) of these parabens were derived from their thermodynamic solution properties using the inverse Kirkwood-Buff integrals (IKBI) method. For all compounds δx 1,3 values are negative in water-rich mixtures but positive in mixtures with methanol mole fraction greater than 0.32. It is conjecturable that in the former case the hydrophobic hydration around non-polar groups of parabens plays a relevant role in the solvation. Besides, the preferential solvation of these solutes by methanol in mixtures of similar co-solvent compositions and in methanol-rich mixtures could be explained in terms of the higher basic behaviour of methanol.

Solvent effects on the kinetics of the chlorine isotopic exchange reaction between chloride ion and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorchloridothioate

International Nuclear Information System (INIS)

Mikolajczyk, M.; Slebocka-Tilk, H.; Reimschussel, W.

1982-01-01

The effect of solvent on the kinetics of the chlorine isotopic exchange reaction between 36 Cl- ions and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorochloridothioate has been investigated in nitromethane, acetonitrile, propylene carbonate, benzonitrile, nitrobenzene, and hexamethyl-phosphoric triamide. The rate constants decrease with increasing electrophilicity of the solvent. A good correlation between the logarithm of the rate constants and acceptor number (AN) of the solvent was obtained with identical slopes for reactions with phosphoryl and thiophosporyl compounds. The slopes for the dependence of ΔH or TΔS vs. AN for chlorine isotopic exchange in (PHO) 2 pace are opposite those for the exchange reaction in (PHO) 2 PSCl, so a constant ratio of k/sub p=O//k/sub p=s/ is observed, resulting from compensation of ΔH by ΔS. The effect of solvent on the initial state (from solubility measurements) and the transition state of the reaction between (PhO) 2 PSCl and the Cl- ion was evaluated. Changes of solvation of (PHO) 2 PSCE have practically no effect on the kinetics of the reactions. Changes of solvation of the chloride ion and of the transition state primarily influence the rate constants and activation parameters of the investigated isotopic-exchange reaction

Time-dependent friction and solvation time correlation function

International Nuclear Information System (INIS)

Samanta, Alok; Ali, Sk Musharaf; Ghosh, Swapan K

2005-01-01

We have derived a new relation between the time-dependent friction and solvation time correlation function (STCF) for non-polar fluids. The friction values calculated using this relation and simulation results on STCF for a Lennard-Jones fluid are shown to have excellent agreement with the same obtained through mode-coupling theory. Also derived is a relation between the time-dependent dielectric friction and STCF for polar fluids. Routes are thus provided to obtain the time-dependent friction (non-polar as well as dielectric) from an experimentally measured quantity like STCF, even if the interparticle interaction potential is not known

Potential role of the nitroacidium ion on HONO emissions from the snowpack.

Science.gov (United States)

Hellebust, Stig; Roddis, Tristan; Sodeau, John R

2007-02-22

The effects of photolysis on frozen, thin films of water-ice containing nitrogen dioxide (as its dimer dinitrogen tetroxide) have been investigated using a combination of Fourier transform reflection-absorption infrared (FT-RAIR) spectroscopy and mass spectrometry. The release of HONO is ascribed to a mechanism in which nitrosonium nitrate (NO+NO3-) is formed. Subsequent solvation of the cation leads to the nitroacidium ion, H2ONO+, i.e., protonated nitrous acid. The pathway proposed explains why the field measurement of HONO at different polar sites is often contradictory.

Electrochemical redox reactions in solvated silica sol-gel glass

International Nuclear Information System (INIS)

Opallo, M.

2002-01-01

The studies of electrochemical redox reactions in solvated silica sol-gel glass were reviewed. The methodology of the experiments with emphasis on the direct preparation of the solid electrolyte and the application ultra microelectrodes was described. Generally, the level of the electrochemical signal is not much below that observed in liquid electrolyte. The current depends on time elapsed after gelation, namely the longer time, the smaller current. The differences between electrochemical behaviour of the redox couples in monoliths and thin layers were described. (author)

Relation between chemical properties in molten acetamide and water at 98 deg. C

International Nuclear Information System (INIS)

Petit, Nicole

1972-01-01

An attempt was made to establish the relation between the chemical properties of various cations in water and in molten acetamide at 98 deg. C. A solvent always possesses properties which have some effect on the reactivity of the solute. Various types of interactions (polar, electrostatic, Van der Waals forces, and hydrogen bonds) bind the solvent molecules to the dissolved molecules and ions. Interactions between the solute species and the solvent species are designated: solvation phenomena. In addition to solvation phenomena, another but less direct type of interaction occurs: the solvated ions find themselves in a sensibly continuous medium having a dielectric constant ε which can vary considerably. As the value of the dielectric constant decreases, the electrostatic interactions between the ions increase. The variation is such that these ions can only be considered free for values of ε > 40. This is the case for acetamide and water at 98 deg. C. The solvation of a chemical species belonging to an oxido-reducing system can only be effected by comparing the behavior of such a system with a reference system relatively insensitive to changes in the solvent. The reference system used was a ferrocene-ion/ferricinium couple. The solvation of a chemical species is characterized by a variable designated: the solvation activity coefficient. The chemical and electrochemical properties of various elements (alkali elements, alkaline earths, Cu, Zn, Cd, Hg, Pb, U, Al, Ce, and Eu) in neutral or acid media in acetamide were studied using various electrochemical techniques (principally polarography). These studies led to the establishment of a table of oxido-reducing potentials for molten acetamide. Comparisons with water at 98 deg. C indicate that the metallic cations are more solvated in acetamide than in water. The evaluation of solvation activity coefficients from polarographic measurements (E 1/2 , D M ) led to an approximate estimation of the differences in behavior

Interface of the polarizable continuum model of solvation with semi-empirical methods in the GAMESS program

DEFF Research Database (Denmark)

Svendsen, Casper Steinmann; Blædel, Kristoffer; Christensen, Anders S

2013-01-01

An interface between semi-empirical methods and the polarized continuum model (PCM) of solvation successfully implemented into GAMESS following the approach by Chudinov et al (Chem. Phys. 1992, 160, 41). The interface includes energy gradients and is parallelized. For large molecules such as ubiq......An interface between semi-empirical methods and the polarized continuum model (PCM) of solvation successfully implemented into GAMESS following the approach by Chudinov et al (Chem. Phys. 1992, 160, 41). The interface includes energy gradients and is parallelized. For large molecules...... such as ubiquitin a reasonable speedup (up to a factor of six) is observed for up to 16 cores. The SCF convergence is greatly improved by PCM for proteins compared to the gas phase....

Re-examining the tetraphenyl-arsonium/tetraphenyl-borate (TATB) hypothesis for single-ion solvation free energies

Science.gov (United States)

Pollard, Travis P.; Beck, Thomas L.

2018-06-01

Attempts to establish an absolute single-ion hydration free energy scale have followed multiple strategies. Two central themes consist of (1) employing bulk pair thermodynamic data and an underlying interfacial-potential-free model to partition the hydration free energy into individual contributions [Marcus, Latimer, and tetraphenyl-arsonium/tetraphenyl-borate (TATB) methods] or (2) utilizing bulk thermodynamic and cluster data to estimate the free energy to insert a proton into water, including in principle an interfacial potential contribution [the cluster pair approximation (CPA)]. While the results for the hydration free energy of the proton agree remarkably well between the three approaches in the first category, the value differs from the CPA result by roughly +10 kcal/mol, implying a value for the effective electrochemical surface potential of water of -0.4 V. This paper provides a computational re-analysis of the TATB method for single-ion free energies using quasichemical theory. A previous study indicated a significant discrepancy between the free energies of hydration for the TA cation and the TB anion. We show that the main contribution to this large computed difference is an electrostatic artifact arising from modeling interactions in periodic boundaries. No attempt is made here to develop more accurate models for the local ion/solvent interactions that may lead to further small free energy differences between the TA and TB ions, but the results clarify the primary importance of interfacial potential effects for analysis of the various free energy scales. Results are also presented, related to the TATB assumption in the organic solvents dimethyl sulfoxide and 1,2-dichloroethane.

Modeling solvation effects in real-space and real-time within density functional approaches

Energy Technology Data Exchange (ETDEWEB)

Delgado, Alain [Istituto Nanoscienze - CNR, Centro S3, via Campi 213/A, 41125 Modena (Italy); Centro de Aplicaciones Tecnológicas y Desarrollo Nuclear, Calle 30 # 502, 11300 La Habana (Cuba); Corni, Stefano; Pittalis, Stefano; Rozzi, Carlo Andrea [Istituto Nanoscienze - CNR, Centro S3, via Campi 213/A, 41125 Modena (Italy)

2015-10-14

The Polarizable Continuum Model (PCM) can be used in conjunction with Density Functional Theory (DFT) and its time-dependent extension (TDDFT) to simulate the electronic and optical properties of molecules and nanoparticles immersed in a dielectric environment, typically liquid solvents. In this contribution, we develop a methodology to account for solvation effects in real-space (and real-time) (TD)DFT calculations. The boundary elements method is used to calculate the solvent reaction potential in terms of the apparent charges that spread over the van der Waals solute surface. In a real-space representation, this potential may exhibit a Coulomb singularity at grid points that are close to the cavity surface. We propose a simple approach to regularize such singularity by using a set of spherical Gaussian functions to distribute the apparent charges. We have implemented the proposed method in the OCTOPUS code and present results for the solvation free energies and solvatochromic shifts for a representative set of organic molecules in water.

Time-dependent radiolytic yields at room temperature and temperature-dependent absorption spectra of the solvated electrons in polyols

International Nuclear Information System (INIS)

Lin Mingzhang; Mostafavi, M.; Lampre, I.; Muroya, Y.; Katsumura, Y.

2007-01-01

The molar extinction coefficients at the absorption maximum of the solvated electron spectrum have been evaluated to be 900, 970, and 1000 mol -1 ·m 2 for 1,2-ethanediol (12ED), 1,2-propanediol (12PD), and 1,3-propanediol (13PD), respectively. These values are two-third or three-fourth of the value usually reported in the published report. Picosecond pulse radiolysis studies have aided in depicting the radiolytic yield of the solvated electron in these solvents as a function of time from picosecond to microsecond. The radiolytic yield in these viscous solvents is found to be strongly different from that of the water solution. The temperature dependent absorption spectra of the solvated electron in 12ED, 12PD, and 13PD have been also investigated. In all the three solvents, the optical spectra shift to the red with increasing temperature. While the shape of the spectra does not change in 13PD, a widening on the blue side of the absorption band is observed in 12ED and 12PD at elevated temperatures. (authors)

Thermodynamics of calcium-isotope-exchange reactions. 1. Exchange between isotopic calcium carbonates and aqueous calcium ions

International Nuclear Information System (INIS)

Zhang, R.S.; Nash, C.P.; Rock, P.A.

1988-01-01

This paper reports the authors results for the direct experimental determination of the equilibrium constant for the calcium-isotope-exchange reaction 40 CaCO 3 (s) + 44 CaCl 2 (aq) reversible 44 CaCO 2 (s) + 40 CaCl 2 (aq). The reaction was studied in electrochemical double cells without liquid junction of the type shown in eq 2. The experimental value of the equilibrium constant at 295 +/- 2 K is K = 1.08 +/- 0.02. The experimental value for K is compared with the values of K calculated for various model reactions according to the statistical thermodynamic theory of isotope effects. The isotopic solid carbonates were modeled according to both the Debye and Kieffer theories. No structured models of solvated isotopic aqueous calcium ions yield calculated equilibrium constants in agreement with their experimental results. This conclusion is in agreement with published molecular dynamics calculations which show that the aqueous solvation of Ca 2 =(aq) is essentially unstructured

Thermodynamics of ionic processes in solutions

International Nuclear Information System (INIS)

Krestov, G.A.

1984-01-01

The present nitions about the mechanism of solvation of atomic-molecular particles and the structure of electrolyte and non electrolyte solutions are given. From common positions a wide range of interrelated problems (general and thermodynamic characteristic of ions, thermodynamic characteristic of ion solvation and various ionic reactions in solutions, structural changes of the solvent in the above processes etc...) is considered. The latest scientific data including those on the effect on the thermodynamio properties of low temperatures, various impurities (air, water), large ions, peculiarities of the structure of solvent molecules reflected. Considerable attention is given to new conceptions definitions, structural notions as well as theoretical and experimental methods of obtaining quantitative characteristics of ion solvation

Electrochemical behaviours of Eu(III/E(II and Ce(IV/Ce(III in H3PO4-H2O media : solvation and complexation reactions

Directory of Open Access Journals (Sweden)

Belqat B.

2018-01-01

Full Text Available Many kinds of rare earth elements (REE such as europium and cerium have been make them essential elements in many high-tech components. The electrochemical studies can be presented as an interesting indication for europium and cerium extraction from phosphoric solutions, including solvation and complexation reactions. The normal redox potentials of Eu3+/Eu2+ and Ce4+/Ce3+ systems have been determined in H3PO4-H2O media with various phosphoric acid concentration. The solvation of these elements in phosphoric media is characterized by their transfer activity coefficients "f" calculated from the corresponding normal redox potentials. The corresponding solvation increases with increasing the H3PO4 concentration. For each REE, the electrochemical properties depend on its number of charges and on its basic properties. Results suggest that solvation and complexation of REE phosphates are important in controlling REE concentration.

Optically Controlled Electron-Transfer Reaction Kinetics and Solvation Dynamics : Effect of Franck-Condon States

NARCIS (Netherlands)

Gupta, Kriti; Patra, Aniket; Dhole, Kajal; Samanta, Alok Kumar; Ghosh, Swapan K.

2017-01-01

Experimental results for optically controlled electron-transfer reaction kinetics (ETRK) and nonequilibrium solvation dynamics (NESD) of Coumarin 480 in DMPC vesicle show their dependence on excitation wavelength λex. However, the celebrated Marcus theory and linear-response-theory-based approaches

Systematic solvate screening of trospium chloride: discovering hydrates of a long-established pharmaceutical

Czech Academy of Sciences Publication Activity Database

Sládková, V.; Skalická, T.; Skořepová, E.; Čejka, J.; Eigner, Václav; Kratochvíl, B.

2015-01-01

Roč. 17, č. 25 (2015), s. 4712-4721 ISSN 1466-8033 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : trospium chloride * solvate screening * x-ray crystallography * Jana2006 Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 3.849, year: 2015

Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li-O2 batteries

Science.gov (United States)

Aetukuri, Nagaphani B.; McCloskey, Bryan D.; García, Jeannette M.; Krupp, Leslie E.; Viswanathan, Venkatasubramanian; Luntz, Alan C.

2015-01-01

Given their high theoretical specific energy, lithium-oxygen batteries have received enormous attention as possible alternatives to current state-of-the-art rechargeable Li-ion batteries. However, the maximum discharge capacity in non-aqueous lithium-oxygen batteries is limited to a small fraction of its theoretical value due to the build-up of insulating lithium peroxide (Li2O2), the battery’s primary discharge product. The discharge capacity can be increased if Li2O2 forms as large toroidal particles rather than as a thin conformal layer. Here, we show that trace amounts of electrolyte additives, such as H2O, enhance the formation of Li2O2 toroids and result in significant improvements in capacity. Our experimental observations and a growth model show that the solvating properties of the additives prompt a solution-based mechanism that is responsible for the growth of Li2O2 toroids. We present a general formalism describing an additive’s tendency to trigger the solution process, providing a rational design route for electrolytes that afford larger lithium-oxygen battery capacities.

I. Activation energies for the gas phase reactions of hydrogen atom with carbon monoxide and with ethylene. II. Rate constants for the reactions of benzyl cation with triethylphosphine and with triethylarsine in 1,2-dichloroethane

International Nuclear Information System (INIS)

Wang, H.Y.

1976-01-01

Two H-atom reactions H + CO + H 2 → HCO + H 2 and H + C 2 H 4 → C 2 H 5 * were separately studied from room temperature to about 100 0 C, and the activation energies for these two reactions were determined in this temperature range. For H + C 2 H 4 system, a small activation energy of 0.2 kcal/mole was obtained in the present narrow temperature range. The low activation energy indicates that the pre-exponential factor has a predominant contribution to the rate constant of this reaction and has about the same magnitude as that of the rate constant. For H + CO system, a fairly large activation energy of more than 7 kcal/mole was speculated in the potential energy surfaces of the system. The activation energy obtained in the present work, however, has a low value of about 2 kcal/mole. This low value reveals the low level of crossing of this reaction in the potential energy surface and thus indicates considerable complexity involved in the surface. Carbonium ions can be formed from chosen solutes in pulse-irradiated 1,2-dichloroethane (RCl) solutions. Upon irradiation, the electrons generated from the ionization of the solvent become localized on chloride ions as a result of their reaction with the neutral solvent molecules. The solvent counterion, RCl + , on the other hand, is free to exchange charge with the solute molecule. By choosing appropriate solutes, carbonium ion can be formed through a dissociative ionization process in the exchange. The benzyl cation was formed from its precursor compound dibenzylmercury and its reactions with two nucleophiles, triethylphosphine and triethylarsine, were separately studied. The formation and decay of benzyl cation were observed at 363 nm, the position of the maximum of its absorption band, and the second-order rate constants for the two reactions were determined at room temperature

Copper-transporting P-type ATPases use a unique ion-release pathway

DEFF Research Database (Denmark)

Andersson, Magnus; Mattle, Daniel; Sitsel, Oleg

2014-01-01

Heavy metals in cells are typically regulated by PIB-type ATPases. The first structure of the class, a Cu(+)-ATPase from Legionella pneumophila (LpCopA), outlined a copper transport pathway across the membrane, which was inferred to be occluded. Here we show by molecular dynamics simulations...... that extracellular water solvated the transmembrane (TM) domain, results indicative of a Cu(+)-release pathway. Furthermore, a new LpCopA crystal structure determined at 2.8-Å resolution, trapped in the preceding E2P state, delineated the same passage, and site-directed-mutagenesis activity assays support...... a functional role for the conduit. The structural similarities between the TM domains of the two conformations suggest that Cu(+)-ATPases couple dephosphorylation and ion extrusion differently than do the well-characterized PII-type ATPases. The ion pathway explains why certain Menkes' and Wilson's disease...

Equilibrium and nonequilibrium solvation and solute electronic structure

International Nuclear Information System (INIS)

Kim, H.J.; Hynes, J.T.

1990-01-01

When a molecular solute is immersed in a polar and polarizable solvent, the electronic wave function of the solute system is altered compared to its vacuum value; the solute electronic structure is thus solvent-dependent. Further, the wave function will be altered depending upon whether the polarization of the solvent is or is not in equilibrium with the solute charge distribution. More precisely, while the solvent electronic polarization should be in equilibrium with the solute electronic wave function, the much more sluggish solvent orientational polarization need not be. We call this last situation non-equilibrium solvation. We outline a nonlinear Schroedinger equation approach to these issues

On the some reactions of mixed ethers of phosphorus acid with acrylonitrile and methyl iodide

International Nuclear Information System (INIS)

Gusev, Yu.K.; Chistokletov, V.N.; Petrov, A.A.

1977-01-01

The bimolecular mechanism has been confirmed of the redgrouping stage of Arbuzov's classical reactions for phosphites containing primary and secondary radicals in reactions of acrylonitrile and methyl iodide with some mixed ethers of phosphoric acid. It is suggested that dealcylation of the intermediate products formed on interaction of olefins activated by electron-acceptor groups with phosphites containing primary radicals occurs according to the Ssub(N)2-mechanism, secondary radicals, according to the mixed Ssub(N)2 and Ssub(N)1-mechanism,and radicals capable of forming stable carbonium ions, according to the Ssub(N)1-mechanism

Effect of the composition of a solution on the enthalpies of solvation of piperidine in methanol-acetonitrile and dimethylsulfoxide-acetonitrile mixed solvents

Science.gov (United States)

Kuz'mina, I. A.; Volkova, M. A.; Sitnikova, K. A.; Sharnin, V. A.

2014-01-01

Heat effects of dissolution of piperidine (ppd) are measured by calorimetry at 298.15 K over the range of composition of acetonitrile-methanol (AN-MeOH) mixed solvents. Based on the Δsol H ○(ppd)AN-MeOH values obtained using the literature data on Δsol H ○ (ppd) in acetonitrile-dimethylsulfoxide (AN-DMSO) mixed solvents and the vaporization enthalpy of ppd, the enthalpies of solvation of amine in AN-MeOH and AN-DMSO binary mixtures are calculated. A rise in the exothermicity of solvation of piperidine is observed upon the transition from AN to DMSO and MeOH, due mainly to the enhanced solvation of the amino group of ppd as a result of changes in the acid-base properties of the mixed solvent.

High-dimensional neural network potentials for solvation: The case of protonated water clusters in helium

Science.gov (United States)

Schran, Christoph; Uhl, Felix; Behler, Jörg; Marx, Dominik

2018-03-01

The design of accurate helium-solute interaction potentials for the simulation of chemically complex molecules solvated in superfluid helium has long been a cumbersome task due to the rather weak but strongly anisotropic nature of the interactions. We show that this challenge can be met by using a combination of an effective pair potential for the He-He interactions and a flexible high-dimensional neural network potential (NNP) for describing the complex interaction between helium and the solute in a pairwise additive manner. This approach yields an excellent agreement with a mean absolute deviation as small as 0.04 kJ mol-1 for the interaction energy between helium and both hydronium and Zundel cations compared with coupled cluster reference calculations with an energetically converged basis set. The construction and improvement of the potential can be performed in a highly automated way, which opens the door for applications to a variety of reactive molecules to study the effect of solvation on the solute as well as the solute-induced structuring of the solvent. Furthermore, we show that this NNP approach yields very convincing agreement with the coupled cluster reference for properties like many-body spatial and radial distribution functions. This holds for the microsolvation of the protonated water monomer and dimer by a few helium atoms up to their solvation in bulk helium as obtained from path integral simulations at about 1 K.

Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

International Nuclear Information System (INIS)

Crowe, Adam J.; Bartlett, Bart M.

2016-01-01

With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg 2+ ), relative to lithium-ion (Li + ) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg 2+ , improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recent advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes. - Graphical abstract: In this short review, we present candidate materials for reversible Mg-battery cathodes that are compatible with magnesium metal in water-free electrolytes. The data suggest that soft, polarizable anions are required for reversible cycling.

Molecular modeling of nucleic Acid structure: electrostatics and solvation.

Science.gov (United States)

Bergonzo, Christina; Galindo-Murillo, Rodrigo; Cheatham, Thomas E

2014-12-19

This unit presents an overview of computer simulation techniques as applied to nucleic acid systems, ranging from simple in vacuo molecular modeling techniques to more complete all-atom molecular dynamics treatments that include an explicit representation of the environment. The third in a series of four units, this unit focuses on critical issues in solvation and the treatment of electrostatics. UNITS 7.5 & 7.8 introduced the modeling of nucleic acid structure at the molecular level. This included a discussion of how to generate an initial model, how to evaluate the utility or reliability of a given model, and ultimately how to manipulate this model to better understand its structure, dynamics, and interactions. Subject to an appropriate representation of the energy, such as a specifically parameterized empirical force field, the techniques of minimization and Monte Carlo simulation, as well as molecular dynamics (MD) methods, were introduced as a way of sampling conformational space for a better understanding of the relevance of a given model. This discussion highlighted the major limitations with modeling in general. When sampling conformational space effectively, difficult issues are encountered, such as multiple minima or conformational sampling problems, and accurately representing the underlying energy of interaction. In order to provide a realistic model of the underlying energetics for nucleic acids in their native environments, it is crucial to include some representation of solvation (by water) and also to properly treat the electrostatic interactions. These subjects are discussed in detail in this unit. Copyright © 2014 John Wiley & Sons, Inc.

Linear solvation energy relationships (LSER): 'rules of thumb' for Vi/100, π*, Βm, and αm estimation and use in aquatic toxicology

Science.gov (United States)

Hickey, James P.

1996-01-01

This chapter provides a listing of the increasing variety of organic moieties and heteroatom group for which Linear Solvation Energy Relationship (LSER) values are available, and the LSER variable estimation rules. The listings include values for typical nitrogen-, sulfur- and phosphorus-containing moieties, and general organosilicon and organotin groups. The contributions by an ion pair situation to the LSER values are also offered in Table 1, allowing estimation of parameters for salts and zwitterions. The guidelines permit quick estimation of values for the four primary LSER variables Vi/100, π*, Βm, and αm by summing the contribtuions from its components. The use of guidelines and Table 1 significantly simplifies computation of values for the LSER variables for most possible organic comppounds in the environment, including the larger compounds of environmental and biological interest.

Enthalpies of fusion and enthalpies of solvation of aromatic hydrocarbons derivatives: Estimation of sublimation enthalpies at 298.15 K

Energy Technology Data Exchange (ETDEWEB)

Solomonov, Boris N., E-mail: boris.solomonov@kpfu.ru; Nagrimanov, Ruslan N.; Varfolomeev, Mikhail A.; Buzyurov, Aleksey V.; Mukhametzyanov, Timur A.

2016-03-20

Graphical abstract: - Highlights: • Solution enthalpies of aromatic hydrocarbons derivatives (ArHD) were measured at 298.15 K. • Solution enthalpies of ArHD in benzene at 298.15 K are equal to their fusion enthalpy at melting point. • Sublimation enthalpies of 80 ArHD were calculated as a sum of fusion and solvation enthalpies. • Obtained sublimation enthalpies are in good agreement with the recommended literature data. - Abstract: Enthalpy of sublimation of solid compound can be found using the values of solution enthalpy and solvation enthalpy in any solvent. In this work enthalpies of solution at infinite dilution of a number of aromatic hydrocarbons derivatives in benzene were measured at 298.15 K. Comparison between experimental and literature solution enthalpies in benzene at 298.15 K and fusion enthalpies at melting temperature of aromatic hydrocarbon derivatives showed, that these values are approximately equal. Thereby, fusion enthalpies at melting temperature can be used instead of their solution enthalpies in benzene at 298.15 K for calculation of sublimation enthalpies at 298.15 K. Solvation enthalpies in benzene at 298.15 K required for this procedure were calculated using group additivity scheme. The sublimation enthalpies of 80 aromatic hydrocarbons derivatives at 298.15 K were evaluated as a difference between fusion enthalpies at melting temperature and solvation enthalpies in benzene at 298.15 K. Obtained in this work values of sublimation enthalpy at 298.15 K for studied compounds were in a good agreement with available literature data.

Thermodynamics of coproportionation reactions of homogeneous samarium (3) and yttrium (3) nitrates solvates with neutral organic phosphorus compounds

International Nuclear Information System (INIS)

Pyartman, A.K.

1995-01-01

Reaction heats of homogeneous samarium (3) and yttrium (3) nitrate solvates coproportionation with neutral organophosphoric compounds (tri-n.-butylphosphate, diisooctylmethylphosphonate, diisoamylmethylphosphonate) at T=298.15 K in hexane have been measured by thermochemical method. It has been ascertained that enthalpies of coproportionation reactions practically do not depend on the nature, concentration of rare earth metal (3) nitrate solvates in hexane, nature of neutral organophosphoric compound and constitute 1.1±-.2 kJ/mol. The Gibbs free energy of coproportionation reactions is -5.43 kJ/mol, while entropy of the reactions in 14.5±0.7 J/mol·K. 8 refs., 1 tab

Impact of structural modification of 1,2,4-thiadiazole derivatives on thermodynamics of solubility and solvation processes in 1-octanol and n-hexane

International Nuclear Information System (INIS)

Surov, Artem O.; Bui, Cong Trinh; Volkova, Tatyana V.; Proshin, Alexey N.; Perlovich, German L.

2016-01-01

Highlights: • Solubility processes of some 1,2,4-thiadiazoles in n-hexane and 1-octanol were investigated. • Solvation processes of some 1,2,4-thiadiazoles in n-hexane and 1-octanol were studied. • Transfer processes from n-hexane to 1-octanol were evaluated. • Impact of various substituents in 1,2,4-thiadiazoles on the mentioned processes was studied. - Abstract: Influence of a structural modification on thermodynamic aspects of solubility and solvation processes of the 1,2,4-thiadiazole drug-like compounds in pharmaceutically relevant solvents n-hexane and 1-octanol was investigated. The solubility of the compounds in 1-octanol does not substantially depend on the nature and position of the substituent in the phenyl moiety. In n-hexane, however, the introduction of any substituent in the phenyl ring of the 1,2,4-thiadiazole molecule reduces the solubility in the solvent. In order to rationalize the relationships between the structure of 1,2,4-thiadiazoles and their solubility, the latter was considered in terms of two fundamental processes: sublimation and solvation. It was found that for the most of the compounds the solubility change in both solvents is a consequence of competition between the sublimation and solvation contributions, i.e. the introduction of substituents leads to growth of the sublimation Gibbs energy and increase in the solvation Gibbs energy. Thermodynamic parameters of the transfer process of the compounds from n-hexane to 1-octanol, which is a model of the blood–brain barrier (BBB), were also analyzed.

Spectroscopic Observation of Water-Mediated Deformation of the CARBOXYLATE-M2+ (M= Mg, Ca) Contact Ion Pair

Science.gov (United States)

Kelleher, Patrick J.; DePalma, Joseph W.; Johnson, Mark

2016-06-01

The binding of alkaline earth dications to the biologically relevant carboxylate ligand has previously been studied using vibrational sum frequency generation (VSFG) spectroscopy of the air-water interface, infrared multiple photon dissociation (IRMPD) spectroscopy of clusters, and DFT methods. These results suggest the presence of both monodentate and bidentate binding motifs of the M2+ ions to the cayboxyl head groups depending on the extent of solvation. We revisit these systems using vibrational predissociation spectroscopy to measure the gas-phase vibrational spectra of the D2-tagged microhydrated [MgOAc(H2O)n=1-5]+ and [CaOAc(H2O)n=1-6]+ clusters. The spectra show that [MgOAc(H2O)n]+ switches from bidentate to monodentate binding promptly at n = 5, while [CaOAc(H2O)n]+ retains its bidentate attachment such that the sixth water molecule initiates the second solvation shell. The difference in binding behavior between these two divalent metal ions is analyzed in the context of the local acidity of the solvent water molecules and the strength of the metal-carboxylate and metal-water interactions. This cluster study provides insight into the chemical physics underlying the unique and surprising impacts of Mg2+ and Ca2+ on the chemistry mediated by sea spray aerosols. Funding for this work was provided by the NSF's Center for Aerosol Impacts on Climate and the Environment.

Complexation-induced supramolecular assembly drives metal-ion extraction.

Science.gov (United States)

Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

2014-09-26

Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Contact ion pair formation between hard acids and soft bases in aqueous solutions observed with 2DIR spectroscopy.

Science.gov (United States)

Sun, Zheng; Zhang, Wenkai; Ji, Minbiao; Hartsock, Robert; Gaffney, Kelly J

2013-12-12

The interaction of charged species in aqueous solution has important implications for chemical, biological, and environmental processes. We have used 2DIR spectroscopy to study the equilibrium dynamics of thiocyanate chemical exchange between free ion (NCS(-)) and contact ion pair configurations (MNCS(+)), where M(2+) = Mg(2+) or Ca(2+). Detailed studies of the influence of anion concentration and anion speciation show that the chemical exchange observed with the 2DIR measurements results from NCS(-) exchanging with other anion species in the first solvation shell surrounding Mg(2+) or Ca(2+). The presence of chemical exchange in the 2DIR spectra provides an indirect, but robust, determinant of contact ion pair formation. We observe preferential contact ion pair formation between soft Lewis base anions and hard Lewis acid cations. This observation cannot be easily reconciled with Pearson's acid-base concept or Collins' Law of Matching Water Affinities. The anions that form contact ion pairs also correspond to the ions with an affinity for water and protein surfaces, so similar physical and chemical properties may control these distinct phenomena.

The influence of polarizability and charge transfer on specific ion effects in the dynamics of aqueous salt solutions

Science.gov (United States)

Nguyen, Mary; Rick, Steven W.

2018-06-01

The diffusion rates for water molecules in salt solutions depend on the identity of the ions, as well as their concentration. Among the alkali metal ions, cesium and potassium increase and sodium strongly decreases the diffusion constant of water. The origin of the difference can be understood by examining the simulation results using different potential models. In this work, aqueous solutions of salts are simulated with a variety of models. Commonly used non-polarizable models, which otherwise reproduce many experimental properties, do not capture the trend in the diffusion constant, while models which include polarization and/or charge transfer interactions do. For the non-polarizable models, the diffusion constant decreases too strongly with salt concentration. The changes in the water diffusion constant with increasing salt concentration match the diffusion constant of the ion. The ion diffusion constant is dependent on the residence time for water in the ion solvation shell. The non-polarizable models over-estimate the residence time, relative to the translational diffusion constant and so tend to under-estimate the ion and water diffusion constants.

Freezing hot electrons. Electron transfer and solvation dynamics at D{sub 2}O and NH{sub 3}-metal interfaces

Energy Technology Data Exchange (ETDEWEB)

Staehler, A.J.

2007-05-15

The present work investigates the electron transfer and solvation dynamics at the D{sub 2}O/Cu(111), D{sub 2}O/Ru(001), and NH{sub 3}/Cu(111) interfaces using femtosecond time-resolved two-photon photoelectron spectroscopy. Within this framework, the influence of the substrate, adsorbate structure and morphology, solvation site, coverage, temperature, and solvent on the electron dynamics are studied, yielding microscopic insight into the underlying fundamental processes. Transitions between different regimes of ET, substrate-dominated, barrier-determined, strong, and weak coupling are observed by systematic variation of the interfacial properties and development of empirical model descriptions. It is shown that the fundamental steps of the interfacial electron dynamics are similar for all investigated systems: Metal electrons are photoexcited to unoccupied metal states and transferred into the adlayer via the adsorbate's conduction band. The electrons localize at favorable sites and are stabilized by reorientations of the surrounding polar solvent molecules. Concurrently, they decay back two the metal substrate, as it offers a continuum of unoccupied states. However, the detailed characteristics vary for the different investigated interfaces: For amorphous ice-metal interfaces, the electron transfer is initially, right after photoinjection, dominated by the substrate's electronic surface band structure. With increasing solvation, a transient barrier evolves at the interface that increasingly screens the electrons from the substrate. Tunneling through this barrier becomes the rate-limiting step for ET. The competition of electron decay and solvation leads to lifetimes of the solvated electrons in the order of 100 fs. Furthermore, it is shown that the electrons bind in the bulk of the ice layers, but on the edges of adsorbed D{sub 2}O clusters and that the ice morphology strongly influences the electron dynamics. For the amorphous NH{sub 3}/Cu(111

A hybrid neutron diffraction and computer simulation study on the solvation of N-methylformamide in dimethylsulfoxide

Science.gov (United States)

Cordeiro, João M. M.; Soper, Alan K.

2013-01-01

The solvation of N-methylformamide (NMF) by dimethylsulfoxide (DMSO) in a 20% NMF/DMSO liquid mixture is investigated using a combination of neutron diffraction augmented with isotopic substitution and Monte Carlo simulations. The aim is to investigate the solute-solvent interactions and the structure of the solution. The results point to the formation of a hydrogen bond (H-bond) between the H bonded to the N of the amine group of NMF and the O of DMSO particularly strong when compared with other H-bonded liquids. Moreover, a second cooperative H-bond is identified with the S atom of DMSO. As a consequence of these H-bonds, molecules of NMF and DMSO are rather rigidly connected, establishing very stable dimmers in the mixture and very well organized first and second solvation shells.

Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

International Nuclear Information System (INIS)

Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

2015-01-01

The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism

Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

Science.gov (United States)

Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

2015-06-01

The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

Energy Technology Data Exchange (ETDEWEB)

Elkins, Madeline H.; Williams, Holly L. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Neumark, Daniel M. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

2015-06-21

The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

The onset of ion solvation by ab initio calculations: Comparison of water and methanol

Czech Academy of Sciences Publication Activity Database

Pluhařová, Eva; Jungwirth, Pavel

2008-01-01

Roč. 73, 6/7 (2008), s. 733-744 ISSN 0010-0765 R&D Projects: GA MŠk LC512; GA ČR GA203/07/1006 Institutional research plan: CEZ:AV0Z40550506 Keywords : ions * water cluster * methanol * ab initio calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.784, year: 2008

Grid inhomogeneous solvation theory: hydration structure and thermodynamics of the miniature receptor cucurbit[7]uril.

Science.gov (United States)

Nguyen, Crystal N; Young, Tom Kurtzman; Gilson, Michael K

2012-07-28

The displacement of perturbed water upon binding is believed to play a critical role in the thermodynamics of biomolecular recognition, but it is nontrivial to unambiguously define and answer questions about this process. We address this issue by introducing grid inhomogeneous solvation theory (GIST), which discretizes the equations of inhomogeneous solvation theory (IST) onto a three-dimensional grid situated in the region of interest around a solute molecule or complex. Snapshots from explicit solvent simulations are used to estimate localized solvation entropies, energies, and free energies associated with the grid boxes, or voxels, and properly summing these thermodynamic quantities over voxels yields information about hydration thermodynamics. GIST thus provides a smoothly varying representation of water properties as a function of position, rather than focusing on hydration sites where solvent is present at high density. It therefore accounts for full or partial displacement of water from sites that are highly occupied by water, as well as for partly occupied and water-depleted regions around the solute. GIST can also provide a well-defined estimate of the solvation free energy and therefore enables a rigorous end-states analysis of binding. For example, one may not only use a first GIST calculation to project the thermodynamic consequences of displacing water from the surface of a receptor by a ligand, but also account, in a second GIST calculation, for the thermodynamics of subsequent solvent reorganization around the bound complex. In the present study, a first GIST analysis of the molecular host cucurbit[7]uril is found to yield a rich picture of hydration structure and thermodynamics in and around this miniature receptor. One of the most striking results is the observation of a toroidal region of high water density at the center of the host's nonpolar cavity. Despite its high density, the water in this toroidal region is disfavored energetically and

Effect of Preferential Solvation of Polymer Chains on Vapor-Pressure Osmometry Results. Computer Simulation Study.

Czech Academy of Sciences Publication Activity Database

Svoboda, Martin; Lísal, Martin; Limpouchová, Z.; Procházka, Karel

2018-01-01

Roč. 23, č. 3 (2018), s. 244-251 ISSN 1023-666X R&D Projects: GA ČR GA15-19542S Institutional support: RVO:67985858 Keywords : vapor-pressure osmometry * simulation * solvatation Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

Solvated Positron Chemistry. II

DEFF Research Database (Denmark)

Mogensen, O. E.

1979-01-01

The reaction of the hydrated positron, eaq+ with Cl−, Br−, and I− ions in aqueous solutions was studied by means of positron The measured angular correlation curves for [Cl−, e+], [Br−, e+, and [I−, e+] bound states were in good agreement with th Because of this agreement and the fact...... that the calculated positron wavefunctions penetrate far outside the X− ions in the [X−, e+] sta propose that a bubble is formed around the [X−, e+] state, similar to the Ps bubble found in nearly all liquids. F−ions did not react w Preliminary results showed that CN− ions react with eaq+ while OH−ions are non...... in the Cl− case) at higher concentrations. This saturation and the high-concentration effects-in the angular correlation results were interpreted as caused by rather complicated spur effects, wh It is proposed that spur electrons may pick off the positron from the [X−, e+ states with an efficiency which...

CL 14: Solvation structure and dynamics of room temperature ionic liquids

International Nuclear Information System (INIS)

Musat, Raluca M.; Polyansky, Dmitriy; Crowell, Robert A.; Thomas, Marie; Wishart, James F.; Takahashi, Kenji; Katsumura, Yosuke

2010-01-01

Room temperature ionic liquids (RTILs) have emerged as a new class of solvents that, due to their unique properties (e.g., low volatility, large electrochemical window, high conductivity, etc.), have several potential applications. Among these are their possible use in nuclear fuel reprocessing, dye sensitized solar cells, and CO 2 sequestration. The properties of a given class of RTILs depend strongly on the choice of the counter anion. In this contribution we present new results using both static and time-resolved EXAFS (ca. 1 ns resolution) and time resolved optical absorption spectroscopy on a series of bromide containing imidazolium salts. The static results provide detailed information of the solvation shell of the bromide ion while the time-resolved data shed light on the nature and chemical behavior of the lowest lying charge transfer band, the physical motion of the bromine atom and its conversion to di-bromide. The photochemistry of the charge transfer (CT) band of the room temperature ionic liquid 1-hexyl-3-methylimidazolium bromide is investigated using ultrafast transient absorption spectroscopy (TA) in the near-IR and steady state UV absorption. Irradiation of the CT band at 266 nm results in the steady state production of di-bromide which absorbs strongly at 266 nm. It is shown that this photoproduct, which is apparently very stable, adversely affects ultrafast transient absorption measurements. Flowing and simultaneously translating the sample mitigates this effect and reveals new transient species and dynamics within the detection window of 850 nm to 1250 nm. (authors)

Poisson-Fermi modeling of ion activities in aqueous single and mixed electrolyte solutions at variable temperature

Science.gov (United States)

Liu, Jinn-Liang; Eisenberg, Bob

2018-02-01

The combinatorial explosion of empirical parameters in tens of thousands presents a tremendous challenge for extended Debye-Hückel models to calculate activity coefficients of aqueous mixtures of the most important salts in chemistry. The explosion of parameters originates from the phenomenological extension of the Debye-Hückel theory that does not take steric and correlation effects of ions and water into account. By contrast, the Poisson-Fermi theory developed in recent years treats ions and water molecules as nonuniform hard spheres of any size with interstitial voids and includes ion-water and ion-ion correlations. We present a Poisson-Fermi model and numerical methods for calculating the individual or mean activity coefficient of electrolyte solutions with any arbitrary number of ionic species in a large range of salt concentrations and temperatures. For each activity-concentration curve, we show that the Poisson-Fermi model requires only three unchanging parameters at most to well fit the corresponding experimental data. The three parameters are associated with the Born radius of the solvation energy of an ion in electrolyte solution that changes with salt concentrations in a highly nonlinear manner.

A new three-particle-interaction model to predict the thermodynamic properties of different electrolytes

International Nuclear Information System (INIS)

Ge Xinlei; Wang Xidong; Zhang Mei; Seetharaman, Seshadri

2007-01-01

In this study, Guggenheim charging process, which involves the radial Boltzmann distribution, was introduced to develop a new predictive model with three parameters, ion-ion distance parameter, ion-solvent parameter, and solvation parameter. In this model, the ion-ion and ion-solvent molecule interaction are all included in the charging process, and it is independent of the temperature and solvent. This new model was applied to correlate the experimental data from literatures for 208 electrolytes aqueous solution at T = 298.15 K of which the concentration range is wide. The calculated results agreed well with the experimental ones for most electrolytes, especially for the prediction in high ionic strength. The estimation of solvation parameter S also gave that the solvation tendency for cations and anions follow a trend, which is in consistent with results published in literature. Investigations were also been made in calculations for electrolytes solutions at other temperatures and non-aqueous system, which proved this model was also feasible

Solvation of carbonaceous molecules by para-H{sub 2} and ortho-D{sub 2} clusters. I. Polycyclic aromatic hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Calvo, F., E-mail: florent.calvo@univ-grenoble-alpes.fr [Univ. Grenoble Alpes, LIPHY, F-38000 Grenoble, France and CNRS, LIPHY, F-38000 Grenoble (France); Yurtsever, E. [Koç University, Rumelifeneriyolu, Sariyer, Istanbul 34450 (Turkey)

2016-06-14

This work theoretically examines the progressive coating of planar polycyclic aromatic hydrocarbon (PAH) molecules ranging from benzene to circumcoronene (C{sub 54}H{sub 18}) by para-hydrogen and ortho-deuterium. The coarse-grained Silvera-Goldman potential has been extended to model the interactions between hydrogen molecules and individual atoms of the PAH and parametrized against quantum chemical calculations for benzene-H{sub 2}. Path-integral molecular dynamics simulations at 2 K were performed for increasingly large amounts of hydrogen coating the PAH up to the first solvation shell and beyond. From the simulations, various properties were determined such as the size of the first shell and its thickness as well as the solvation energy. The degree of delocalization was notably quantified from an energy landscape perspective, by monitoring the fluctuations among inherent structures sampled by the trajectories. Our results generally demonstrate a high degree of localization owing to relatively strong interactions between hydrogen and the PAH, and qualitatively minor isotopic effects. In the limit of large hydrogen amounts, the shell size and solvation energy both follow approximate linear relations with the numbers of carbon and hydrogen in the PAH.

Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

DEFF Research Database (Denmark)

Brandt van Driel, Tim; Kjær, Kasper Skov; Hartsock, Robert W.

2016-01-01

The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynami...... of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis....

Large-scale atomistic and quantum-mechanical simulations of a Nafion membrane: Morphology, proton solvation and charge transport

Directory of Open Access Journals (Sweden)

Pavel V. Komarov

2013-09-01

Full Text Available Atomistic and first-principles molecular dynamics simulations are employed to investigate the structure formation in a hydrated Nafion membrane and the solvation and transport of protons in the water channel of the membrane. For the water/Nafion systems containing more than 4 million atoms, it is found that the observed microphase-segregated morphology can be classified as bicontinuous: both majority (hydrophobic and minority (hydrophilic subphases are 3D continuous and organized in an irregular ordered pattern, which is largely similar to that known for a bicontinuous double-diamond structure. The characteristic size of the connected hydrophilic channels is about 25–50 Å, depending on the water content. A thermodynamic decomposition of the potential of mean force and the calculated spectral densities of the hindered translational motions of cations reveal that ion association observed with decreasing temperature is largely an entropic effect related to the loss of low-frequency modes. Based on the results from the atomistic simulation of the morphology of Nafion, we developed a realistic model of ion-conducting hydrophilic channel within the Nafion membrane and studied it with quantum molecular dynamics. The extensive 120 ps-long density functional theory (DFT-based simulations of charge migration in the 1200-atom model of the nanochannel consisting of Nafion chains and water molecules allowed us to observe the bimodality of the van Hove autocorrelation function, which provides the direct evidence of the Grotthuss bond-exchange (hopping mechanism as a significant contributor to the proton conductivity.

17O NMR Studies of the Solvation State of cissolidustrans Isomers of Amides and Model Protected Peptides

Science.gov (United States)

Gerothanassis; Vakka; Troganis

1996-06-01

17O shielding constants have been utilized to investigate solvation differences of the cissolidustrans isomers of N-methylformamide (NMF), N-ethylformamide (NEF), and tert-butylformamide (TBF) in a variety of solvents with particular emphasis on aqueous solution. Comparisons are also made with protected peptides of the formulas CH3CO-YOH, CH3CO-Y-NHR (Y = Pro, Sar), and CH3CO-Y-Z-NHR (Y = Pro; Z = D-Ala) selectively enriched in 17O at the acetyl oxygen atom. Hydration at the amide oxygen induces large and specific modifications of the 17O shielding constants, which are practically the same for the cis and trans isomers of NMF, NEF, and the protected peptides. For tert-butylformamide, the strong deshielding of the trans isomer compared to that of the cis isomer may be attributed to an out-of-plane (torsion-angle) deformation of the amide bond andsolidusor a significant reduction of solvation of the trans isomer due to steric inhibition of the bulky tert-butyl group. Good linear correlation between delta(17O) of amides and delta(17O) of acetone was found for different solvents which have varying dielectric constants and solvation abilities. Sum-over-states calculations, within the solvaton model, underestimate effects of the dielectric constant of the medium on 17O shielding, while finite-perturbation-theory calculations give good agreement with the experiment.

Establishing linear solvation energy relationships between VOCs and monolayer-protected gold nanoclusters using quartz crystal microbalance.

Science.gov (United States)

Li, Chi-Lin; Lu, Chia-Jung

2009-08-15

Linear solvation energy relationships (LSERs) have been recognized as a useful model for investigating the chemical forces behind the partition coefficients between vapor molecules and absorbents. This study is the first to determine the solvation properties of monolayer-protected gold nanoclusters (MPCs) with different surface ligands. The ratio of partition coefficients/MPC density (K/rho) of 18 volatile organic compounds (VOCs) for four different MPCs obtained through quartz crystal microbalance (QCM) experiments were used for the LSER model calculations. LSER modeling results indicate that all MPC surfaces showed a statistically significant (pattraction, 4-methoxythiophenol-capped MPCs can also interact with polar organics (s=1.04). Showing a unique preference for the hydrogen bond basicity of vapors (b=1.11), 2-benzothiazolethiol-capped MPCs provide evidence of an intra-molecular, proton-shift mechanism on surface of nano-gold.

Molecular Design of Sulfonated Triblock Copolymer Permselective Membranes

Science.gov (United States)

2008-07-03

on DNA solvation in water [39] and simulations of polyacrylic acid with calcium counterion.[40] Mesoscale approaches to polyelectrolyte modeling...interacts strongly with both proton and potassium cation. Addition of three extra DMMP molecules does not change the nature of proton solvation. The ion...the potassium ion with K-O distance of 0.22nm. This does not mean a coordination of DMMP molecules by the ion. However, this result suggests a very

Probing subsistence of ion-pair and triple-ion of an ionic salt in liquid environments by means of conductometric contrivance

International Nuclear Information System (INIS)

Banik, Ishani; Roy, Mahendra Nath

2013-01-01

Highlights: • Study of ion-solvation of [Bu 4 NBF 4 ] in CH 3 CN, CH 3 OH, DMSO, and 1,3-DO. • Triple-ion formation in 1,3-Dioxolane. • Ion–solvent interaction is stronger in DMSO. • Ion–solvent interaction dominates over ion–ion interaction in the studied solutions. -- Abstract: Qualitative and quantitative analyses of molecular interaction prevailing in ionic salt-organic solvent media, probed by electrical conductances have been reported. Tetrabutylammonium tetrafluoroborate [Bu 4 NBF 4 ] in acetonitrile (CH 3 CN), methanol (CH 3 OH), dimethylsulfoxide (DMSO) and 1,3-dioxolane (1,3-DO) have been studied at 298.15 K. The extent of interaction is expressed in terms of the association constant (K A ) and shows the interaction to be a function of viscosity. Limiting molar conductances (Λ o ), association constants (K A ), and the association diameter (R) for ion-pair formation have been analyzed using the Fuoss conductance-concentration equation (1978). The observed molar conductivities were explained by the formation of ion-pairs (M + +X − ↔ MX, K P ) and triple-ions (2M + + X − ↔ M 2 X + ; M + + 2X − ↔ MX 2 − , K T ). The Walden product is obtained and discussed. The deviation of the conductometric curves (Λ vs c 1/2 ) from linearity for the electrolyte in 1,3-dioxolane indicates triple-ion formation, and therefore the corresponding conductance data have been analyzed by using the Fuoss–Kraus theory of triple-ions. The limiting ionic conductances (λ o ± ) have been calculated from the appropriate division of the limiting molar conductivity value of tetrabutylammonium tetraphenylborate [Bu 4 NBPh 4 ] as the “reference electrolyte” method along with a numerical evaluation of ion-pair and triple-ion formation constants (K P ≈ K A and K T ). The results have been interpreted in terms of solvent properties and configurational theory

Nucleofugalities of Neutral Leaving Groups in 80 % Aqueous Acetonitrile

Directory of Open Access Journals (Sweden)

Sandra Jurić

2016-06-01

Full Text Available Nucleofugalites of tetrahydrothiophene, dimethyl sulfide and differently substituted pyridines in 80 % aqueous acetonitrile have been derived from the SN1 solvolysis rate constants of the corresponding X,Y-substituted benzhydryl derivatives (1–10. In sol-volysis of sulfonium ions in 80 % aqueous acetonitrile, where acetonitrile is a good cation solvator, the solvation of the reactant ground state is an important rate determining variable since the positive charge is almost entirely located on the leaving group. As a consequence, reaction rates of sulfonium ions are more sensitive to the substrate structure in 80 % aqueous acetonitrile than in pure and aqueous alcohols, which are less efficient as cation solvators. In solvolysis of pyridinium ions the solvation of the reactant ground state is less important, since the positive charge is considerably distributed between the carbon at the reaction center and the leaving group. In such cases the important rate determining variable is solvation of the transition state. Slower reactions of pyridinium sub-strates progress over later, carbocation-like transition states in which the solvation is more important, so those substrates solvolyze slightly faster in aqueous acetonitrile than in methanol (k80AN > kM. Faster reactions proceed over earlier TS in which the solvation is diminished, so those substrates solvolyze somewhat faster in methanol than in aqueous acetonitrile (k80AN kM. This work is licensed under a Creative Commons Attribution 4.0 International License.

First crystal structures of pharmaceutical ibrutinib: systematic solvate screening and characterization

Czech Academy of Sciences Publication Activity Database

Zvoníček, V.; Skořepová, E.; Dušek, Michal; Babor, M.; Zvatora, P.; Šoós, M.

2017-01-01

Roč. 17, č. 6 (2017), s. 3116-3127 ISSN 1528-7483 R&D Projects: GA MŠk LO1603; GA ČR GA17-23196S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : Ibrutinib solvates * anticancer drug * Raman spectroscopy * powder X-ray diffraction * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 4.055, year: 2016

Variation of the solvation number of Eu(III) in mixed system of methanol and water

International Nuclear Information System (INIS)

Suganuma, H.; Arisaka, M.; Omori, T.; Satoh, I.; Choppin, G.R.

1999-01-01

The stability constants (β 1 ) of the monofluoride complex of Eu(III) have been determined in mixed solvents of methanol and water at a 0.10 M ionic strength using a solvent extraction technique. The values of ln β 1 increase as the mole fraction of methanol in the mixed solvent system increases. The variation in the stability constants can be correlated with both the large effect due to the solvation of F and the small effect due to both (1) the solvation of cations in connection with complexation and (2) the electrostatic attraction between Eu 3+ and F - . Based on the variation in the sum of (1) and (2) in water and the mixed solvent solutions, it was determined that the coordination number (CN) of Eu(III) varied from a mixture of CN = 9 and 8 to CN = 8 at about a 0.03 mole fraction of methanol in the mixed solvent. (orig.)

Characterization of a Distributed Plasma Ionization Source (DPIS) for Ion Mobility Spectrometry and Mass Spectrometry

International Nuclear Information System (INIS)

Waltman, Melanie J.; Dwivedi, Prabha; Hill, Herbert; Blanchard, William C.; Ewing, Robert G.

2008-01-01

A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry and ion mobility spectrometry. The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions depending on the polarity of the applied potential. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H2O)nH+ with (H2O)2H+ as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO3-, NO3-, NO2-, O3- and O2- of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and environmental pollutants were selected to evaluate the new ionization source. The source was operated continuously for several months and although deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions. The results indicated that the DPIS may have a longer operating life than a conventional corona discharge.

Phospholipid bilayer affinities and solvation characteristics by electrokinetic chromatography with a nanodisc pseudostationary phase.

Science.gov (United States)

Penny, William M; Steele, Harmen B; Ross, J B Alexander; Palmer, Christopher P

2017-03-01

Phospholipid bilayer nanodiscs composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine and synthetic maleic acid-styrene copolymer belts have been introduced as a pseudostationary phase (PSP) in electrokinetic chromatography and demonstrated good performance. The nanodiscs provide a suitable migration range and high theoretical plate counts. Using this nanodisc pseudostationary phase, the affinity of the bilayer structure for probe solutes was determined and characterized. Good correlation is observed between retention factors and octanol water partition coefficients for particular categories of solutes, but the general correlation is weak primarily because the nanodiscs show stronger affinity than octanol for hydrogen bond donors. This suggests that a more appropriate application of this technology is to measure and characterize interactions between solutes and lipid bilayers directly. Linear solvation energy relationship analysis of the nanodisc-solute interactions in this study demonstrates that the nanodiscs provide a solvation environment with low cohesivity and weak hydrogen bond donating ability, and provide relatively strong hydrogen bond acceptor strength. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A linear solvation energy relationship model of organic chemical partitioning to dissolved organic carbon.

Science.gov (United States)

Kipka, Undine; Di Toro, Dominic M

2011-09-01

Predicting the association of contaminants with both particulate and dissolved organic matter is critical in determining the fate and bioavailability of chemicals in environmental risk assessment. To date, the association of a contaminant to particulate organic matter is considered in many multimedia transport models, but the effect of dissolved organic matter is typically ignored due to a lack of either reliable models or experimental data. The partition coefficient to dissolved organic carbon (K(DOC)) may be used to estimate the fraction of a contaminant that is associated with dissolved organic matter. Models relating K(DOC) to the octanol-water partition coefficient (K(OW)) have not been successful for many types of dissolved organic carbon in the environment. Instead, linear solvation energy relationships are proposed to model the association of chemicals with dissolved organic matter. However, more chemically diverse K(DOC) data are needed to produce a more robust model. For humic acid dissolved organic carbon, the linear solvation energy relationship predicts log K(DOC) with a root mean square error of 0.43. Copyright © 2011 SETAC.

A 13C NMR Study of 7-Norbornadienyl Cation by Modified Hammett-Brown Equation

International Nuclear Information System (INIS)

Park, Jeong Kyu; Shin, Jung Hyu

1999-01-01

A series of the para-substituted 7-aryl-norbornadienyl cation (3) was prepared in FSO 3 H/SO 2 ClF solution at -100 .deg. C and their 13 C NMR shifts were measured at -80 .deg. C. The plots of the chemical shifts (changes in chemical shifts) of cationic carbon, Δδ C+ , against our calculated new substituent constant, σ c+ s, gave an excellent correlation (r = 0.994), with a p c+ value of 12.63. These results indicate that the new substituent onstants, σ c+ s, can be successfully employed to compare the relative charge demand of the carbonium ion by π- and πσ-participation

Ion-solvent interactions and the complex behaviour of U(IV) and U(VI) with chloro-ligands in ethanol-water mixtures

International Nuclear Information System (INIS)

Kim, J.I.; Duschner, H.; Hashimoto, T.; Born, H.J.

1975-01-01

The complex chemical behaviour of U(IV) and U(VI) in amphiprotic solutions, especially in mixtures of solvents, was investigated using ion exchange and solvent extraction methods. The experimental data was used, on the one hand, in order to obtain complexing constants in dependence of ligands and their concentration as well as of the agent and to classify these in a universal scale of ion activities with water as reference point, and on the other hand, to explain the interactions between central atom, ligand and solvating molecule. One aim of these investigations is to understand the basic mechanisms in adjusting the equilibrium between two different phases in the separation chemistry of these elements. (orig./LH) [de

Switchover of reactions of solvated electrons with nitrate ions and ammonium ions in propanol-water solvents

International Nuclear Information System (INIS)

Kang, T.B.; Freeman, G.R.

1993-01-01

The reaction rate constants of e s - with ammonium nitrate (∼0.1 mol m -3 ) in 1-propanol-water and 2-propanol-water binary solvents correspond to [e s - + (NO 3 - ) s ] reaction in the water-rich solvents, and to [e s - + (NH 4 + ) s ] reaction in alcohol-rich solvents. The overall rate constant is smaller in solvents with 40-99 mol% water, with a minimum at 70 mol% water. The Arrhenius temperature coefficient is 26 kJ mol -1 in each pure propanol solvent, increases to 29 kJ mol -1 at 40 mol% water, then decreases to 17 kJ mol -1 in pure water solvent. The high reaction rates in the single component solvents, alcohol or water, are limited mainly by solvent processes related to shear viscosity (diffusion) and dielectric relaxation (dipole reorientation). Rate constants reported for concentrated solutions (50-1000 mol m -3 ) of ammonium and nitrate salts in methanol have been quantitatively reinterpreted in terms of the ion atmosphere model. 28 refs., 5 figs., 2 tabs

Comparison of molecular mechanics-Poisson-Boltzmann surface area (MM-PBSA) and molecular mechanics-three-dimensional reference interaction site model (MM-3D-RISM) method to calculate the binding free energy of protein-ligand complexes: Effect of metal ion and advance statistical test

Science.gov (United States)

Pandey, Preeti; Srivastava, Rakesh; Bandyopadhyay, Pradipta

2018-03-01

The relative performance of MM-PBSA and MM-3D-RISM methods to estimate the binding free energy of protein-ligand complexes is investigated by applying these to three proteins (Dihydrofolate Reductase, Catechol-O-methyltransferase, and Stromelysin-1) differing in the number of metal ions they contain. None of the computational methods could distinguish all the ligands based on their calculated binding free energies (as compared to experimental values). The difference between the two comes from both polar and non-polar part of solvation. For charged ligand case, MM-PBSA and MM-3D-RISM give a qualitatively different result for the polar part of solvation.

Contribution to the study of solvated electrons in water and alcohols and of radiolytic processes in organic carbonates by picosecond pulse radiolysis

International Nuclear Information System (INIS)

Torche, Faycal

2012-01-01

This work is part of the study area of the interaction of radiation with polar liquids. Using the picosecond electron accelerator ELYSE, studies were conducted using the techniques of pulse radiolysis combined with absorption spectrophotometry Time-resolved in the field of a picosecond. This work is divided into two separate chapters. The first study addresses the temporal variation of the radiolytic yield of solvated electron in water and simple alcohols. Due to original detection system mounted on the accelerator ELYSE, composed of a flash lamp specifically designed for the detection and a streak-camera used for the first time in absorption spectroscopy, it was possible to record the time-dependent radiolytic yields of the solvated electron from ten picoseconds to a few hundred nanoseconds. The scavenging of the electron solvated by methyl viologen, was utilized to reevaluate the molar extinction coefficient of the absorption spectrum of solvated electron in water and ethanol from isobestic points which corresponds to the intersection of the absorption spectra of solvated electron which disappears and methyl viologen which is formed during the reaction. The second chapter is devoted to the study of liquid organic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and propylene carbonate (PC). This family of carbonate which compose the electrolytes lithium batteries, has never been investigated by pulse radiolysis. The studies were focused on the PC in the light of these physicochemical characteristics, including its very high dielectric constant and its strong dipole moment of 4.9 D. The first results were obtained on aqueous solutions containing propylene carbonate to observe the reactions of reduction and oxidation of PC by radiolytic species of water (solvated electron and OH radicals). Then, after the identification (spectral and kinetic) of the species formed by interaction with the OH radical as the PC* radical resulting from the

Development and application of QM/MM methods to study the solvation effects and surfaces

Energy Technology Data Exchange (ETDEWEB)

Dibya, Pooja Arora [Iowa State Univ., Ames, IA (United States)

2010-01-01

Quantum mechanical (QM) calculations have the advantage of attaining high-level accuracy, however QM calculations become computationally inefficient as the size of the system grows. Solving complex molecular problems on large systems and ensembles by using quantum mechanics still poses a challenge in terms of the computational cost. Methods that are based on classical mechanics are an inexpensive alternative, but they lack accuracy. A good trade off between accuracy and efficiency is achieved by combining QM methods with molecular mechanics (MM) methods to use the robustness of the QM methods in terms of accuracy and the MM methods to minimize the computational cost. Two types of QM combined with MM (QM/MM) methods are the main focus of the present dissertation: the application and development of QM/MM methods for solvation studies and reactions on the Si(100) surface. The solvation studies were performed using a discreet solvation model that is largely based on first principles called the effective fragment potential method (EFP). The main idea of combining the EFP method with quantum mechanics is to accurately treat the solute-solvent and solvent-solvent interactions, such as electrostatic, polarization, dispersion and charge transfer, that are important in correctly calculating solvent effects on systems of interest. A second QM/MM method called SIMOMM (surface integrated molecular orbital molecular mechanics) is a hybrid QM/MM embedded cluster model that mimics the real surface.3 This method was employed to calculate the potential energy surfaces for reactions of atomic O on the Si(100) surface. The hybrid QM/MM method is a computationally inexpensive approach for studying reactions on larger surfaces in a reasonably accurate and efficient manner. This thesis is comprised of four chapters: Chapter 1 describes the general overview and motivation of the dissertation and gives a broad background of the computational methods that have been employed in this work

New Insights of Graphite Anode Stability in Rechargeable Batteries: Li-Ion Coordination Structures Prevail over Solid Electrolyte Interphases

KAUST Repository

Ming, Jun

2018-01-04

Graphite anodes are not stable in most noncarbonate solvents (e.g., ether, sulfoxide, sulfone) upon Li ion intercalation, known as an urgent issue in present Li ions and next-generation Li–S and Li–O2 batteries for storage of Li ions within the anode for safety features. The solid electrolyte interphase (SEI) is commonly believed to be decisive for stabilizing the graphite anode. However, here we find that the solvation structure of the Li ions, determined by the electrolyte composition including lithium salts, solvents, and additives, plays a more dominant role than SEI in graphite anode stability. The Li ion intercalation desired for battery operation competes with the undesired Li+–solvent co-insertion, leading to graphite exfoliation. The increase in organic lithium salt LiN(SO2CF3)2 concentration or, more effectively, the addition of LiNO3 lowers the interaction strength between Li+ and solvents, suppressing the graphite exfoliation caused by Li+–solvent co-insertion. Our findings refresh the knowledge of the well-known SEI for graphite stability in metal ion batteries and also provide new guidelines for electrolyte systems to achieve reliable and safe Li–S full batteries.

Comparison of the Marcus and Pekar partitions in the context of non-equilibrium, polarizable-continuum solvation models

International Nuclear Information System (INIS)

You, Zhi-Qiang; Herbert, John M.; Mewes, Jan-Michael; Dreuw, Andreas

2015-01-01

The Marcus and Pekar partitions are common, alternative models to describe the non-equilibrium dielectric polarization response that accompanies instantaneous perturbation of a solute embedded in a dielectric continuum. Examples of such a perturbation include vertical electronic excitation and vertical ionization of a solution-phase molecule. Here, we provide a general derivation of the accompanying polarization response, for a quantum-mechanical solute described within the framework of a polarizable continuum model (PCM) of electrostatic solvation. Although the non-equilibrium free energy is formally equivalent within the two partitions, albeit partitioned differently into “fast” versus “slow” polarization contributions, discretization of the PCM integral equations fails to preserve certain symmetries contained in these equations (except in the case of the conductor-like models or when the solute cavity is spherical), leading to alternative, non-equivalent matrix equations. Unlike the total equilibrium solvation energy, however, which can differ dramatically between different formulations, we demonstrate that the equivalence of the Marcus and Pekar partitions for the non-equilibrium solvation correction is preserved to high accuracy. Differences in vertical excitation and ionization energies are <0.2 eV (and often <0.01 eV), even for systems specifically selected to afford a large polarization response. Numerical results therefore support the interchangeability of the Marcus and Pekar partitions, but also caution against relying too much on the fast PCM charges for interpretive value, as these charges differ greatly between the two partitions, especially in polar solvents

Comparison of the Marcus and Pekar partitions in the context of non-equilibrium, polarizable-continuum solvation models

Energy Technology Data Exchange (ETDEWEB)

You, Zhi-Qiang; Herbert, John M., E-mail: herbert@chemistry.ohio-state.edu [Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210 (United States); Mewes, Jan-Michael; Dreuw, Andreas [Interdisciplinary Center for Scientific Computing, Ruprechts-Karls University, Im Neuenheimer Feld 368, 69120 Heidelberg (Germany)

2015-11-28

The Marcus and Pekar partitions are common, alternative models to describe the non-equilibrium dielectric polarization response that accompanies instantaneous perturbation of a solute embedded in a dielectric continuum. Examples of such a perturbation include vertical electronic excitation and vertical ionization of a solution-phase molecule. Here, we provide a general derivation of the accompanying polarization response, for a quantum-mechanical solute described within the framework of a polarizable continuum model (PCM) of electrostatic solvation. Although the non-equilibrium free energy is formally equivalent within the two partitions, albeit partitioned differently into “fast” versus “slow” polarization contributions, discretization of the PCM integral equations fails to preserve certain symmetries contained in these equations (except in the case of the conductor-like models or when the solute cavity is spherical), leading to alternative, non-equivalent matrix equations. Unlike the total equilibrium solvation energy, however, which can differ dramatically between different formulations, we demonstrate that the equivalence of the Marcus and Pekar partitions for the non-equilibrium solvation correction is preserved to high accuracy. Differences in vertical excitation and ionization energies are <0.2 eV (and often <0.01 eV), even for systems specifically selected to afford a large polarization response. Numerical results therefore support the interchangeability of the Marcus and Pekar partitions, but also caution against relying too much on the fast PCM charges for interpretive value, as these charges differ greatly between the two partitions, especially in polar solvents.

17O NMR Studies of the Solvation State of cis/trans Isomers of Amides and Model Protected Peptides

Science.gov (United States)

Gerothanassis, Ioannis P.; Vakka, Constantina; Troganis, Anastasios

1996-06-01

17O shielding constants have been utilized to investigate solvation differences of the cis/trans isomers ofN-methylformamide (NMF),N-ethylformamide (NEF), andtert-butylformamide (TBF) in a variety of solvents with particular emphasis on aqueous solution. Comparisons are also made with protected peptides of the formulas CH3CO-YOH, CH3CO-Y-NHR (Y = Pro, Sar), and CH3CO-Y-Z-NHR (Y = Pro; Z =D-Ala) selectively enriched in17O at the acetyl oxygen atom. Hydration at the amide oxygen induces large and specific modifications of the17O shielding constants, which are practically the same for the cis and trans isomers of NMF, NEF, and the protected peptides. Fortert-butylformamide, the strong deshielding of the trans isomer compared to that of the cis isomer may be attributed to an out-of-plane (torsion-angle) deformation of the amide bond and/or a significant reduction of solvation of the trans isomer due to steric inhibition of the bulkytert-butyl group. Good linear correlation between δ(17O) of amides and δ(17O) of acetone was found for different solvents which have varying dielectric constants and solvation abilities. Sum-over-states calculations, within the solvaton model, underestimate effects of the dielectric constant of the medium on17O shielding, while finite-perturbation-theory calculations give good agreement with the experiment.

Electron detachment energies in high-symmetry alkali halide solvated-electron anions

Science.gov (United States)

Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

2003-07-01

We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

Molecular Dynamics Simulation of the Antiamoebin Ion Channel: Linking Structure and Conductance

Science.gov (United States)

Wilson, Michael A.; Wei, Chenyu; Bjelkmar, Paer; Wallace, B. A.; Pohorille, Andrew

2011-01-01

Molecular dynamics simulations were carried out in order to ascertain which of the potential multimeric forms of the transmembrane peptaibol channel, antiamoebin, is consistant with its measured conductance. Estimates of the conductance obtained through counting ions that cross the channel and by solving the Nernst-Planck equation yield consistent results, indicating that the motion of ions inside the channel can be satisfactorily described as diffusive.The calculated conductance of octameric channels is markedly higher than the conductance measured in single channel recordings, whereas the tetramer appears to be non-conducting. The conductance of the hexamer was estimated to be 115+/-34 pS and 74+/-20 pS, at 150 mV and 75 mV, respectively, in satisfactory agreement with the value of 90 pS measured at 75 mV. On this basis we propose that the antiamoebin channel consists of six monomers. Its pore is large enough to accommodate K(+) and Cl(-) with their first solvation shells intact. The free energy barrier encountered by K(+) is only 2.2 kcal/mol whereas Cl(-) encounters a substantially higher barrier of nearly 5 kcal/mol. This difference makes the channel selective for cations. Ion crossing events are shown to be uncorrelated and follow Poisson statistics. keywords: ion channels, peptaibols, channel conductance, molecular dynamics

Effect of halogen substitution on the enthalpies of solvation and hydrogen bonding of organic solutes in chlorobenzene and 1,2-dichlorobenzene derived using multi-parameter correlations

Energy Technology Data Exchange (ETDEWEB)

Varfolomeev, Mikhail A.; Rakipov, Ilnaz T.; Khachatrian, Artashes A. [Department of Physical Chemistry, Kazan Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation); Acree, William E., E-mail: acree@unt.edu [Department of Chemistry, 1155 Union Circle # 305070, University of North Texas, Denton, TX 76203-5017 (United States); Brumfield, Michela [Department of Chemistry, 1155 Union Circle # 305070, University of North Texas, Denton, TX 76203-5017 (United States); Abraham, Michael H. [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)

2015-10-10

Graphical abstract: - Highlights: • Enthalpies of solution measured for 43 solutes dissolved in chlorobenzene. • Enthalpies of solution measured for 72 solutes dissolved in 1,2-dichlorobenzene. • Mathematical expressions derived for predicting enthalpies of solvation of solutes in chlorobenzene. • Mathematical expressions derived for predicting enthalpies of solvation of solutes in 1,2-chlorobenzene. - Abstract: Enthalpies of solution at infinite dilution at 298 K, Δ{sub soln}H{sup A/Solvent}, have been measured by isothermal solution calorimetry for 43 and 72 organic solutes dissolved in chlorobenzene and 1,2-dichlorobenzene, respectively. The measured Δ{sub soln}H{sup A/Solvent} data, along with published Δ{sub soln}H{sup A/Solvent} values taken from the published literature for solutes dissolved in both chlorobenzene solvents, were converted to enthalpies of solvation, Δ{sub solv}H{sup A/Solvent}, using standard thermodynamic equations. Abraham model correlations were developed from the experimental Δ{sub solv}H{sup A/Solvent} data. The best derived correlations describe the experimental gas-to-chlorobenzene and gas-to-1,2-dichlorobenzene enthalpies of solvation to within standard deviations of 1.5 kJ mol{sup −1} and 1.9 kJ mol{sup −1}, respectively. Enthalpies of X−H…π (X – O, N, and C) hydrogen bond formation of proton donor solutes (alcohols, amines, chlorinated hydrocarbons, etc.) with chlorobenzene and 1,2-dichlorobenzene were calculated based on the Abraham solvation equation. Obtained values are in good agreement with the results determined using conventional methods.

Ion-ion correlation, solvent excluded volume and pH effects on physicochemical properties of spherical oxide nanoparticles.

Science.gov (United States)

Ovanesyan, Zaven; Aljzmi, Amal; Almusaynid, Manal; Khan, Asrar; Valderrama, Esteban; Nash, Kelly L; Marucho, Marcelo

2016-01-15

One major source of complexity in the implementation of nanoparticles in aqueous electrolytes arises from the strong influence that biological environments has on their physicochemical properties. A key parameter for understanding the molecular mechanisms governing the physicochemical properties of nanoparticles is the formation of the surface charge density. In this article, we present an efficient and accurate approach that combines a recently introduced classical solvation density functional theory for spherical electrical double layers with a surface complexation model to account for ion-ion correlation and excluded volume effects on the surface titration of spherical nanoparticles. We apply the proposed computational approach to account for the charge-regulated mechanisms on the surface chemistry of spherical silica (SiO2) nanoparticles. We analyze the effects of the nanoparticle size, as well as pH level and electrolyte concentration of the aqueous solution on the nanoparticle's surface charge density and Zeta potential. We validate our predictions for 580Å and 200Å nanoparticles immersed in acid, neutral and alkaline mono-valent aqueous electrolyte solutions against experimental data. Our results on mono-valent electrolyte show that the excluded volume and ion-ion correlations contribute significantly to the surface charge density and Zeta potential of the nanoparticle at high electrolyte concentration and pH levels, where the solvent crowding effects and electrostatic screening have shown a profound influence on the protonation/deprotonation reactions at the liquid/solute interface. The success of this approach in describing physicochemical properties of silica nanoparticles supports its broader application to study other spherical metal oxide nanoparticles. Copyright © 2015 Elsevier Inc. All rights reserved.

Ion-specific weak adsorption of salts and water/octanol transfer free energy of a model amphiphilic hexapeptide.

Science.gov (United States)

Déjugnat, Christophe; Dufrêche, Jean-François; Zemb, Thomas

2011-04-21

An amphiphilic hexapeptide has been used as a model to quantify how specific ion effects induced by addition of four salts tune the hydrophilic/hydrophobic balance and induce temperature-dependant coacervate formation from aqueous solution. The hexapeptide chosen is present as a dimer with low transfer energy from water to octanol. Taking sodium chloride as the reference state in the Hofmeister scale, we identify water activity effects and therefore measure the free energy of transfer from water to octanol and separately the free energy associated to the adsorption of chaotropic ions or the desorption of kosmotropic ions for the same amphiphilic peptide. These effects have the same order of magnitude: therefore, both energies of solvation as well as transfer into octanol strongly depend on the nature of the electrolytes used to formulate any buffer. Model peptides could be used on separation processes based on criteria linked to "Hofmeister" but different from volume and valency.

Developing New Electrolytes for Advanced Li-ion Batteries

Science.gov (United States)

McOwen, Dennis Wayne

synthesized for this investigation: dilithium 1,2,5-thiadiazolidine-3,4-dione-1,1-dioxide (Li2TDD), lithium ethyl N-trifluoroacetylcarbamate (LiETAC), lithium hexafluoroisopropoxide (LiHFI), lithium pentafluorophenolate (LiPFPO), and lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI). Using crystalline solvate structure analysis and electrolyte solvation numbers, each of these lithium salts were compared to more well-characterized lithium salts, such as LiPF6 and LiBF4. From this study, links between anion structural characteristics and the anion...Li+ cation interactions (i.e., ionic association strength) were made. From the screening of the five lithium salts that were synthesized, LiTDI was determined to be a promising candidate for Li-ion battery electrolytes. Further characterization of carbonate- and mixed carbonate-LiTDI electrolytes (e.g., ionic conductivity) confirmed this to be the case. Coin cells containing LiTDI or LiPF6 electrolytes showed that cells with either electrolyte could deliver nearly identical power density at 25 °C. Additionally, thermogravimetric analysis (TGA) and NMR suggested that the LiTDI salt and carbonate-LiTDI electrolytes are thermally stable up to at least 60 °C. Further supporting this finding, coin cells cycled at 60 °C with LiPF6 lost significantly more capacity than those with LiTDI. Therefore, LiTDI is a prime candidate for the complete replacement of LiPF6 to significantly increase Li-ion battery tolerance to heat, improving the safety characteristics. In addition to searching for new lithium salts, the effect of lithium salt concentration on electrolyte physicochemical properties was investigated. This radically different approach to modifying electrolyte properties determined that amorphous, highly concentrated carbonate-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolytes have drastically different behavior than more dilute electrolytes. For example, the thermal stability and anodic stability vs. a Pt

Effect of Intercalated Water on Potassium Ion Transport through Kv1.2 Channels Studied via On-the-Fly Free-Energy Parametrization.

Science.gov (United States)

Paz, S Alexis; Maragliano, Luca; Abrams, Cameron F

2018-05-08

We introduce a two-dimensional version of the method called on-the-fly free energy parametrization (OTFP) to reconstruct free-energy surfaces using Molecular Dynamics simulations, which we name OTFP-2D. We first test the new method by reconstructing the well-known dihedral angles free energy surface of solvated alanine dipeptide. Then, we use it to investigate the process of K + ions translocation inside the Kv1.2 channel. By comparing a series of two-dimensional free energy surfaces for ion movement calculated with different conditions on the intercalated water molecules, we first recapitulate the widely accepted knock-on mechanism for ion translocation and then confirm that permeation occurs with water molecules alternated among the ions, in accordance with the latest experimental findings. From a methodological standpoint, our new OTFP-2D algorithm demonstrates the excellent sampling acceleration of temperature-accelerated molecular dynamics and the ability to efficiently compute 2D free-energy surfaces. It will therefore be useful in large variety complex biomacromolecular simulations.

Extending the Solvation-Layer Interface Condition Continum Electrostatic Model to a Linearized Poisson-Boltzmann Solvent.

Science.gov (United States)

Molavi Tabrizi, Amirhossein; Goossens, Spencer; Mehdizadeh Rahimi, Ali; Cooper, Christopher D; Knepley, Matthew G; Bardhan, Jaydeep P

2017-06-13

We extend the linearized Poisson-Boltzmann (LPB) continuum electrostatic model for molecular solvation to address charge-hydration asymmetry. Our new solvation-layer interface condition (SLIC)/LPB corrects for first-shell response by perturbing the traditional continuum-theory interface conditions at the protein-solvent and the Stern-layer interfaces. We also present a GPU-accelerated treecode implementation capable of simulating large proteins, and our results demonstrate that the new model exhibits significant accuracy improvements over traditional LPB models, while reducing the number of fitting parameters from dozens (atomic radii) to just five parameters, which have physical meanings related to first-shell water behavior at an uncharged interface. In particular, atom radii in the SLIC model are not optimized but uniformly scaled from their Lennard-Jones radii. Compared to explicit-solvent free-energy calculations of individual atoms in small molecules, SLIC/LPB is significantly more accurate than standard parametrizations (RMS error 0.55 kcal/mol for SLIC, compared to RMS error of 3.05 kcal/mol for standard LPB). On parametrizing the electrostatic model with a simple nonpolar component for total molecular solvation free energies, our model predicts octanol/water transfer free energies with an RMS error 1.07 kcal/mol. A more detailed assessment illustrates that standard continuum electrostatic models reproduce total charging free energies via a compensation of significant errors in atomic self-energies; this finding offers a window into improving the accuracy of Generalized-Born theories and other coarse-grained models. Most remarkably, the SLIC model also reproduces positive charging free energies for atoms in hydrophobic groups, whereas standard PB models are unable to generate positive charging free energies regardless of the parametrized radii. The GPU-accelerated solver is freely available online, as is a MATLAB implementation.

Effects of solvation shells and cluster size on the reaction of aluminum clusters with water

Directory of Open Access Journals (Sweden)

Weiwei Mou

2011-12-01

Full Text Available Reaction of aluminum clusters, Aln (n = 16, 17 and 18, with liquid water is investigated using quantum molecular dynamics simulations, which show rapid production of hydrogen molecules assisted by proton transfer along a chain of hydrogen bonds (H-bonds between water molecules, i.e. Grotthuss mechanism. The simulation results provide answers to two unsolved questions: (1 What is the role of a solvation shell formed by non-reacting H-bonds surrounding the H-bond chain; and (2 whether the high size-selectivity observed in gas-phase Aln-water reaction persists in liquid phase? First, the solvation shell is found to play a crucial role in facilitating proton transfer and hence H2 production. Namely, it greatly modifies the energy barrier, generally to much lower values (< 0.1 eV. Second, we find that H2 production by Aln in liquid water does not depend strongly on the cluster size, in contrast to the existence of magic numbers in gas-phase reaction. This paper elucidates atomistic mechanisms underlying these observations.

Ligand Conformational and Solvation/Desolvation Free Energy in Protein-Ligand Complex Formation

Czech Academy of Sciences Publication Activity Database

Kolář, Michal; Fanfrlík, Jindřich; Hobza, Pavel

2011-01-01

Roč. 115, č. 16 (2011), s. 4718-4724 ISSN 1520-6106 R&D Projects: GA MŠk LC512; GA ČR GAP208/11/0295 Grant - others:Korea Science and Engineering Foundation(KR) R32-2008-000-10180-0; European Science Fund(XE) CZ.1.05/2.1.00/03.0058 Institutional research plan: CEZ:AV0Z40550506 Keywords : solvation free energy * SMD * HIV protease inhibitors Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.696, year: 2011

Conformational Behavior of Polymer Chains of Different Architectures in Strongly Endothermic Solvent Mixtures: Specific Solvation Effects.

Czech Academy of Sciences Publication Activity Database

Suchá, L.; Limpouchová, Z.; Procházka, Karel

2017-01-01

Roč. 295, č. 8 (2017), s. 1391-1403 ISSN 0303-402X R&D Projects: GA ČR GA15-19542S Institutional support: RVO:67985858 Keywords : cononsolvency * preferential solvation * star polymer Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.723, year: 2016

Ion-exchange behaviour of hydrous zirconia in mixed solvents: capacity and kinetics of exchange

International Nuclear Information System (INIS)

Misak, N.Z.; Ghoneimy, H.F.

1982-01-01

The capacity of the Li + form of hydrous zirconia for Na + and Cs + increases in the presence of methanol. This may be due to the greater stability of Li + in methanol/water than in pure water and to dehydration of Na + and Cs + and their stronger interaction with the exchange sites, which may facilitate their replacing Li + . The ion-exchange capacity of zirconia for NO 3 - , Cl - and Br - is almost the same in aqueous solution and is not affected by addition of up to 90% (v/v) methanol, which probably shows that these anions are electrostatically bound in zirconia without specific interactions. The internal diffusion coefficients of the Na + /H + and Cl - /OH - systems decrease in the presence of alcohol: the decrease is highest with methanol and similar for ethanol and propan-2-ol. This is discussed in the light of ion solvation and alcohol penetration inside zirconia. (author)

Differential solvation of intrinsically disordered linkers drives the formation of spatially organized droplets in ternary systems of linear multivalent proteins

Science.gov (United States)

Harmon, Tyler S.; Holehouse, Alex S.; Pappu, Rohit V.

2018-04-01

Intracellular biomolecular condensates are membraneless organelles that encompass large numbers of multivalent protein and nucleic acid molecules. The bodies assemble via a combination of liquid–liquid phase separation and gelation. A majority of condensates included multiple components and show multilayered organization as opposed to being well-mixed unitary liquids. Here, we put forward a simple thermodynamic framework to describe the emergence of spatially organized droplets in multicomponent systems comprising of linear multivalent polymers also known as associative polymers. These polymers, which mimic proteins and/or RNA have the architecture of domains or motifs known as stickers that are interspersed by flexible spacers known as linkers. Using a minimalist numerical model for a four-component system, we have identified features of linear multivalent molecules that are necessary and sufficient for generating spatially organized droplets. We show that differences in sequence-specific effective solvation volumes of disordered linkers between interaction domains enable the formation of spatially organized droplets. Molecules with linkers that are preferentially solvated are driven to the interface with the bulk solvent, whereas molecules that have linkers with negligible effective solvation volumes form cores in the core–shell architectures that emerge in the minimalist four-component systems. Our modeling has relevance for understanding the physical determinants of spatially organized membraneless organelles.

Ion-specific weak adsorption of salts and water/octanol transfer free energy of a model amphiphilic hexa-peptide

International Nuclear Information System (INIS)

Dejugnat, Ch.; Dufreche, J.F.; Zemb, Th.; Dejugnat, Ch.

2011-01-01

An amphiphilic hexa-peptide has been used as a model to quantify how specific ion effects induced by addition of four salts tune the hydrophilic/hydrophobic balance and induce temperature-dependant coacervate formation from aqueous solution. The hexa-peptide chosen is present as a dimer with low transfer energy from water to octanol. Taking sodium chloride as the reference state in the Hofmeister scale, we identify water activity effects and therefore measure the free energy of transfer from water to octanol and separately the free energy associated to the adsorption of chaotropic ions or the desorption of kosmotropic ions for the same amphiphilic peptide. These effects have the same order of magnitude: therefore, both energies of solvation as well as transfer into octanol strongly depend on the nature of the electrolytes used to formulate any buffer. Model peptides could be used on separation processes based on criteria linked to 'Hofmeister' but different from volume and valency. (authors)

Differential Deformability of the DNA Minor Groove and Altered BI/BII Backbone Conformational Equilibrium by the Monovalent Ions Li+, Na+, K+ and Rb+ via Water-Mediated Hydrogen Bonding

Science.gov (United States)

Savelyev, Alexey; MacKerell, Alexander D.

2015-01-01

Recently, we reported the differential impact of the monovalent cations Li+, Na+, K+ and Rb+ on DNA conformational properties. These were identified from variations in the calculated solution-state X-ray DNA spectra as a function of the ion type in the solvation buffer in MD simulations using our recently developed polarizable force field based on the classical Drude oscillator. Changes in the DNA structure were found to mainly involve variations in the minor groove width. Because minor groove dimensions vary significantly in protein-DNA complexes and have been shown to play a critical role in both specific and nonspecific DNA readout, understanding the origins of the observed differential DNA modulation by the first-group monovalent ions is of great biological importance. In the present study we show that the primary microscopic mechanism for the phenomenon is the formation of the water-mediated hydrogen bonds between solvated cations located inside the minor groove and simultaneously to two DNA strands, a process whose intensity and impact on DNA structure depends on both the type of the ion and DNA sequence. Additionally, it is shown that formation of such ion-DNA hydrogen bond complexes appreciably modulates the conformation of the backbone by increasing the population of the BII substate. Notably, the differential impact of the ions on DNA conformational behavior is only predicted by the Drude polarizable model for DNA, with virtually no effect observed from MD simulations utilizing the additive CHARMM36 model. Analysis of dipole moments of the water shows the Drude SWM4 model to possess high sensitivity to changes in the local environment, which indicates the important role of electronic polarization in the salt-dependent conformational properties. This also suggests that inclusion of polarization effects is required to model even relatively simple biological systems such as DNA in various ionic solutions. PMID:26575937

Solvation analysis of some Solvatochromic probes in binary mixtures of reline, ethaline, and glyceline with DMSO

Czech Academy of Sciences Publication Activity Database

Harifi-Mood, A.R.; Ghobadi, R.; Matić, S.; Minofar, Babak; Řeha, David

2016-01-01

Roč. 22, OCT 2016 (2016), s. 845-853 ISSN 0167-7322 R&D Projects: GA ČR GA13-21053S; GA MŠk(CZ) LM2015055 Institutional support: RVO:61388971 Keywords : Deep eutectic solvents * Solvatochromic parameters * Preferential solvation Subject RIV: EE - Microbiology, Virology Impact factor: 3.648, year: 2016

Ion exchange of some transition metal cations on hydrated titanium dioxide in aqueous ammonia solutions

International Nuclear Information System (INIS)

Bilewicz, A.; Narbutt, J.; Dybczynski, R.

1992-01-01

The adsorption of transition metal cations on hydrated titanium dioxide in complexing ammonia and amine solutions has been studied as a function of ammonia (amine) concentration. The relationships between the distribution coefficients and ammonia concentration as well as the effects of various amines on sorption of transition metals indicate that a coordinate bond is formed between the metal ions and the hydroxy groups of the sorbent. The distribution coefficients of silver(I) and cobalt(II), which form strong ammonia complexes in aqueous solutions, decrease with increasing concentration of ammonia already at concentrations exceeding 10 -3 *mol*dm -3 . Cations of zinc, manganese and mercury which form much weaker ammonia complexes do not exhibit any effect of ammonia concentration in the whole range investigated. In the case of sorption of macroamounts of ammonia or amine complexes of silver, the molecular sieve effect plays an important role. The differences in the affinity of hydrated titanium dioxide for ammonia solvates of various transition metal ions can serve as a tool for effective separation of these ions in ammonia solutions. (author) 10 refs.; 4 figs.; 1 tab

Expanding the structural landscape of niclosamide: a high Z ' polymorph, two new solvates and monohydrate H_A

DEFF Research Database (Denmark)

Sovago, Ioana; Bond, Andrew D.

2015-01-01

to be twinned by twofold rotation around that axis. The acetonitrile molecules occupy channels in the structure. A complete structure is provided for niclosamide monohydrate, C13H8Cl2N2O4·H2O, polymorph HA, obtained by Rietveld refinement against laboratory powder X-ray diffraction data. It has been suggested...... that this compound is related to the methanol solvate of niclosamide [Harriss, Wilson & Radosevljevic Evans (2014). Acta Cryst. C70, 758-763], but it is found that the two are not fully isostructural: they contain isostructural two-dimensional layers, but the layers are arranged differently in the two structures....... This suggests that HA may have the potential for polytypism, and features in the Rietveld difference curve indicate that a polytype fully isostructural with the methanol solvate might be present....

Thermodynamic aspects of solubility, solvation and partitioning processes of some sulfonamides

Energy Technology Data Exchange (ETDEWEB)

Perlovich, German L., E-mail: glp@isc-ras.r [Department of Computer-Aided Molecular Design, Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka (Russian Federation); Institute of Solution Chemistry, Russian Academy of Sciences, 153045 Ivanovo (Russian Federation); Ryzhakov, Alex M. [Institute of Solution Chemistry, Russian Academy of Sciences, 153045 Ivanovo (Russian Federation); Strakhova, Nadezda N.; Kazachenko, Vladimir P. [Department of Computer-Aided Molecular Design, Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka (Russian Federation); Schaper, Klaus-Juergen [Research Center Borstel, Leibniz Center for Medicine and Biosciences, D-23845 Borstel (Germany); Raevsky, Oleg A. [Department of Computer-Aided Molecular Design, Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432 Chernogolovka (Russian Federation)

2011-05-15

Research highlights: {yields} The thermodynamic aspects of sublimation processes of some sulfonamides were studied by investigating the temperature dependence of vapor pressure using the transpiration method. {yields} Solubility processes of the compounds in water, phosphate buffer with pH 7.4 and n-octanol were investigated and corresponding thermodynamic functions were calculated as well. {yields} Thermodynamic characteristics of the sulfonamides solvation were evaluated. - Abstract: The thermodynamic aspects of sublimation processes of three sulfonamides with the general structures C{sub 6}H{sub 5}-SO{sub 2}NH-C{sub 6}H{sub 4}-R (R = 4-NO{sub 2}) and 4-NH{sub 2}-C{sub 6}H{sub 4}-SO{sub 2}NH-C{sub 6}H{sub 4}-R (R = 4-NO{sub 2}; 4-CN) were studied by investigating the temperature dependence of vapor pressure using the transpiration method. These data together with those obtained earlier for C{sub 6}H{sub 5}-SO{sub 2}NH-C{sub 6}H{sub 4}-R (R = 4-Cl) and 4-NH{sub 2}-C{sub 6}H{sub 4}-SO{sub 2}NH-C{sub 6}H{sub 4}-R (R = 4-Cl; 4-OMe; 4-C{sub 2}H{sub 5}) were analyzed and compared. A correlation was derived between sublimation Gibbs free energies and the sum of H-bond acceptor factors of the molecules. Solubility processes of the compounds in water, phosphate buffer with pH 7.4 and n-octanol (as phases modeling various drug delivery pathways) were investigated and corresponding thermodynamic functions were calculated as well. Thermodynamic characteristics of the sulfonamides solvation were evaluated. Also in this case a correlation between solubility/solvation Gibbs free energy values and the sum of H-bond acceptor factors was observed. For the sulfonamides with various substituents at para-position the processes of transfer from one solvent (water or buffer) to n-octanol were studied by a diagram method combined with analysis of enthalpic and entropic terms. Distinguishing between enthalpy and entropy, as is possible through the present approach, leads to the insight

Simultaneous ion and neutral evaporation in aqueous nanodrops: experiment, theory, and molecular dynamics simulations.

Science.gov (United States)

Higashi, Hidenori; Tokumi, Takuya; Hogan, Christopher J; Suda, Hiroshi; Seto, Takafumi; Otani, Yoshio

2015-06-28

We use a combination of tandem ion mobility spectrometry (IMS-IMS, with differential mobility analyzers), molecular dynamics (MD) simulations, and analytical models to examine both neutral solvent (H2O) and ion (solvated Na(+)) evaporation from aqueous sodium chloride nanodrops. For experiments, nanodrops were produced via electrospray ionization (ESI) of an aqueous sodium chloride solution. Two nanodrops were examined in MD simulations: a 2500 water molecule nanodrop with 68 Na(+) and 60 Cl(-) ions (an initial net charge of z = +8), and (2) a 1000 water molecule nanodrop with 65 Na(+) and 60 Cl(-) ions (an initial net charge of z = +5). Specifically, we used MD simulations to examine the validity of a model for the neutral evaporation rate incorporating both the Kelvin (surface curvature) and Thomson (electrostatic) influences, while both MD simulations and experimental measurements were compared to predictions of the ion evaporation rate equation of Labowsky et al. [Anal. Chim. Acta, 2000, 406, 105-118]. Within a single fit parameter, we find excellent agreement between simulated and modeled neutral evaporation rates for nanodrops with solute volume fractions below 0.30. Similarly, MD simulation inferred ion evaporation rates are in excellent agreement with predictions based on the Labowsky et al. equation. Measurements of the sizes and charge states of ESI generated NaCl clusters suggest that the charge states of these clusters are governed by ion evaporation, however, ion evaporation appears to have occurred with lower activation energies in experiments than was anticipated based on analytical calculations as well as MD simulations. Several possible reasons for this discrepancy are discussed.

A theoretical study of alkane protonation in HF/SbF5 superacid system

Directory of Open Access Journals (Sweden)

Esteves Pierre M.

2000-01-01

Full Text Available Ab initio calculations for the protonation of the C-H and C-C bonds of methane, ethane, propane and isobutane by a superacid moiety was carried out. For the C-H protonation (H/H exchange the transition state resembles an H-carbonium ion coordinated with the superacid. The activation energy for the H/H exchange was about 16 kcal.mol-1, at B3LYP/6-31++G** + RECP (Sb level, regardless the type of C-H bond being protonated. For the C-C protonation the activation energy depends on the structure of the hydrocarbon and was always higher than the activation energy for C-H protonation, indicating a higher steric demand.

Trimesic acid dimethyl sulfoxide solvate: space group revision

Directory of Open Access Journals (Sweden)

Sylvain Bernès

2008-07-01

Full Text Available The structure of the title solvate, C9H6O6·C2H6OS, was determined 30 years ago [Herbstein, Kapon & Wasserman (1978. Acta Cryst. B34, 1613–1617], with data collected at room temperature, and refined in the space group P21. The present redetermination, based on high-resolution diffraction data, shows that the actual space group is more likely to be P21/m. The crystal structure contains layers of trimesic acid molecules lying on mirror planes. A mirror plane also passes through the S and O atoms of the solvent molecule. The molecules in each layer are interconnected through strong O—H...O hydrogen bonds, forming a two-dimensional supramolecular network within each layer. The donor groups are the hydroxyls of the trimesic acid molecules, while the acceptors are the carbonyl or the sulfoxide O atoms.

Triethyl orthoformate as a new film-forming electrolytes solvent for lithium-ion batteries with graphite anodes

International Nuclear Information System (INIS)

Wang Lishi; Huang Yudai; Jia Dianzeng

2006-01-01

Triethyl orthoformate (TEOF) as a new solvent used in propylene carbonate (PC)-based electrolytes together with graphitic anodes in lithium-ion batteries has been investigated. It can be observed that TEOF was capable of suppressing the co-intercalation of PC solvated lithium-ions into the graphite layer during the first lithiation process and the irreversible discharge capacity of the first cycle is the smallest when using 1.0 M LiPF 6 in PC and TEOF at solvent ratio of 1:1 as the electrolytes. The CV, FTIR, EIS, SEM results show that the PC-based electrolytes containing the solvent TEOF can generate an effective solid electrolytes interphase (SEI) film during the first cycling process, and the film is probably mainly composed of ROCO 2 Li, ROLi, Li 2 CO 3 , etc. The formation of a stable passivating film on the graphite surface is believed to be the reason for the improved cell performance. All these results show that TEOF possesses a promising performance for use as an effective film-forming electrolytes solvent in lithium-ion batteries with graphitic anodes

Synthesis and IR spectroscopic investigation of solvated complexes of dioxomolybdenum (6) with salicylal-S-methyl isothiosemicarbazone

International Nuclear Information System (INIS)

Abramenko, V.L.; Sergienko, V.S.

1996-01-01

The complex of MoO 2 L (H 2 L-S-methylizothiosemicarbazone of salicyl aldehyde) and its seven solvated derivatives MoO 2 LxSolv, have been synthesized, their IR spectroscopic study being conducted. The conclusions on the structure of the complexes studied are confirmed by ata of x-ray diffraction analysis. Refs. 4, tabs. 1

Structural aspects of the solvation shell of lysine and acetylated lysine: A Car-Parrinello and classical molecular dynamics investigation

International Nuclear Information System (INIS)

Carnevale, V.; Raugei, S.

2009-01-01

Lysine acetylation is a post-translational modification, which modulates the affinity of protein-protein and/or protein-DNA complexes. Its crucial role as a switch in signaling pathways highlights the relevance of charged chemical groups in determining the interactions between water and biomolecules. A great effort has been recently devoted to assess the reliability of classical molecular dynamics simulations in describing the solvation properties of charged moieties. In the spirit of these investigations, we performed classical and Car-Parrinello molecular dynamics simulations on lysine and acetylated-lysine in aqueous solution. A comparative analysis between the two computational schemes is presented with a focus on the first solvation shell of the charged groups. An accurate structural analysis unveils subtle, yet statistically significant, differences which are discussed in connection to the significant electronic density charge transfer occurring between the solute and the surrounding water molecules.

Hydroxamic acid interactions with solvated cerium hydroxides in the flotation of monazite and bastnäsite—Experiments and DFT study

Energy Technology Data Exchange (ETDEWEB)

Sarvaramini, A., E-mail: amin.sarvaramini.1@ulaval.ca; Azizi, D., E-mail: dariush.azizi.1@ulaval.ca; Larachi, F., E-mail: faical.larachi@gch.ulaval.ca

2016-11-30

Highlights: • Experimental and DFT studies of hydroxamic acid adsorption on monazite and bastnäsite. • Highest bastnäsite and monazite floatability observed at pH 7–9. • First solvation layer of cerium hydroxides consisted of up to 10 water molecules. • Solvated Ce(OH){sub 2}{sup +} and Ce(OH){sup 2+} cations interact with up to 3 collector anions. • Interaction of zero-charge solvated Ce(OH){sub 3} involves up to 2 collector anions. - Abstract: Density functional theory (DFT) simulations and experiments were performed to clarify the interaction mechanisms between hydroxamic acid collectors and cerium hydroxides during the flotation of bastnäsite and monazite minerals. These minerals showed considerable floatability at moderately alkaline pH which was related to the adsorption of hydroxamic acids on their surfaces as confirmed by vibrational spectroscopic and zeta potential measurements. DFT simulations showed that at moderately alkaline pH, the interactions between solvated Ce(OH){sup 2+} and Ce(OH){sub 2}{sup +} and heptyl-hydroxamic acid (HHA) anions resulted in the formation of, respectively, [Ce(OH)(HHA){sub x}(H{sub 2}O){sub y}]{sup 2−x} (x[y = ] = 1[6],2[3],3[1]) and [Ce(OH){sub 2}(HHA){sub x}(H{sub 2}O){sub y}]{sup 1−x} (x[y = ] = 1[5],2[1],3[0]) complexes. The collector anions were found to interact directly through formation of two covalent bonds between their two polar-head oxygen atoms and cerium in the hydroxide complexes. However, formation of such new bonds resulted in breakage of a few covalent/electrostatic bonds between cerium and water molecules initially present in the first hydration shell of the rare-earth metal cation. Building up in the electric double layer of the semi-soluble minerals, these complexes, and by extension, those from other rare-earth elements belonging to monazite and bastnäsite, are speculated to play a role in the interactions between rare-earth minerals and hydroxamic acid collectors.

Hybrid Perovskite Thin-Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases

KAUST Repository

Munir, Rahim

2016-11-07

Solution-processed hybrid perovskite semiconductors attract a great deal of attention, but little is known about their formation process. The one-step spin-coating process of perovskites is investigated in situ, revealing that thin-film formation is mediated by solid-state precursor solvates and their nature. The stability of these intermediate phases directly impacts the quality and reproducibility of thermally converted perovskite films and their photovoltaic performance.

Hybrid Perovskite Thin-Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases

KAUST Repository

Munir, Rahim; Sheikh, Arif D.; Abdelsamie, Maged; Hu, Hanlin; Yu, Liyang; Zhao, Kui; Kim, Taesoo; El Tall, Omar; Li, Ruipeng; Smilgies, Detlef M.; Amassian, Aram

2016-01-01

Solution-processed hybrid perovskite semiconductors attract a great deal of attention, but little is known about their formation process. The one-step spin-coating process of perovskites is investigated in situ, revealing that thin-film formation is mediated by solid-state precursor solvates and their nature. The stability of these intermediate phases directly impacts the quality and reproducibility of thermally converted perovskite films and their photovoltaic performance.

Crystal structure and packing analysis of nitrofurantoin N,N-dimethylformamide solvate

Energy Technology Data Exchange (ETDEWEB)

Cvetkovski, A., E-mail: aleksandar.cvetkovski@ugd.edu.mk [University Goce Delcev, Faculty of Medical Sciences, Krste Misirkov bb (Macedonia, The Former Yugoslav Republic of); Ferretti, V. [University of Ferrara, Department of Chemical and Pharmaceutical Sciences (Italy)

2016-07-15

The N, N′-dimethylformamide solvated crystal of the drug nitrofurantoin has been prepared and analysed by single-crystal X-ray diffraction. The two co-crystallized molecules, in the 1 : 1 stoichiometric ratio, are linked by a medium/strong N–H···O hydrogen bond (N···O is 2.759 (3) Å) and a weaker C–H···O interaction to form isolated supramolecular adducts, that in turn are packed into the lattice framework mainly through C–H···O hydrogen bonds. Two-dimensional fingerprint plots of Hirshfeld surfaces are used to visualize, analyze and compare intermolecular interactions found in the title compound and in similar structures.

The effect of solvation on the radiation damage rate constants for adenine

DEFF Research Database (Denmark)

Milhøj, Birgitte Olai; Sauer, Stephan P. A.

2016-01-01

in calculations of Gibbs free energies and reaction rates for the reaction between the OH radical and the DNA nucleobase adenine using Density Functional Theory at the ωB97X-D/6-311++G(2df,2pd) level with the Eckart tunneling correction. The solvent, water, has been included through either the implicit...... polarizable continuum model (PCM) or through explicit modelling of micro-solvation by a single water molecule at the site of reaction as well as the combination of both. Scrutiny of the thermodynamics and kinetics of the individual sub-reactions suggests that the qualitative differences introduced...

SO2 Solvation in the 1-Ethyl-3-Methylimidazolium Thiocyanate Ionic Liquid by Incorporation into the Extended Cation-Anion Network.

Science.gov (United States)

Firaha, Dzmitry S; Kavalchuk, Mikhail; Kirchner, Barbara

We have carried out an ab initio molecular dynamics study on the sulfur dioxide (SO 2 ) solvation in 1-ethyl-3-methylimidazolium thiocyanate for which we have observed that both cations and anions play an essential role in the solvation of SO 2 . Whereas, the anions tend to form a thiocyanate- and much less often an isothiocyanate-SO 2 adduct, the cations create a "cage" around SO 2 with those groups of atoms that donate weak interactions like the alkyl hydrogen atoms as well as the heavy atoms of the [Formula: see text]-system. Despite these similarities between the solvation of SO 2 and CO 2 in ionic liquids, an essential difference was observed with respect to the acidic protons. Whereas CO 2 avoids accepting hydrogen bonds form the acidic hydrogen atoms of the cations, SO 2 can from O(SO 2 )-H(cation) hydrogen bonds and thus together with the strong anion-adduct it actively integrates in the hydrogen bond network of this particular ionic liquid. The fact that SO 2 acts in this way was termed a linker effect by us, because the SO 2 can be situated between cation and anion operating as a linker between them. The particular contacts are the H(cation)[Formula: see text]O(SO 2 ) hydrogen bond and a S(anion)-S(SO 2 ) sulfur bridge. Clearly, this observation provides a possible explanation for the question of why the SO 2 solubility in these ionic liquids is so high.

Proton transfer through hydrogen bonds in two-dimensional water layers: A theoretical study based on ab initio and quantum-classical simulations

International Nuclear Information System (INIS)

Bankura, Arindam; Chandra, Amalendu

2015-01-01

The dynamics of proton transfer (PT) through hydrogen bonds in a two-dimensional water layer confined between two graphene sheets at room temperature are investigated through ab initio and quantum-classical simulations. The excess proton is found to be mostly solvated as an Eigen cation where the hydronium ion donates three hydrogen bonds to the neighboring water molecules. In the solvation shell of the hydronium ion, the three coordinated water molecules with two donor hydrogen bonds are found to be properly presolvated to accept a proton. Although no hydrogen bond needs to be broken for transfer of a proton to such presolvated water molecules from the hydronium ion, the PT rate is still found to be not as fast as it is for one-dimensional chains. Here, the PT is slowed down as the probability of finding a water with two donor hydrogen bonds in the solvation shell of the hydronium ion is found to be only 25%-30%. The hydroxide ion is found to be solvated mainly as a complex anion where it accepts four H-bonds through its oxygen atom and the hydrogen atom of the hydroxide ion remains free all the time. Here, the presolvation of the hydroxide ion to accept a proton requires that one of its hydrogen bonds is broken and the proton comes from a neighboring water molecule with two acceptor and one donor hydrogen bonds. The coordination number reduction by breaking of a hydrogen bond is a slow process, and also the population of water molecules with two acceptor and one donor hydrogen bonds is only 20%-25% of the total number of water molecules. All these factors together tend to slow down the hydroxide ion migration rate in two-dimensional water layers compared to that in three-dimensional bulk water

Computational 17O-NMR spectroscopy of organic acids and peracids: comparison of solvation models

International Nuclear Information System (INIS)

Baggioli, Alberto; Castiglione, Franca; Raos, Guido; Crescenzi, Orlando; Field, Martin J.

2013-01-01

We examine several computational strategies for the prediction of the 17 O-NMR shielding constants for a selection of organic acids and peracids in aqueous solution. In particular, we consider water (the solvent and reference for the chemical shifts), hydrogen peroxide, acetic acid, lactic acid and peracetic acid. First of all, we demonstrate that the PBE0 density functional in combination with the 6-311+G(d,p) basis set provides an excellent compromise between computational cost and accuracy in the calculation of the shielding constants. Next, we move on to the problem of the solvent representation. Our results confirm the shortcomings of the Polarizable Continuum Model (PCM) in the description of systems susceptible to strong hydrogen bonding interactions, while at the same time they demonstrate its usefulness within a molecular-continuum approach, whereby PCM is applied to describe the solvation of the solute surrounded by some explicit solvent molecules. We examine different models of the solvation shells, sampling their configurations using both energy minimizations of finite clusters and molecular dynamics simulations of bulk systems. Hybrid molecular dynamics simulations, in which the solute is described at the PM6 semiempirical level and the solvent by the TIP3P model, prove to be a promising sampling method for medium-to-large sized systems. The roles of solvent shell size and structure are also briefly discussed. (authors)

Solvation Dynamics in Different Phases of the Lyotropic Liquid Crystalline System.

Science.gov (United States)

Roy, Bibhisan; Satpathi, Sagar; Gavvala, Krishna; Koninti, Raj Kumar; Hazra, Partha

2015-09-03

Reverse hexagonal (HII) liquid crystalline material based on glycerol monooleate (GMO) is considered as a potential carrier for drugs and other important biomolecules due to its thermotropic phase change and excellent morphology. In this work, the dynamics of encapsulated water, which plays important role in stabilization and formation of reverse hexagonal mesophase, has been investigated by time dependent Stokes shift method using Coumarin-343 as a solvation probe. The formation of the reverse hexagonal mesophase (HII) and transformation to the L2 phase have been monitored using small-angle X-ray scattering and polarized light microscopy experiments. REES studies suggest the existence of different polar regions in both HII and L2 systems. The solvation dynamics study inside the reverse hexagonal (HII) phase reveals the existence of two different types of water molecules exhibiting dynamics on a 120-900 ps time scale. The estimated diffusion coefficients of both types of water molecules obtained from the observed dynamics are in good agreement with the measured diffusion coefficient collected from the NMR study. The calculated activation energy is found to be 2.05 kcal/mol, which is associated with coupled rotational-translational water relaxation dynamics upon the transition from "bound" to "quasi-free" state. The observed ∼2 ns faster dynamics of the L2 phase compared to the HII phase may be associated with both the phase transformation as well as thermotropic effect on the relaxation process. Microviscosities calculated from time-resolved anisotropy studies infer that the interface is almost ∼22 times higher viscous than the central part of the cylinder. Overall, our results reveal the unique dynamical features of water inside the cylinder of reverse hexagonal and inverse micellar phases.

Organic solvation of intercalated cations in V/sub 2/O/sub 5/ xerogels

International Nuclear Information System (INIS)

Lemordant, D.; Bouhaouss, A.; Aldbert, P.; Baffier, N.

1986-01-01

V/sub 2/O/sub 5/ xerogels (V/sub 2/O/sub 5/, 1.6H/sub 2/O) undergo a topotactic reversible exchange reaction at room temperature in organic solvents containing monovalent alkali or divalent (Mn/sup 2+/) cations. Basal spacing are dependent on solvent type and charge-to-radius ratio of guest cations. From the interlayer distances, two solvation stages have been inferred, depending on the nature of the solvent and of the cation, except with Cs/sup +/ for which no intracrystalline swelling by organic solvents is observed

Watching the Solvation of Atoms in Liquids One Solvent Molecule at a Time

Science.gov (United States)

Bragg, Arthur E.; Glover, William J.; Schwartz, Benjamin J.

2010-06-01

We use mixed quantum-classical molecular dynamics simulations and ultrafast transient hole-burning spectroscopy to build a molecular-level picture of the motions of solvent molecules around Na atoms in liquid tetrahydrofuran. We find that even at room temperature, the solvation of Na atoms occurs in discrete steps, with the number of solvent molecules nearest the atom changing one at a time. This explains why the rate of solvent relaxation differs for different initial nonequilibrium states, and reveals how the solvent helps determine the identity of atomic species in liquids.

The molecular mechanism of multi-ion conduction in K{sup +} channels

Energy Technology Data Exchange (ETDEWEB)

Gwan, J.F.

2007-01-19

Steered molecular dynamics (SMD) simulation method is applied to a fully solvated membrane-channel model for studying the ion permeation process in potassium channels. The channel model is based on the crystallographic structure of a prokaryotic K{sup +} channel- the KcsA channel, which is a representative of most known eukaryotic K{sup +} channels. It has long been proposed that the ion transportation in a conventional K{sup +}-channel follows a multi-ion fashion: permeating ions line in a queue in the channel pore and move in a single file through the channel. The conventional view of multi-ion transportation is that the electrostatic repulsion between ions helps to overcome the attraction between ions and the channel pore. In this study, we proposed two SMD simulation schemes, referred to 'the single-ion SMD' simulations and 'the multi-ion SMD' simulations. Concerted movements of a K-W-K sequence in the selectivity filter were observed in the single-ion SMD simulations. The analysis of the concerted movement reveals the molecular mechanism of the multi-ion transportation. It shows that, rather than the long range electrostatic interaction, the short range polar interaction is a more dominant factor in the multi-ion transportation. The polar groups which play a role in the concerted transportation are the water molecules and the backbone carbonyl groups of the selectivity filter. The polar interaction is sensitive to the relative orientation of the polar groups. By changing the orientation of a polar group, the interaction may switch from attractive to repulsive or vice versa. By this means, the energy barrier between binding sites in the selectivity filter can be switched on and off, and therefore the K{sup +} may be able to move to the neighboring binding site without an external driving force. The concerted transportation in the selectivity filter requires a delicate cooperation between K{sup +}, waters, and the backbone carbonyl groups. To

Solvation thermodynamics of phenylalcohols in lamellar phase surfactant dispersions

International Nuclear Information System (INIS)

Martyniak, A.; Scheuermann, R.; Dilger, H.; Tucker, I.M.; Burkert, T.; Hashmi, A.S.K.; Vujosevic', D.; Roduner, E.

2006-01-01

The distribution and the stability of five phenylalcohols in a lamellar phase composed of simple bilayers separated by water at 298 and 348K is explored using avoided-level-crossing muon-spin resonance (ALC-μSR). The dependence of the alignment of the bilayer chains on temperature appears to be a crucial factor determining the phenylalcohol partitioning: increasing order of the surfactant tails leads to expulsion of the solute. Moreover, we observed a systematic trend, the longer the chain the deeper the phenyl group dips into the lipid bilayer. Recent studies have shown that the hydrophobic effect is adequate to describe membrane partitioning of small amphiphilic molecules. The solvation thermodynamic properties ΔG sol , ΔH sol , and ΔS sol which determine the solute transfer from the double layer into water prove that the distribution also strongly depends on shape, chemical nature and different structure of phenylalcohols

Solvation thermodynamics of phenylalcohols in lamellar phase surfactant dispersions

Energy Technology Data Exchange (ETDEWEB)

Martyniak, A. [Institut fuer Physikalische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Scheuermann, R. [Laboratory for muon Spin Spectroscopy, Paul Scherrer Institute, CH-5232 Villigen (Switzerland); Dilger, H. [Institut fuer Physikalische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Tucker, I.M. [Unilever Research and Development, Port Sunlight, Wirral CH63 3JW (United Kingdom); Burkert, T. [Institut fuer Organische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Hashmi, A.S.K. [Institut fuer Organische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Vujosevic' , D. [Institut fuer Physikalische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany); Roduner, E. [Institut fuer Physikalische Chemie, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany)]. E-mail: e.roduner@ipc.uni-stuttgart.de

2006-03-31

The distribution and the stability of five phenylalcohols in a lamellar phase composed of simple bilayers separated by water at 298 and 348K is explored using avoided-level-crossing muon-spin resonance (ALC-{mu}SR). The dependence of the alignment of the bilayer chains on temperature appears to be a crucial factor determining the phenylalcohol partitioning: increasing order of the surfactant tails leads to expulsion of the solute. Moreover, we observed a systematic trend, the longer the chain the deeper the phenyl group dips into the lipid bilayer. Recent studies have shown that the hydrophobic effect is adequate to describe membrane partitioning of small amphiphilic molecules. The solvation thermodynamic properties {delta}G{sub sol}, {delta}H{sub sol}, and {delta}S{sub sol} which determine the solute transfer from the double layer into water prove that the distribution also strongly depends on shape, chemical nature and different structure of phenylalcohols.

Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

International Nuclear Information System (INIS)

Grodkowski, J.; Bobrowski, K.; Mehnert, R.; Brede, O.

1989-01-01

The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl 4 and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN +radical ) and the former to the known carbonium ion of malachite green dye (MG + ). Observation of the consecutive charge transfer via the schemes: DCE +radical → BPh +radical → MGCN +radical and DCE +radical → MGCN +radical → TMPD +radical , allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV MGCN +radical radical cation is located in the ''aniline'' part of the molecule. (author)

Pulse radiolysis of malachite green leucocyanide in alcoholic solvents, the influence of oxygen

International Nuclear Information System (INIS)

Grodkowski, J.; Stuglik, Z.; Wieczorek, G.

1992-01-01

The solutions of malachite green leucocyanide (MGCN) in methanol, n-propanol and 2-propanol were investigated using pulse radiolysis. In the presence of oxygen, MG + -carbonium ions were radiolytically formed in two different time steps. The yield of MG + in the slower process was dependent on oxygen concentration and was proportional to the yield of intermediate MG radicals. The yield of MG was about ten times higher in 2-propanol than in methanol and n-propanol solutions. The reactants responsible for MG oxidation to MG + were RO 2 , hydroxyalkylperoxyl radicals derived from alcohols. The rate constant for MG reaction with RO 2 were estimated as (6.5±1) x 10 8 M -1 s -1 . The molar extinction coefficient of MG was calculated. (author)

Molecular beam studies of reaction dynamics

International Nuclear Information System (INIS)

Lee, Yuan T.

1991-03-01

The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation

Molecular beam studies of reaction dynamics

Energy Technology Data Exchange (ETDEWEB)

Lee, Y.T. [Lawrence Berkeley Laboratory, CA (United States)

1993-12-01

The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation.

Solvation of a Small Metal-Binding Peptide in Room-Temperature Ionic Liquids

Energy Technology Data Exchange (ETDEWEB)

Shim, Youngseon; Jung, Younjoon [Seoul National Univ., Seoul (Korea, Republic of); Kim, Hyung J. [Carnegie Mellon Univ., Pittsburgh (United States)

2012-11-15

Structural properties of a small hexapeptide molecule modeled after metal-binding siderochrome immersed in a room-temperature ionic liquid (RTIL) are studied via molecular dynamics simulations. We consider two different RTILs, each of which is made up of the same cationic species, 1-butyl-3-methylimidazolium (BMI{sup +}), but different anions, hexafluorophosphate (PF{sub 6}{sup -}) and chloride (Cl{sup -}). We investigate how anionic properties such as hydrophobicity/hydrophilicity or hydrogen bonding capability affect the stabilization of the peptide in RTILs. To examine the effect of peptide-RTIL electrostatic interactions on solvation, we also consider a hypothetical solvent BMI{sup 0}Cl{sup 0}, a non-ionic counter-part of BMI{sup +}Cl{sup -}. For reference, we investigate solvation structures in common polar solvents, water and dimethylsulfoxide (DMSO). Comparison of BMI{sup +}Cl{sup -} and BMI{sup 0}Cl{sup 0} shows that electrostatic interactions of the peptide and RTIL play a significant role in the conformational fluctuation of the peptide. For example, strong electrostatic interactions between the two favor an extended conformation of the peptide by reducing its structural fluctuations. The hydrophobicity/hydrophilicity of RTIL anions also exerts a notable influence; specifically, structural fluctuations of the peptide become reduced in more hydrophilic BMI{sup +}Cl{sup -}, compared with those in more hydrophobic BMI{sup +}PF{sub 6}{sup -}. This is ascribed to the good hydrogen-bond accepting power of chloride anions, which enables them to bind strongly to hydroxyl groups of the peptide and to stabilize its structure. Transport properties of the peptide are examined briefly. Translations of the peptide significantly slow down in highly viscous RTILs.

Lieb-Liniger-like model of quantum solvation in CO-{sup 4}He{sub N} clusters

Energy Technology Data Exchange (ETDEWEB)

Farrelly, D. [Departamento de Matemáticas y Computación, Universidad de La Rioja, 26006 Logroño (Spain); Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300 (United States); Iñarrea, M.; Salas, J. P. [Área de Física Aplicada, Universidad de La Rioja, 26006 Logroño (Spain); Lanchares, V. [Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300 (United States)

2016-05-28

Small {sup 4}He clusters doped with various molecules allow for the study of “quantum solvation” as a function of cluster size. A peculiarity of quantum solvation is that, as the number of {sup 4}He atoms is increased from N = 1, the solvent appears to decouple from the molecule which, in turn, appears to undergo free rotation. This is generally taken to signify the onset of “microscopic superfluidity.” Currently, little is known about the quantum mechanics of the decoupling mechanism, mainly because the system is a quantum (N + 1)-body problem in three dimensions which makes computations difficult. Here, a one-dimensional model is studied in which the {sup 4}He atoms are confined to revolve on a ring and encircle a rotating CO molecule. The Lanczos algorithm is used to investigate the eigenvalue spectrum as the number of {sup 4}He atoms is varied. Substantial solvent decoupling is observed for as few as N = 5 {sup 4}He atoms. Examination of the Hamiltonian matrix, which has an almost block diagonal structure, reveals increasingly weak inter-block (solvent-molecule) coupling as the number of {sup 4}He atoms is increased. In the absence of a dopant molecule the system is similar to a Lieb-Liniger (LL) gas and we find a relatively rapid transition to the LL limit as N is increased. In essence, the molecule initially—for very small N—provides a central, if relatively weak, attraction to organize the cluster; as more {sup 4}He atoms are added, the repulsive interactions between the identical bosons start to dominate as the solvation ring (shell) becomes more crowded which causes the molecule to start to decouple. For low N, the molecule pins the atoms in place relative to itself; as N increases the atom-atom repulsion starts to dominate the Hamiltonian and the molecule decouples. We conclude that, while the notion of superfluidity is a useful and correct description of the decoupling process, a molecular viewpoint provides complementary insights into the

Dispersion and Solvation Effects on the Structure and Dynamics of N719 Adsorbed to Anatase Titania (101) Surfaces in Room-Temperature Ionic Liquids: An ab Initio Molecular Simulation Study

KAUST Repository

Byrne, Aaron

2015-12-24

Ab initio, density functional theory (DFT)-based molecular dynamics (MD) has been carried out to investigate the effect of explicit solvation on the dynamical and structural properties of a [bmim][NTf2] room-temperature ionic liquid (RTIL), solvating a N719 sensitizing dye adsorbed onto an anatase titania (101) surface. The effect of explicit dispersion on the properties of this dye-sensitized solar cell (DSC) interface has also been studied. Upon inclusion of dispersion interactions in simulations of the solvated system, the average separation between the cations and anions decreases by 0.6 Å; the mean distance between the cations and the surface decreases by about 0.5 Å; and the layering of the RTIL is significantly altered in the first layer surrounding the dye, with the cation being on average 1.5 Å further from the center of the dye. Inclusion of dispersion effects when a solvent is not explicitly included (to dampen longer-range interactions) can result in unphysical "kinking" of the adsorbed dye\\'s configuration. The inclusion of solvent shifts the HOMO and LUMO levels of the titania surface by +3 eV. At this interface, the interplay between the effects of dispersion and solvation combines in ways that are often subtle, such as enhancement or inhibition of specific vibrational modes. © 2015 American Chemical Society.

Pulse radiolysis study on temperature and pressure dependence of the yield of solvated electron in methanol from room temperature to supercritical condition

International Nuclear Information System (INIS)

Han, Zhenhui; He, Hui; Lin, Mingzhang; Muroya, Yusa; Katsumura, Yosuke

2012-09-01

A new concept of nuclear reactor, supercritical water-cooled reactor (SCWR), has been proposed, which is based on the success of the use of supercritical water (SCW) in fossil fuel power plants for more than three decades. This new concept reactor has advantages of higher thermal conversion efficiency, simplicity in structure, safety, etc, and it has been selected as one of the reactor concepts for the next generation nuclear reactor systems. In these reactors, the same as in boiling water reactors (BWR) and pressurized water reactors (PWR), water is used not only as a coolant but also as a moderator. It is very important to understand the behavior of the radiolysis products of water under the supercritical condition, since the water is exposed to a strong radiation field under very high temperature condition. Usually, in order to predict the concentrations of water decomposition products with carrying out some kinds of computer simulations, knowledge of the temperature and/or pressure dependent G-values (denoting the experimentally measured radiolytic yields) as well as of the rate constants of a set of reactions becomes very important. Therefore, in recent years, two groups from Argonne National Laboratory and The University of Tokyo, simultaneously conducted two projects aimed at obtaining basic data on radiolysis of SCW. However, it is still lack of reliable radiolytic yields of water decomposition products in very high temperature region. As we known, the properties of solvated electrons in polar liquid are very helpful for our understanding how they play a central role in many processes, such as solvation and reducing reactions. The solvated electron can also be used as a probe to determine the dynamic nature of the polar liquid systems. Comparing to water, the primary alcohols have much milder critical points, for example, for water and methanol, the critical temperature and pressure are 374 deg. C and 22.1 MPa and 239.5 deg. C and 8.1 MPa, respectively

The mechanism for enhanced oxidation degradation of dioxin-like PCBs (PCB-77) in the atmosphere by the solvation effect.

Science.gov (United States)

Xin, Mei-Ling; Yang, Jia-Wen; Li, Yu

2017-07-11

The reaction pathways of PCB-77 in the atmosphere with ·OH, O 2 , NO x , and 1 O 2 were inferred based on density functional theory calculations with the 6-31G* basis set. The structures the reactants, transition states, intermediates, and products were optimized. The energy barriers and reaction heats were obtained to determine the energetically favorable reaction pathways. To study the solvation effect, the energy barriers and reaction rates for PCB-77 with different polar and nonpolar solvents (cyclohexane, benzene, carbon tetrachloride, chloroform, acetone, dichloromethane, ethanol, methanol, acetonitrile, dimethylsulfoxide, and water) were calculated. The results showed that ·OH preferentially added to the C5 atom of PCB-77, which has no Cl atom substituent, to generate the intermediate IM5. This intermediate subsequently reacted with O 2 via pathway A to generate IM5a, with an energy barrier of 7.27 kcal/mol and total reaction rate of 8.45 × 10 -8  cm 3 /molecule s. Pathway B involved direct dehydrogenation of IM5 to produce the OH-PCBs intermediate IM5b, with an energy barrier of 28.49 kcal/mol and total reaction rate of 1.15 × 10 -5  cm 3 /molecule s. The most likely degradation pathway of PCB-77 in the atmosphere is pathway A to produce IM5a. The solvation effect results showed that cyclohexane, carbon tetrachloride, and benzene could reduce the reaction energy barrier of pathway A. Among these solvents, the solvation effect of benzene was the largest, and could reduce the total reaction energy barrier by 25%. Cyclohexane, carbon tetrachloride, benzene, dichloromethane, acetone, and ethanol could increase the total reaction rate of pathway A. The increase in the reaction rate of pathway A with benzene was 8%. The effect of solvents on oxidative degradation of PCB-77 in the atmosphere is important. Graphical abstract The reaction pathways of PCB-77 in the atmosphere with •OH, O2, NOx, and 1O2 were inferred based on density functional theory

Using Gas-Phase Guest-Host Chemistry to Probe the Structures of b Ions of Peptides

Science.gov (United States)

Somogyi, Árpád; Harrison, Alex G.; Paizs, Béla

2012-12-01

Middle-sized b n ( n ≥ 5) fragments of protonated peptides undergo selective complex formation with ammonia under experimental conditions typically used to probe hydrogen-deuterium exchange in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Other usual peptide fragments like y, a, a*, etc., and small b n ( n ≤ 4) fragments do not form stable ammonia adducts. We propose that complex formation of b n ions with ammonia is characteristic to macrocyclic isomers of these fragments. Experiments on a protonated cyclic peptide and N-terminal acetylated peptides fully support this hypothesis; the protonated cyclic peptide does form ammonia adducts while linear b n ions of acetylated peptides do not undergo complexation. Density functional theory (DFT) calculations on the proton-bound dimers of all-Ala b 4 , b 5 , and b 7 ions and ammonia indicate that the ionizing proton initially located on the peptide fragment transfers to ammonia upon adduct formation. The ammonium ion is then solvated by N+-H…O H-bonds; this stabilization is much stronger for macrocyclic b n isomers due to the stable cage-like structure formed and entropy effects. The present study demonstrates that gas-phase guest-host chemistry can be used to selectively probe structural features (i.e., macrocyclic or linear) of fragments of protonated peptides. Stable ammonia adducts of b 9 , b 9 -A, and b 9 -2A of A8YA, and b 13 of A20YVFL are observed indicating that even these large b-type ions form macrocyclic structures.

Effect of temperature on solvation behaviour of diclofenac sodium salt in aqueous glycine and L-proline solutions

International Nuclear Information System (INIS)

Ryshetti, Suresh; Gardas, Ramesh L; Tangeda, Savitha Jyostna

2015-01-01

Highlights: • Solvation behaviour of diclofenac drug studied in aqueous solutions. • Density and speed of sound of drug in aq. glycine and L-proline are measured. • Hydrophobic nature of diclofenac sodium salt is studied. • Effect of temperature on solvation of diclofenac sodium salt is analysed. - Abstract: Apparent molar volume (V 2,ϕ ) and apparent molar isentropic compressibility (K s,2,ϕ ) of diclofenac sodium salt (DSS) drug within the concentration range of (0.001 to 0.008) mol · kg −1 in (0.01, 0.03 and 0.05) mol · kg −1 aqueous glycine and L-proline solutions are computed from the experimental density (ρ) and speed of sound (u) values at T = (293.15 to 313.15) K and atmospheric pressure. Derived parameters such as partial molar properties, transfer partial molar properties, hydration numbers and Hepler’s constant are computed from the data of V 2,ϕ and K s,2,ϕ . These parameters have been used to understand the effect of temperature on interactions between DSS drug and aqueous glycine/L-proline solution. Furthermore, the structure making and breaking ability of DSS drug in probed solutions are analysed at experimental conditions

Energetic aspects of diclofenac acid in crystal modifications and in solutions--mechanism of solvation, partitioning and distribution.

Science.gov (United States)

Perlovich, German L; Surov, Artem O; Hansen, Lars Kr; Bauer-Brandl, Annette

2007-05-01

Temperature dependency of saturated vapor pressure and heat capacity for the diclofenac acid (Form II) were measured and thermodynamic functions of sublimation calculated (DeltaG(sub)(298) = 49.3 kJ x mol(-1); DeltaH(sub)(298) = 115.6 +/- 1.3 kJ x mol(-1); DeltaS(sub)(298) = 222 +/- 4 J x mol(-1) x K(-1)). Crystal polymorphic Forms I (P2(1)/c) and II (C2/c) of diclofenac acid have been prepared and characterized by X-ray diffraction experiments. The difference between crystal lattice energies of the two forms were obtained by solution calorimetry: DeltaDeltaH(sol)(I --> II) = 1.6 +/- 0.4 kJ x mol(-1). Temperature dependencies of the solubility in buffers with pH 2.0 and 7.4, n-octanol and n-hexane were measured. The thermodynamic functions of solubility, solvation, and transfer processes were deduced. Specific and non-specific solvation terms were distinguished using the transfer from the "inert" n-hexane to the other solvents. The transfer of diclofenac acid molecules from the buffers to n-octanol (partitioning and distribution) is an entropy driven process. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association.

Accurate calculation of conformational free energy differences in explicit water: the confinement-solvation free energy approach.

Science.gov (United States)

Esque, Jeremy; Cecchini, Marco

2015-04-23

The calculation of the free energy of conformation is key to understanding the function of biomolecules and has attracted significant interest in recent years. Here, we present an improvement of the confinement method that was designed for use in the context of explicit solvent MD simulations. The development involves an additional step in which the solvation free energy of the harmonically restrained conformers is accurately determined by multistage free energy perturbation simulations. As a test-case application, the newly introduced confinement/solvation free energy (CSF) approach was used to compute differences in free energy between conformers of the alanine dipeptide in explicit water. The results are in excellent agreement with reference calculations based on both converged molecular dynamics and umbrella sampling. To illustrate the general applicability of the method, conformational equilibria of met-enkephalin (5 aa) and deca-alanine (10 aa) in solution were also analyzed. In both cases, smoothly converged free-energy results were obtained in agreement with equilibrium sampling or literature calculations. These results demonstrate that the CSF method may provide conformational free-energy differences of biomolecules with small statistical errors (below 0.5 kcal/mol) and at a moderate computational cost even with a full representation of the solvent.

Anisotropy enhanced X-ray scattering from solvated transition metal complexes

DEFF Research Database (Denmark)

Biasin, Elisa; van Driel, Tim B.; Levi, Gianluca

2018-01-01

Time-resolved X-ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X-ray free-electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV-Vis pump laser pulse with the sample......, which induces anisotropic structural changes that can be captured by femtosecond X-ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural...... sensitivity of the time-resolved X-ray scattering experiment. This method is applied on time-resolved X-ray scattering patterns measured upon photoexcitation of a solvated di-platinum complex at an XFEL, and the key parameters involved are explored. It is shown that a combined analysis of the anisotropic...

Generalized linear solvation energy model applied to solute partition coefficients in ionic liquid-supercritical carbon dioxide systems

Czech Academy of Sciences Publication Activity Database

Planeta, Josef; Karásek, Pavel; Hohnová, Barbora; Šťavíková, Lenka; Roth, Michal

2012-01-01

Roč. 1250, SI (2012), s. 54-62 ISSN 0021-9673 R&D Projects: GA ČR(CZ) GAP206/11/0138; GA ČR(CZ) GAP106/12/0522; GA ČR(CZ) GPP503/11/P523 Institutional research plan: CEZ:AV0Z40310501 Keywords : ionic liquid * supercritical carbon dioxide * solvation energy model Subject RIV: BJ - Thermodynamics Impact factor: 4.612, year: 2012

Film Thickness Formation in Nanoscale due to Effects of Elastohydrodynamic, Electrostatic and Surface force of Solvation and Van der Waals

Directory of Open Access Journals (Sweden)

M.F. Abd Al-Samieh

2017-03-01

Full Text Available The mechanism of oil film with a thickness in the nanoscale is discussed in this paper. A polar lubricant of propylene carbonate is used as the intervening liquid between contiguous bodies in concentrated contacts. A pressure caused by the hydrodynamic viscous action in addition to double layer electrostatic force, Van der Waals inter-molecular forces, and solvation pressure due to inter-surface forces is considered in calculating the ultrathin lubricating films. The numerical solution has been carried out, using the Newton-Raphson iteration technique, applied for the convergence of the hydrodynamic pressure. The results show that, at separations beyond about five molecular diameters of the intervening liquid, the formation of a lubricant film thickness is governed by combined effects of viscous action and surface force of an attractive Van der Waals force and a repulsive double layer force. At smaller separations below about five molecular diameters of the intervening liquid, the effect of solvation force is dominant in determining the oil film thickness

Solvation Structure and Thermodynamic Mapping (SSTMap): An Open-Source, Flexible Package for the Analysis of Water in Molecular Dynamics Trajectories.

Science.gov (United States)

Haider, Kamran; Cruz, Anthony; Ramsey, Steven; Gilson, Michael K; Kurtzman, Tom

2018-01-09

We have developed SSTMap, a software package for mapping structural and thermodynamic water properties in molecular dynamics trajectories. The package introduces automated analysis and mapping of local measures of frustration and enhancement of water structure. The thermodynamic calculations are based on Inhomogeneous Fluid Solvation Theory (IST), which is implemented using both site-based and grid-based approaches. The package also extends the applicability of solvation analysis calculations to multiple molecular dynamics (MD) simulation programs by using existing cross-platform tools for parsing MD parameter and trajectory files. SSTMap is implemented in Python and contains both command-line tools and a Python module to facilitate flexibility in setting up calculations and for automated generation of large data sets involving analysis of multiple solutes. Output is generated in formats compatible with popular Python data science packages. This tool will be used by the molecular modeling community for computational analysis of water in problems of biophysical interest such as ligand binding and protein function.

High quality NMR structures: a new force field with implicit water and membrane solvation for Xplor-NIH

Energy Technology Data Exchange (ETDEWEB)

Tian, Ye [Sanford-Burnham-Prebys Medical Discovery Institute (United States); Schwieters, Charles D. [National Institutes of Health, Center for Information Technology (United States); Opella, Stanley J. [University of California San Diego, Department of Chemistry and Biochemistry (United States); Marassi, Francesca M., E-mail: fmarassi@sbmri.org [Sanford-Burnham-Prebys Medical Discovery Institute (United States)

2017-01-15

Structure determination of proteins by NMR is unique in its ability to measure restraints, very accurately, in environments and under conditions that closely mimic those encountered in vivo. For example, advances in solid-state NMR methods enable structure determination of membrane proteins in detergent-free lipid bilayers, and of large soluble proteins prepared by sedimentation, while parallel advances in solution NMR methods and optimization of detergent-free lipid nanodiscs are rapidly pushing the envelope of the size limit for both soluble and membrane proteins. These experimental advantages, however, are partially squandered during structure calculation, because the commonly used force fields are purely repulsive and neglect solvation, Van der Waals forces and electrostatic energy. Here we describe a new force field, and updated energy functions, for protein structure calculations with EEFx implicit solvation, electrostatics, and Van der Waals Lennard-Jones forces, in the widely used program Xplor-NIH. The new force field is based primarily on CHARMM22, facilitating calculations with a wider range of biomolecules. The new EEFx energy function has been rewritten to enable OpenMP parallelism, and optimized to enhance computation efficiency. It implements solvation, electrostatics, and Van der Waals energy terms together, thus ensuring more consistent and efficient computation of the complete nonbonded energy lists. Updates in the related python module allow detailed analysis of the interaction energies and associated parameters. The new force field and energy function work with both soluble proteins and membrane proteins, including those with cofactors or engineered tags, and are very effective in situations where there are sparse experimental restraints. Results obtained for NMR-restrained calculations with a set of five soluble proteins and five membrane proteins show that structures calculated with EEFx have significant improvements in accuracy, precision

Tailoring electrode/electrolyte interfacial properties in flexible supercapacitors by applying pressure

Energy Technology Data Exchange (ETDEWEB)

Masarapu, Charan; Wang, Lian-Ping; Li, Xin; Wei, Bingqing [Department of Mechanical Engineering, University of Delaware, Newark, DE (United States)

2012-05-15

Electrode/electrolyte interfacial properties of flexible supercapacitors assembled with nanostructured activated carbon fabric (ACF) electrodes can be tailored by applying a pressure and tuning electrolyte ion size relative to electrode pore size. Experimental results reveal that increasing pressure between the supercapacitor electrodes can significantly improve capacitive performance. The ratio of solvated ion size in the electrolyte to the pore size on the electrodes determines the minimum pressure necessary to achieve an optimum performance. For a specific electrode material, this minimum pressure for optimum performance is primarily governed by the size of the larger solvated ions (either the anions or cations), and is lower ({proportional_to}689 KPa) when the ratio of the solvated ion size to the pore size is higher than 0.6, and is higher (at least 1379 KPa) when the ratio is lower than 0.6. An analytical model capable of predicting the experimental performance data has been developed. These results together provide a fundamental understanding of pressure dependence of electrode/electrolyte interfacial properties and pave the way for practical applications of flexible supercapacitors. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

The scavenging of the precursors of the solvated electrons fom the positron lifetime spectroscopy and the Doppler broadening of annihilation line shape technique

International Nuclear Information System (INIS)

Abbe, J.C.; Duplatre, G.; Maddock, A.G.; Haessler, A.

1979-01-01

The electron scavenging properties in water of two series of solutes are investigated, using the positron as a probe. For a better interpretation of the data, both the lifetime specroscopy and the Doppler broadening of annihilation line shape technique are used. All solutes inhibit the positronium (Ps) formation, by the scavenging of electron. The first series consists of the halate ions, that should follow the Hunt linear relation between the rate constant for reaction with the solvated electrons, ksub(e - sub(aq)+S) and that for its precursors(s), 1/C 37 . The Ps inhibition constants, k, are 0.14, 1.44 and 3.45M -1 for ClO 3 - , BrO 3 - and IO 3 - respectively. This sequence is quantitatively consistent with that of the respective ksub(e - sub(aq)+S). The second series includes the SeO 4 -- , Te(OH) 6 and BrO 4 - species, and the Ps inhibition constants are 5.62, 10.5 and 14.3 respectively. Theses values are much higher than expected from the ksub(e - sub(aq)+S) constants, on basis of the Hunt relation, in agreement with previous results from pulse radiolysis experiments

Evaluation of Stability of Complexes of Inner Transition Metal Ions with 2-Oxo-1-pyrrolidine Acetamide and Role of Systematic Errors

Directory of Open Access Journals (Sweden)

Sangita Sharma

2011-01-01

Full Text Available BEST FIT models were used to study the complexation of inner transition metal ions like Y(III, La(III, Ce(III, Pr(III, Nd(III, Sm(III, Gd(III, Dy(III and Th(IV with 2-oxo-1-pyrrolidine acetamide at 30 °C in 10%, 20, 30, 40, 50% and 60% v/v dioxane-water mixture at 0.2 M ionic strength. Irving Rossotti titration method was used to get titration data. Calculations were carried out with PKAS and BEST Fortran IV computer programs. The expected species like L, LH+, ML, ML2 and ML(OH3, were obtained with SPEPLOT. Stability of complexes has increased with increasing the dioxane content. The observed change in stability can be explained on the basis of electrostatic effects, non electrostatic effects, solvating power of solvent mixture, interaction between ions and interaction of ions with solvents. Effect of systematic errors like effect of dissolved carbon dioxide, concentration of alkali, concentration of acid, concentration of ligand and concentration of metal have also been explained here.

Linear solvation energy relationships: "rule of thumb" for estimation of variable values

Science.gov (United States)

Hickey, James P.; Passino-Reader, Dora R.

1991-01-01

For the linear solvation energy relationship (LSER), values are listed for each of the variables (Vi/100, π*, &betam, αm) for fundamental organic structures and functional groups. We give the guidelines to estimate LSER variable values quickly for a vast array of possible organic compounds such as those found in the environment. The difficulty in generating these variables has greatly discouraged the application of this quantitative structure-activity relationship (QSAR) method. This paper present the first compilation of molecular functional group values together with a utilitarian set of the LSER variable estimation rules. The availability of these variable values and rules should facilitate widespread application of LSER for hazard evaluation of environmental contaminants.

Radiolysis studies on reactive intermediates. Final report, February 1, 1970-August 31, 1980

International Nuclear Information System (INIS)

Kevan, L.

1980-08-01

Research highlights are briefly reviewed concerning studies of excess and solvated electrons, development of new electron spin resonance methods for maximizing the geometrical information about the surroundings of paramagnetic species in disordered systems, atom and ion solvation, and studies on other reactive intermediates. Titles of 155 research publications and 182 scientific talks presented on these areas are given

Relation between the ion size and pore size for an electric double-layer capacitor.

Science.gov (United States)

Largeot, Celine; Portet, Cristelle; Chmiola, John; Taberna, Pierre-Louis; Gogotsi, Yury; Simon, Patrice

2008-03-05

The research on electrochemical double layer capacitors (EDLC), also known as supercapacitors or ultracapacitors, is quickly expanding because their power delivery performance fills the gap between dielectric capacitors and traditional batteries. However, many fundamental questions, such as the relations between the pore size of carbon electrodes, ion size of the electrolyte, and the capacitance have not yet been fully answered. We show that the pore size leading to the maximum double-layer capacitance of a TiC-derived carbon electrode in a solvent-free ethyl-methylimmidazolium-bis(trifluoro-methane-sulfonyl)imide (EMI-TFSI) ionic liquid is roughly equal to the ion size (approximately 0.7 nm). The capacitance values of TiC-CDC produced at 500 degrees C are more than 160 F/g and 85 F/cm(3) at 60 degrees C, while standard activated carbons with larger pores and a broader pore size distribution present capacitance values lower than 100 F/g and 50 F/cm(3) in ionic liquids. A significant drop in capacitance has been observed in pores that were larger or smaller than the ion size by just an angstrom, suggesting that the pore size must be tuned with sub-angstrom accuracy when selecting a carbon/ion couple. This work suggests a general approach to EDLC design leading to the maximum energy density, which has been now proved for both solvated organic salts and solvent-free liquid electrolytes.

Towards room-temperature performance for lithium-polymer batteries

International Nuclear Information System (INIS)

Kerr, J.B.; Liu, Gao; Curtiss, L.A.; Redfern, Paul C.

2003-01-01

Recent work on molecular simulations of the mechanisms of lithium ion conductance has pointed towards two types of limiting process. One has involved the commonly cited segmental motion while the other is related to energy barriers in the solvation shell of polymeric ether oxygens around the lithium ions. Calculations of the barriers to lithium ion migration have provided important indicators as to the best design of the polymer. The theoretical work has coincided with and guided some recent developments on polymer synthesis for lithium batteries. Structural change of the polymer solvation shell has been pursued by the introduction of trimethylene oxide (TMO) units into the polymer. The conductivity measurements on polymers containing TMO unit are encouraging. The architecture of the polymer networks has been varied upon which the solvating groups are attached and significant improvements in sub-ambient performance are observed as a result. However, the above-ambient temperature performance appears controlled by an Arrhenius process that is not completely consistent with the theoretical calculations described here and may indicate the operation of a different mechanism. The new polymers possess significantly lower T g values in the presence of lithium salts, which indicates weaker binding of the lithium ions by the polymers. These properties provide considerable improvement in the transport properties close to the electrode surfaces resulting in decreased impedances at the surfaces both at lithium metal and in composite electrodes. The greater flexibility of the solvation groups combined with appropriate architecture not only has applications in lithium metal-polymer batteries but also in lithium ion liquid and gel systems as well as in fuel cell electrodes

Interface of the polarizable continuum model of solvation with semi-empirical methods in the GAMESS program.

Directory of Open Access Journals (Sweden)

Casper Steinmann

Full Text Available An interface between semi-empirical methods and the polarized continuum model (PCM of solvation successfully implemented into GAMESS following the approach by Chudinov et al (Chem. Phys. 1992, 160, 41. The interface includes energy gradients and is parallelized. For large molecules such as ubiquitin a reasonable speedup (up to a factor of six is observed for up to 16 cores. The SCF convergence is greatly improved by PCM for proteins compared to the gas phase.

Cation solvation with quantum chemical effects modeled by a size-consistent multi-partitioning quantum mechanics/molecular mechanics method.

Science.gov (United States)

Watanabe, Hiroshi C; Kubillus, Maximilian; Kubař, Tomáš; Stach, Robert; Mizaikoff, Boris; Ishikita, Hiroshi

2017-07-21

In the condensed phase, quantum chemical properties such as many-body effects and intermolecular charge fluctuations are critical determinants of the solvation structure and dynamics. Thus, a quantum mechanical (QM) molecular description is required for both solute and solvent to incorporate these properties. However, it is challenging to conduct molecular dynamics (MD) simulations for condensed systems of sufficient scale when adapting QM potentials. To overcome this problem, we recently developed the size-consistent multi-partitioning (SCMP) quantum mechanics/molecular mechanics (QM/MM) method and realized stable and accurate MD simulations, using the QM potential to a benchmark system. In the present study, as the first application of the SCMP method, we have investigated the structures and dynamics of Na + , K + , and Ca 2+ solutions based on nanosecond-scale sampling, a sampling 100-times longer than that of conventional QM-based samplings. Furthermore, we have evaluated two dynamic properties, the diffusion coefficient and difference spectra, with high statistical certainty. Furthermore the calculation of these properties has not previously been possible within the conventional QM/MM framework. Based on our analysis, we have quantitatively evaluated the quantum chemical solvation effects, which show distinct differences between the cations.

Ions, solutes and solvents, oh my!

Energy Technology Data Exchange (ETDEWEB)

Kemp, Daniel David [Iowa State Univ., Ames, IA (United States)

2009-08-01

Modern methods in ab initio quantum mechanics have become efficient and accurate enough to study many gas-phase systems. However, chemists often work in the solution phase. The presence of solvent molecules has been shown to affect reaction mechanisms1, lower reaction energy barriers2, participate in energy transfer with the solute3 and change the physical properties of the solute4. These effects would be overlooked in simple gas phase calculations. Careful study of specific solvents and solutes must be done in order to fully understand the chemistry of the solution phase. Water is a key solvent in chemical and biological applications. The properties of an individual water molecule (a monomer) and the behavior of thousands of molecules (bulk solution) are well known for many solvents. Much is also understood about aqueous microsolvation (small clusters containing ten water molecules or fewer) and the solvation characteristics when bulk water is chosen to solvate a solute. However, much less is known about how these properties behave as the cluster size transitions from the microsolvated cluster size to the bulk. This thesis will focus on species solvated with water clusters that are large enough to exhibit the properties of the bulk but small enough to consist of fewer than one hundred solvent molecules. New methods to study such systems will also be presented.

Pressure effect on the amide I frequency of the solvated α-helical structure in water

International Nuclear Information System (INIS)

Takekiyo, T; Yoshimura, Y; Shimizu, A; Koizumi, T; Kato, M; Taniguchi, Y

2007-01-01

As a model system of the pressure dependence of the amide I mode of the solvated α-helical structure in a helical peptide, we have calculated the frequency shifts of the amide I modes as a function of the distance between trans-N-methylacetamide (t-NMA) dimer and a water molecule (d C=O···H-O ) by the density-functional theory (DFT) method at the B3LYP/6-31G++(d,p) level. Two amide I frequencies at 1652 and 1700 cm -1 were observed under this calculation. The former is ascribed to the amide I mode forming the intermolecular hydrogen bond (H-bond) between t-NMA and H 2 O in addition to the intermolecular H-bond in the t-NMA dimer. The latter is due to the amide I mode forming only the intermolecular H-bond in the t-NMA dimer. We have found that the amide I frequency at 1652 cm -1 shifts to a lower frequency with decreasing d C=O···H-O ) (i.e., increasing pressure), whereas that at 1700 cm -1 shifts to a higher frequency. The amide I frequency shift of 1652 cm -1 is larger than that of 1700 cm -1 by the intermolecular H-bond. Thus, our results clearly indicate that the pressure-induced amide I frequency shift of the solvated α-helical structure correlates with the change in d C=O···H-O )

Pulse radiolysis of malachite green leucocyanide in alcoholic solvents, the influence of oxygen

Energy Technology Data Exchange (ETDEWEB)

Grodkowski, J; Stuglik, Z; Wieczorek, G [Institute of Nuclear Chemistry and Technology, Warsaw (Poland)

1992-04-01

The solutions of malachite green leucocyanide (MGCN) in methanol, n-propanol and 2-propanol were investigated using pulse radiolysis. In the presence of oxygen, MG{sup +}-carbonium ions were radiolytically formed in two different time steps. The yield of MG{sup +} in the slower process was dependent on oxygen concentration and was proportional to the yield of intermediate MG radicals. The yield of MG was about ten times higher in 2-propanol than in methanol and n-propanol solutions. The reactants responsible for MG oxidation to MG{sup +} were RO{sub 2}, hydroxyalkylperoxyl radicals derived from alcohols. The rate constant for MG reaction with RO{sub 2} were estimated as (6.5{+-}1) x 10{sup 8}M{sup -1}s{sup -1}. The molar extinction coefficient of MG was calculated. (author).

New chiral zwitterionic phosphorus heterocycles: synthesis, structure, properties and application as chiral solvating agents.

Science.gov (United States)

Sheshenev, Andrey E; Boltukhina, Ekaterina V; Grishina, Anastasiya A; Cisařova, Ivana; Lyapkalo, Ilya M; Hii, King Kuok Mimi

2013-06-17

A family of new chiral zwitterionic phosphorus-containing heterocycles (zPHC) have been derived from methylene-bridged bis(imidazolines). These structures were unambiguously determined, including single-crystal XRD analysis for two compounds. The stability, acid/base and electronic properties of these dipolar phosphorus heterocycles were subsequently investigated. zPHCs can be successfully employed as a new class of chiral solvating agents for the enantiodifferentiation of chiral carboxylic and sulfonic acids by NMR spectroscopy. The stoichiometry and binding constants for the donor-acceptor complexes formed were established by NMR titration methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

The physical picturethat emerges is that there is a strong contact ion pair (CIP) and strong to moderate solvent separated ion pair(SSIP) in these solutions. Analysis of local ion clusters shows that ions are dominantly solvated by watermolecules. The 12-6-1 potential model predicts running coordination numbers closest to ...

Continuum model of non-equilibrium solvation and solvent effect on ultra-fast processes

International Nuclear Information System (INIS)

Li Xiangyuan; Fu Kexiang; Zhu Quan

2006-01-01

In the past 50 years, non-equilibrium solvation theory for ultra-fast processes such as electron transfer and light absorption/emission has attracted particular interest. A great deal of research efforts was made in this area and various models which give reasonable qualitative descriptions for such as solvent reorganization energy in electron transfer and spectral shift in solution, were developed within the framework of continuous medium theory. In a series of publications by the authors, we clarified that the expression of the non-equilibrium electrostatic free energy that is at the dominant position of non-equilibrium solvation and serves as the basis of various models, however, was incorrectly formulated. In this work, the authors argue that reversible charging work integration was inappropriately applied in the past to an irreversible path linking the equilibrium or the non-equilibrium state. Because the step from the equilibrium state to the nonequilibrium state is factually thermodynamically irreversible, the conventional expression for non-equilibrium free energy that was deduced in different ways is unreasonable. Here the authors derive the non-equilibrium free energy to a quite different form according to Jackson integral formula. Such a difference throws doubts to the models including the famous Marcus two-sphere model for solvent reorganization energy of electron transfer and the Lippert-Mataga equation for spectral shift. By introducing the concept of 'spring energy' arising from medium polarizations, the energy constitution of the non-equilibrium state is highlighted. For a solute-solvent system, the authors separate the total electrostatic energy into different components: the self-energies of solute charge and polarized charge, the interaction energy between them and the 'spring energy' of the solvent polarization. With detailed reasoning and derivation, our formula for non-equilibrium free energy can be reached through different ways. Based on the

Efficient molecular mechanics simulations of the folding, orientation, and assembly of peptides in lipid bilayers using an implicit atomic solvation model

Science.gov (United States)

Bordner, Andrew J.; Zorman, Barry; Abagyan, Ruben

2011-10-01

Membrane proteins comprise a significant fraction of the proteomes of sequenced organisms and are the targets of approximately half of marketed drugs. However, in spite of their prevalence and biomedical importance, relatively few experimental structures are available due to technical challenges. Computational simulations can potentially address this deficit by providing structural models of membrane proteins. Solvation within the spatially heterogeneous membrane/solvent environment provides a major component of the energetics driving protein folding and association within the membrane. We have developed an implicit solvation model for membranes that is both computationally efficient and accurate enough to enable molecular mechanics predictions for the folding and association of peptides within the membrane. We derived the new atomic solvation model parameters using an unbiased fitting procedure to experimental data and have applied it to diverse problems in order to test its accuracy and to gain insight into membrane protein folding. First, we predicted the positions and orientations of peptides and complexes within the lipid bilayer and compared the simulation results with solid-state NMR structures. Additionally, we performed folding simulations for a series of host-guest peptides with varying propensities to form alpha helices in a hydrophobic environment and compared the structures with experimental measurements. We were also able to successfully predict the structures of amphipathic peptides as well as the structures for dimeric complexes of short hexapeptides that have experimentally characterized propensities to form beta sheets within the membrane. Finally, we compared calculated relative transfer energies with data from experiments measuring the effects of mutations on the free energies of translocon-mediated insertion of proteins into lipid bilayers and of combined folding and membrane insertion of a beta barrel protein.

Concentration Fluctuations and Capacitive Response in Dense Ionic Solutions.

Science.gov (United States)

Uralcan, Betul; Aksay, Ilhan A; Debenedetti, Pablo G; Limmer, David T

2016-07-07

We use molecular dynamics simulations in a constant potential ensemble to study the effects of solution composition on the electrochemical response of a double layer capacitor. We find that the capacitance first increases with ion concentration following its expected ideal solution behavior but decreases upon approaching a pure ionic liquid in agreement with recent experimental observations. The nonmonotonic behavior of the capacitance as a function of ion concentration results from the competition between the independent motion of solvated ions in the dilute regime and solvation fluctuations in the concentrated regime. Mirroring the capacitance, we find that the characteristic decay length of charge density correlations away from the electrode is also nonmonotonic. The correlation length first decreases with ion concentration as a result of better electrostatic screening but increases with ion concentration as a result of enhanced steric interactions. When charge fluctuations induced by correlated ion-solvent fluctuations are large relative to those induced by the pure ionic liquid, such capacitive behavior is expected to be generic.

LINEAR SOLVATION ENERGY RELATIONSHIPS FOR CHARACTERIZATION OF MLC SYSTEMS WITH SODIUM DODECYL SULPHATE MOBILE PHASES MODIFIED BY ALIPHATIC ALCOHOLS OR CARBOXYLIC ACIDS

NARCIS (Netherlands)

Markov, Vadym V.; Boichenko, Alexander P.; Loginova, Lidia P.

2012-01-01

The Linear Solvation Energy Relationships (LSER) have been successfully used for the modeling of partition and retention of the set of test compounds in different systems. The properties of micellar chromatographic systems with the mobile phases on the basis of sodium dodecylsulphate modified (ODS)

Solid polymer electrolyte lithium batteries

Science.gov (United States)

Alamgir, Mohamed; Abraham, Kuzhikalail M.

1993-01-01

This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

Effects of compatibility of polymer binders with solvate ionic liquid electrolytes on discharge and charge reactions of lithium-sulfur batteries

Science.gov (United States)

Nakazawa, Toshitada; Ikoma, Ai; Kido, Ryosuke; Ueno, Kazuhide; Dokko, Kaoru; Watanabe, Masayoshi

2016-03-01

Electrochemical reactions in Li-S cells with a solvate ionic liquid (SIL) electrolyte composed of tetraglyme (G4) and Li[TFSA] (TFSA: bis(trifluoromethanesulfonyl)amide) are studied. The sulfur cathode (S cathode) comprises sulfur, carbon powder, and a polymer binder. Poly(ethylene oxide) (PEO) and poly(vinyl alcohol) (PVA-x) with different degrees of saponification (x%) are used as binders to prepare the composite cathodes. For the Li-S cell containing PEO binder, lithium polysulfides (Li2Sm, 2 ≤ m ≤ 8), reaction intermediates of the S cathode, dissolve into the electrolyte, and Li2Sm acts as a redox shuttle in the Li-S cell. In contrast, in the Li-S cell with PVA-x binder, the dissolution of Li2Sm is suppressed, leading to high columbic efficiencies during charge-discharge cycles. The compatibility of the PVA-x binder with the SIL electrolyte changes depending on the degree of saponification. Decreasing the degree of saponification leads to increased electrolyte uptake by the PVA-x binder, increasing the charge and discharge capacities of Li-S cell. The rate capability of Li-S cell is also enhanced by the partial swelling of the PVA-x binder. The enhanced performance of Li-S cell containing PVA-x is attributed to the lowering of resistance of Li+ ion transport in the composite cathode.

Pharmaceutical solvates, hydrates and amorphous forms: A special emphasis on cocrystals.

Science.gov (United States)

Healy, Anne Marie; Worku, Zelalem Ayenew; Kumar, Dinesh; Madi, Atif M

2017-08-01

Active pharmaceutical ingredients (APIs) may exist in various solid forms, which can lead to differences in the intermolecular interactions, affecting the internal energy and enthalpy, and the degree of disorder, affecting the entropy. Differences in solid forms often lead to differences in thermodynamic parameters and physicochemical properties for example solubility, dissolution rate, stability and mechanical properties of APIs and excipients. Hence, solid forms of APIs play a vital role in drug discovery and development in the context of optimization of bioavailability, filing intellectual property rights and developing suitable manufacturing methods. In this review, the fundamental characteristics and trends observed for pharmaceutical hydrates, solvates and amorphous forms are presented, with special emphasis, due to their relative abundance, on pharmaceutical hydrates with single and two-component (i.e. cocrystal) host molecules. Copyright © 2017 Elsevier B.V. All rights reserved.

Cryogenic ion chemistry and spectroscopy.

Science.gov (United States)

Wolk, Arron B; Leavitt, Christopher M; Garand, Etienne; Johnson, Mark A

2014-01-21

stereoselectively catalyze bromination of biaryl substrates. This procedure directly reveals the particular H-bond donor and acceptor groups that enforce the folded structure of the bare ion as well as provide contact points for noncovalent interaction with substrates. We then show how photochemical hole-burning involving only vibrational excitations can be used in a double-resonance mode to systematically disentangle overlapping spectra that arise when several conformers of a dipeptide are prepared in the ion source. Finally, we highlight our ability to systematically capture reaction intermediates and spectroscopically characterize their structures. Through this method, we can identify the pathway for water-network-mediated, proton-coupled transformation of nitrosonium, NO(+) to HONO, a key reaction controlling the cations present in the ionosphere. Through this work, we reveal the critical role played by water molecules occupying the second solvation shell around the ion, where they stabilize the emergent product ion in a fashion reminiscent of the solvent coordinate responsible for the barrier to charge transfer in solution. Looking to the future, we predict that the capture and characterization of fleeting intermediate complexes in the homogeneous catalytic activation of small molecules like water, alkanes, and CO2 is a likely avenue rich with opportunity.

Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

Science.gov (United States)

Duncan, Michael

2006-03-01

Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

A Density Functional Theory Evaluation of Hydrophobic Solvation: Ne, Ar and Kr in a 50-Water Cluster. Implications for the Hydrophobic Effect.

Science.gov (United States)

Kobko, Nadya; Marianski, Mateusz; Asensio, Amparo; Wieczorek, Robert; Dannenberg, J J

2012-06-15

The physical explanation for the hydrophobic effect has been the subject of disagreement. Physical organic chemists tend to use a explanation related to pressure, while many biochemists prefer an explanation that involves decreased entropy of the aqueous solvent. We present DFT calculations at the B3LYP/6-31G(d,p) and X3LYP/6-31G(d,p) levels on the solvation of three noble gases (Ne, Ar, and Kr) in clusters of 50 waters. Vibrational analyses show no substantial decreases in the vibrational entropies of the waters in any of the three clusters. The observed positive free energies of transfer from the gas phase or from nonpolar solvents to water appear to be due to the work needed to make a suitable hole in the aqueous solvent. We distinguish between hydrophobic solvations (explicitly studied here) and the hydrophobic effect that occurs when a solute (or transition state) can decrease its volume through conformational change (which is not possible for the noble gases).

Long-range dipolar order and dispersion forces in polar liquids

Science.gov (United States)

Besford, Quinn Alexander; Christofferson, Andrew Joseph; Liu, Maoyuan; Yarovsky, Irene

2017-11-01

Complex solvation phenomena, such as specific ion effects, occur in polar liquids. Interpretation of these effects in terms of structure and dispersion forces will lead to a greater understanding of solvation. Herein, using molecular dynamics, we probe the structure of polar liquids through specific dipolar pair correlation functions that contribute to the potential of mean force that is "felt" between thermally rotating dipole moments. It is shown that unique dipolar order exists at separations at least up to 20 Å for all liquids studied. When the structural order is compared with a dipolar dispersion force that arises from local co-operative enhancement of dipole moments, a strong agreement is found. Lifshitz theory of dispersion forces was compared with the structural order, where the theory is validated for all liquids that do not have significant local dipole correlations. For liquids that do have significant local dipole correlations, specifically liquid water, Lifshitz theory underestimates the dispersion force by a factor of 5-10, demonstrating that the force that leads to the increased structure in liquid water is missed by Lifshitz theory of van der Waals forces. We apply similar correlation functions to an ionic aqueous system, where long-range order between water's dipole moment and a single chloride ion is found to exist at 20 Å of separation, revealing a long-range perturbation of water's structure by an ion. Furthermore, we found that waters within the 1st, 2nd, and 3rd solvation shells of a chloride ion exhibit significantly enhanced dipolar interactions, particularly with waters at larger distances of separation. Our results provide a link between structures, dispersion forces, and specific ion effects, which may lead to a more robust understanding of solvation.

Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Murugesan, Vijayakumar; Han, Kee Sung; Hu, Jianzhi; Mueller, Karl T.

2017-03-19

Electrolytes help harness the energy from electrochemical processes by serving as solvents and transport media for redox-active ions. Molecular-level interactions between ionic solutes and solvent molecules – commonly referred to as solvation phenomena – give rise to many functional properties of electrolytes such as ionic conductivity, viscosity, and stability. It is critical to understand the evolution of solvation phenomena as a function of competing counterions and solvent mixtures to predict and design the optimal electrolyte for a target application. Probing oxygen environments is of great interest as oxygens are located at strategic molecular sites in battery solvents and are directly involved in inter- and intramolecular solvation interactions. NMR signals from 17O nuclei in battery electrolytes offer nondestructive bulk measurements of isotropic shielding, electric field gradient tensors, and transverse and longitudinal relaxation rates, which are excellent means for probing structure, bonding, and dynamics of both solute and solvent molecules. This article describes the use of 17O NMR spectroscopy in probing the solvation structures of various electrolyte systems ranging from transition metal ions in aqueous solution to lithium cations in organic solvent mixtures.

Effects of electrostatic interactions on electron transfer reactions

International Nuclear Information System (INIS)

Hickel, B.

1987-01-01

The fast reactions of electron transfer are studied by pulse radiolysis. This technique allows the creation in about 10 -8 second radicals and radical ions with high redox potentials. For solvated electrons electrostatic interaction on the kinetics of reactions limited by diffusion is described by Debye's equation when ion mobility is known. Deviation from theory can occur in ion pairs formation. This is evidenced experimentally for anions by cation complexation with a cryptate. Relatively slow reactions are more sensitive to electrostatic interactions than limited by diffusion. If ion pairs are not formed kinetics constant depends on dielectric constant of solvent and reaction radius. Experimentally is studied the effect of electrostatic interaction on the rate constants of solvated electrons with anions and cations in water-ethanol mixtures where the dielectric constant change from 80 to 25 at room temperature. 17 refs

NMR Study of Solvation Effect on Geometry of Proton-Bound Homodimers of Increasing Size

KAUST Repository

Gurinov, Andrei A.

2017-10-24

Hydrogen bond geometries in the proton-bound homodimers of quinoline and acridine derivatives in an aprotic polar solution have been experimentally studied using 1H NMR at 120 K. The reported results show that increase of the dielec-tric permittivity of the medium results in contraction of the N…N distance. The degree of contraction depends on the homodimer\\'s size and its substituent-specific solvation features. Neither of these effects can be reproduced using conven-tional implicit solvent models employed in computational studies. In general, the N…N distance in the homodimers of pyridine, quinoline, and acridine derivatives decreases in the sequence gas phase > solid state > polar solvent.

NMR Study of Solvation Effect on Geometry of Proton-Bound Homodimers of Increasing Size

KAUST Repository

Gurinov, Andrei A.; Denisov, Gleb S.; Borissova, Alexandra O.; Goloveshkin, Alexander S.; Greindl, Julian; Limbach, Hans-Heinrich; Shenderovich, Ilya G.

2017-01-01

Hydrogen bond geometries in the proton-bound homodimers of quinoline and acridine derivatives in an aprotic polar solution have been experimentally studied using 1H NMR at 120 K. The reported results show that increase of the dielec-tric permittivity of the medium results in contraction of the N…N distance. The degree of contraction depends on the homodimer's size and its substituent-specific solvation features. Neither of these effects can be reproduced using conven-tional implicit solvent models employed in computational studies. In general, the N…N distance in the homodimers of pyridine, quinoline, and acridine derivatives decreases in the sequence gas phase > solid state > polar solvent.

Effects of solvation on partition and dimerization of benzoic acid in mixed solvent systems.

Science.gov (United States)

Yamada, H; Yajima, K; Wada, H; Nakagawa, G

1995-06-01

The partition of benzoic acid between 0.1M perchloric acid solution and two kinds of mixed solvents has been carried out at 25 degrees C. The partition and dimerization constants of benzoic acid have been determined in the 1-octanol-benzene and 2-octanone-benzene systems. In both the mixed solvent systems, with increasing content of 1-octanol and 2-octanone in each mixed solvent, the partition constant of benzoic acid has been found to increase, and the dimerization constant of benzoic acid in each organic phase to decrease. These phenomena are attributable to solvation of monomeric benzoic acid by 1-octanol and 2-octanone molecules in each mixed solvent.

The spectroscopy and structure of some lanthanide chlorides in amide solutions

International Nuclear Information System (INIS)

Legendziewicz, J.; Bukietynska, K; Jezowsky-Trzebiatowska, B.

1974-01-01

The absorption spectra of Pr, Nd, Ho, and Er anhydrous and hydrated chlorides in formamide, methyl-, dimethyl-, and diethylformamide solutions have been investigated in the range of 8000 - 4200 cm -1 . By the Judd-Oefelt method of intensity analysis and by calculating the nepheloauxetic effect, the first coordination sphere of lanthanide ions and the approximate symmetry of amide solvates of anhydrous and hydrated lanthanide chlorides were determined. A difference between symmetry and coordination numbers for light and heavy lanthanide solvates has been found. Some considerations regarding the structure of lanthanide solvates and structure of amide molecules have been made. (B.T.)

DFT study of the interaction between DOTA chelator and competitive alkali metal ions.

Science.gov (United States)

Frimpong, E; Skelton, A A; Honarparvar, B

2017-09-01

1, 4, 7, 10-tetraazacyclododecane-1, 4, 7, 10-tetracetic acid (DOTA) is an important chelator for radiolabeling of pharmaceuticals. The ability of alkali metals found in the body to complex with DOTA and compete with radio metal ions can alter the radiolabeling process. Non-covalent interactions between DOTA complexed with alkali metals Li + , Na + , K + and Rb + , are investigated with density functional theory using B3LYP and ωB97XD functionals. Conformational possibilities of DOTA were explored with a varying number of carboxylic pendant arms of DOTA in close proximity to the ions. It is found that the case in which four arms of DOTA are interacting with ions is more stable than other conformations. The objective of this study is to explore the electronic structure properties upon complexation of alkali metals Li + Na + , K + and Rb + with a DOTA chelator. Interaction energies, relaxation energies, entropies, Gibbs free energies and enthalpies show that the stability of DOTA, complexed with alkali metals decreases down the group of the periodic table. Implicit water solvation affects the complexation of DOTA-ions leading to decreases in the stability of the complexes. NBO analysis through the natural population charges and the second order perturbation theory, revealed a charge transfer between DOTA and alkali metals. Conceptual DFT-based properties such as HOMO/LUMO energies, ΔE HOMO-LUMO and chemical hardness and softness indicated a decrease in the chemical stability of DOTA-alkali metal complexes down the alkali metal series. This study serves as a guide to researchers in the field of organometallic chelators, particularly, radiopharmaceuticals in finding the efficient optimal match between chelators and various metal ions. Copyright © 2017 Elsevier Inc. All rights reserved.

Rate constants for some electrophilic reactions of benzyl, benzhydryl, and trityl cations in solution

International Nuclear Information System (INIS)

Ujdak, R.J.; Jones, R.L.; Dorfman, L.M.

1976-01-01

Absolute rate constants have been determined by the pulse radiolysis technique for several electrophilic reactions of the benzyl, the benzhydryl, and the trityl cation in 1,2-dichloroethane solution. The rate constants for the reactions of these carbonium ions with chloride ion, with bromide ion, and with iodide ion are all very nearly the same, namely 6 x 10 10 M -1 s -1 at 24 0 C. The values very likely represent the diffusion controlled limit for the ion combination reactions. The rate constants for the reactions with triethylamine, tri-n-propylamine, and tri-n-butylamine range from 2.0 x 10 9 to 7 x 10 6 M -1 s -1 at 24 0 C. With increasing phenyl substitution, the decreasing trend in the magnitude of the rate constant is consistent with the combined electronic and steric effects. With increasing size of the amine, the decrease in the value of the rate constant seems to indicate that the steric effect predominates. The values of the rate constants for reactions of benzyl and benzhydryl cation with methanol, ethanol, and 2-propanol indicate the following. The rate constant is higher for reaction with the alcohol dimer in solution than with alcohol monomer. The rate constants for reaction with alcohol monomer have values of 1 x 10 8 M -1 s -1 or lower

Zero-Gap Alkaline Water Electrolysis Using Ion-Solvating Polymer Electrolyte Membranes at Reduced KOH Concentrations

DEFF Research Database (Denmark)

Kraglund, Mikkel Rykær; Aili, David; Jankova Atanasova, Katja

2016-01-01

Membranes based on poly(2,2'-(m-phenylene)-5,5-bibenzimidazole) (m-PBI) can dissolve large amounts of aqueous KOH to give electrolyte systems with ion conductivity in a practically useful range. The conductivity of the membrane strongly depends on the concentration of the aqueous KOH phase......, reaching about 10-1 S cm-1 or higher in 15-25 wt% KOH. Herein, m-PBI membranes are systematically characterized with respect to performance and short-term stability as electrolyte in a zero-gap alkaline water electrolyzer at different KOH concentrations. Using plain uncatalyzed nickel foam electrodes......, the cell based on m-PBI outperforms the cell based on the commercially available state-of-the-art diaphragm and reaches a current density of 1500 mA cm-2 at 2.4 V in 20 wt% KOH at 80°C. The cell performance remained stable during two days of operation, though post analysis of the membrane using size...

Protonic charge defect structures in floating water bridges observed as Zundel and Eigen solvation arrangements

Science.gov (United States)

Teschke, Omar; de Castro, Jose Roberto; Valente Filho, Juracyr Ferraz; Soares, David Mendez

2017-10-01

Protonic arrangements were detected in water bridge structures using confocal Raman microscopy, and the spectra show two formed structures. The measured Raman spectra were modified using the voltage applied to the bridge structure, which changed the proportion of these two species. Initially, for a 6.3 kV applied voltage, there was a measurable increase in the bridge current above the Ohmic contribution and the observed Raman spectrum of this new injected specie corresponded to the computed spectrum for the Zundel protonic arrangement. As the voltage further increases a contribution from the Eigen proton solvation specie is added to the measured spectrum.

Effect of ionic liquid on the solvation behavior of nonaqueous N,N′-salicylidenephenylediamine Schiff base (Salophen) solutions at 298.15 K

International Nuclear Information System (INIS)

Shekaari, Hemayat; Elhami-Kalvanagh, Rasoul; Bezaatpour, Abolfazl

2013-01-01

Highlights: • Salophen schiff base and ionic liquid, [BMIm]Br were synthesized. • Thermodynamic properties of Salophen + [BMIm]Br + organic solvents were measured. • The calculated parameters were used to interpretation of the solute–solvent interactions. • The results show that the predominant interactions are nonpolar–nonpolar interactions. • Solubility of Salophen increase with increasing of [BMIm]Br concentrations. -- Abstract: Thermodynamic properties of N,N′-salicylidenephenylediamine Schiff base (Salophen) in the solutions of ionic liquid, 1-butyl-3-methylimidazolium bromide ([BMIm]Br) + organic solvents (N,N-dimethylacetamide DMA, and dimethylsulfoxide DMSO) have been measured at 298.15 K. The measured density and viscosity values have been used to calculate apparent molar volumes, V ϕ , standard partial molar volumes, V ϕ 0 , standard partial molar volumes of transfer, Δ tr V ϕ 0 , viscosity B-coefficients, and solvation numbers, B/V ϕ 0 , for the solutions being studied. All of these parameters were used to interpret the solute–solvent interactions and solvation process occurring between ionic liquid and Salophen

A chiral aluminum solvating agent (CASA) for 1H NMR chiral analysis of alcohols at low temperature.

Science.gov (United States)

Seo, Min-Seob; Jang, Sumin; Kim, Hyunwoo

2018-03-16

A chiral aluminum solvating agent (CASA) was demonstrated to be a general and efficient reagent for 1H NMR chiral analysis of alcohols. The sodium salt of the CASA (CASA-Na) showed a complete baseline peak separation of the hydroxyl group for various chiral alcohols including primary, secondary, and tertiary alcohols with alkyl and aryl substituents in CD3CN. Due to the weak intermolecular interaction, 1H NMR measurement at low temperature (-40 to 10 °C) was required.

Quantum chemical approach for condensed-phase thermochemistry (V): Development of rigid-body type harmonic solvation model

Science.gov (United States)

Tarumi, Moto; Nakai, Hiromi

2018-05-01

This letter proposes an approximate treatment of the harmonic solvation model (HSM) assuming the solute to be a rigid body (RB-HSM). The HSM method can appropriately estimate the Gibbs free energy for condensed phases even where an ideal gas model used by standard quantum chemical programs fails. The RB-HSM method eliminates calculations for intra-molecular vibrations in order to reduce the computational costs. Numerical assessments indicated that the RB-HSM method can evaluate entropies and internal energies with the same accuracy as the HSM method but with lower calculation costs.

An analysis of 3D solvation structure in biomolecules: application to coiled coil serine and bacteriorhodopsin.

Science.gov (United States)

Hirano, Kenji; Yokogawa, Daisuke; Sato, Hirofumi; Sakaki, Shigeyoshi

2010-06-17

Three-dimensional (3D) solvation structure around coiled coil serine (Coil-Ser) and inner 3D hydration structure in bacteriorhodopsin (bR) were studied using a recently developed method named multicenter molecular Ornstein-Zernike equation (MC-MOZ) theory. In addition, a procedure for analyzing the 3D solvent distribution was proposed. The method enables us to calculate the coordination number of solvent water as well as the strength of hydrogen bonding between the water molecule and the protein. The results for Coil-Ser and bR showed very good agreement with the experimental observations.

Ultrafast electron dynamics at alkali/ice structures adsorbed on a metal surface

International Nuclear Information System (INIS)

Meyer, Michael

2011-01-01

The goal of this work is to study the interaction between excess electrons in water ice structures adsorbed on metal surfaces and other charged or neutral species, like alkali ions, or chemically reactive molecules, like chlorofluorocarbons (CFC), respectively. The excess electrons in the ice can interact with the ions directly or indirectly via the hydrogen bonded water molecules. In both cases the presence of the alkali influences the population, localization, and lifetime of electronic states of excess electrons in the ice adlayer. These properties are of great relevance when considering the highly reactive character of the excess electrons, which can mediate chemical reactions by dissociative electron attachment (DEA). The influence of alkali adsorption on electron solvation and transfer dynamics in ice structures is investigated for two types of adsorption configurations using femtosecond time-resolved two-photon photoelectron spectroscopy. In the first system alkali atoms are coadsorbed on top of a wetting amorphous ice film adsorbed on Cu(111). At temperatures between 60 and 100 K alkali adsorption leads to the formation of positively charged alkali ions at the ice/vacuum interface. The interaction between the alkali ions at the surface and the dipole moments of the surrounding water molecules results in a reorientation of the water molecules. As a consequence new electron trapping sites, i.e. at local potential minima, are formed. Photoinjection of excess electrons into these alkali-ion covered amorphous ice layers, results in the trapping of a solvated electron at an alkali-ion/water complex. In contrast to solvation in pure amorphous ice films, where the electrons are located in the bulk of the ice layer, solvated electrons at alkali-ion/water complexes are located at the ice/vacuum interface. They exhibit lifetimes of several picoseconds and show a fast energetic stabilization. With ongoing solvation, i.e. pump-probe time delay, the electron transfer is

Anomalous or regular capacitance? The influence of pore size dispersity on double-layer formation

Science.gov (United States)

Jäckel, N.; Rodner, M.; Schreiber, A.; Jeongwook, J.; Zeiger, M.; Aslan, M.; Weingarth, D.; Presser, V.

2016-09-01

The energy storage mechanism of electric double-layer capacitors is governed by ion electrosorption at the electrode surface. This process requires high surface area electrodes, typically highly porous carbons. In common organic electrolytes, bare ion sizes are below one nanometer but they are larger when we consider their solvation shell. In contrast, ionic liquid electrolytes are free of solvent molecules, but cation-anion coordination requires special consideration. By matching pore size and ion size, two seemingly conflicting views have emerged: either an increase in specific capacitance with smaller pore size or a constant capacitance contribution of all micro- and mesopores. In our work, we revisit this issue by using a comprehensive set of electrochemical data and a pore size incremental analysis to identify the influence of certain ranges in the pore size distribution to the ion electrosorption capacity. We see a difference in solvation of ions in organic electrolytes depending on the applied voltage and a cation-anion interaction of ionic liquids in nanometer sized pores.

Radiolysis studies on reactive intermediates

International Nuclear Information System (INIS)

Kevan, L.

1977-11-01

A more quantitative characterization of the structure and reaction mechanism of solvated electrons produced by high energy chemistry was developed. Neutral atoms may undergo solvation in polar media to cause significant geometrical rearrangement. The geometrical arrangement of six OH bond oriented water molecules around a localized electron is the preferred geometry in frozen aqueous systems even at low solute ion concentration. The energy level structure of electrons in polar aqueous and alcoholic glasses was systematized from a comparison of photoconductivity and optical spectra. Experimental and theoretical evidence on electron solvation was evaluated to suggest the dominance of first solvation shell orientation in the solvation process. A laser photolysis study as a function of temperature suggests that electron solvation in ethanol glass occurs by a hindered molecular reorientation mechanism. In mixed polar and nonpolar glassy matrices it was shown that the electron is first solvated in the nonpolar matrix and is later transformed to a more stable species surrounded by the polar molecules. It was found that the spin lattice relaxation of solvated electrons is dominated by a new mechanism characteristic of disordered matrices which involves relaxation by tunneling modes in the matrix. The noninteracting spin packet model of electron spin resonance lines was shown to apply to solvated electrons in deuterated matrices but not in protiated matrices. A new type of recombination fluorescence experiment was devised which allows easy distinction between tunnelling and diffusive recombination mechanisms between solvate electrons and cations. Several theoretical studies have helped to delimit the applicability of an electron tunneling mechanism to solvated electron reactions. Electron spin echospectrometry was used to demonstrate that silver atoms undergo dramatic solvation and desolvation changes in frozen aqueous systems

Theoretical-experimental study of the solvation enthalpy of acetone in dilute aqueous solution

International Nuclear Information System (INIS)

Arroyo, S. Tolosa; Martin, J.A. Sanson; Garcia, A. Hidalgo

2005-01-01

The present paper describes molecular dynamics simulations of aqueous solutions at infinite dilution with acetone as solute. Lennard-Jones with electrostatic term (12-6-1 potentials) were employed to describe the solute-solvent interactions. The Morokuma decomposition scheme of ab initio interaction energies at the SCF level and the ESIE charges on the solute atoms were used to reproduce the exchange and Coulomb electrostatic contributions of the solute-water interaction potential. Some extensions, such as including the dispersion component evaluated at MP2 level, were added to the traditional calculation procedures in order to improve the results of the solvation enthalpy. The results obtained with the EX-DIS-ES model were compared with the experimental calorimetry values, the observed agreement being acceptable

Solvents effects on electrochemical characteristics of graphite fluoride-lithium batteries

Energy Technology Data Exchange (ETDEWEB)

Nobuatsu, W.; Hidekazu, T.; Rika, H.; Tsuyoshi, N.

1982-11-01

A study was made of the electrochemical characteristics of graphite fluoride-lithium batteries in various non-aqueous solvents. Two types of graphite fluorides (C/sub 2/F) /SUB n/ and (CF) /SUB n/ were used as cathode materials. The discharge characteristics of graphite fluorides were better in dimethylsulfoxide, ..gamma..-butyrolactone, propylene carbonate and sulfolane in that order. The relation between electrod potential of graphite fluoride and solvation energy of lithium ion with each solvent indicates that solvated lithium ion is intercalated into graphite fluoride layers by the electrode reaction. Both the difference in the overpotentials and in the rates of OCV recovery among these solvents further supports the proposed reaction mechanism.

Nonequilibrium quantum solvation with a time-dependent Onsager cavity

Science.gov (United States)

Kirchberg, H.; Nalbach, P.; Thorwart, M.

2018-04-01

We formulate a theory of nonequilibrium quantum solvation in which parameters of the solvent are explicitly depending on time. We assume in a simplest approach a spherical molecular Onsager cavity with a time-dependent radius. We analyze the relaxation properties of a test molecular point dipole in a dielectric solvent and consider two cases: (i) a shrinking Onsager sphere and (ii) a breathing Onsager sphere. Due to the time-dependent solvent, the frequency-dependent response function of the dipole becomes time-dependent. For a shrinking Onsager sphere, the dipole relaxation is in general enhanced. This is reflected in a temporally increasing linewidth of the absorptive part of the response. Furthermore, the effective frequency-dependent response function shows two peaks in the absorptive part which are symmetrically shifted around the eigenfrequency. By contrast, a breathing sphere reduces damping as compared to the static sphere. Interestingly, we find a non-monotonous dependence of the relaxation rate on the breathing rate and a resonant suppression of damping when both rates are comparable. Moreover, the linewidth of the absorptive part of the response function is strongly reduced for times when the breathing sphere reaches its maximal extension.

The reactivity of allyl and propargyl alcohols with solvated electrons: temperature and solvent effects

International Nuclear Information System (INIS)

Afanassiev, A.M.; Okazaki, K.; Freeman, G.R.

1979-01-01

The rate constants K 1 for the reaction of solvated electrons with allyl alcohol in a number of hydroxylic solvents differ by up to two orders of magnitude and decrease in the order tert-butyl alcohol > 2-propanol > l-propanol approximately ethanol > methanol approximately ethylene glycol > water. In methanol and ethylene glycol the rate constants (7 x 10 7 M -1 s -1 at 298 K) and activation energies (16 kJ/mol) are equal, in spite of a 32-fold difference in solvent viscosity (0.54 and 17.3 cP, respectively) and 3-fold difference in its activation energy (11 and 32 kJ/mol, respectively). The reaction in tert-butyl alcohol is nearly diffusion controlled and has a high activation energy that is characteristic of transport in that liquid (E 1 = 31 kJ/mol, E sub(eta) = 39 kJ/mol). The activation energies in the other alcohols are all 16 kJ/mol, and it is 14 kJ/mol in water. They do not correlate with transport properties. The solvent effect is connected primarily with the entropy of activation. The rate constants correlate with the solvated electron trap depth. When the electron affinity of the scavenger is small, a favorable configuration of solvent molecules about the electron/scavenger encounter pair is required for the electron jump to take place. The behavior of the rate parameters for propargyl alcohol is similar to that for allyl alcohol, but k 1 , A 1 , and E 1 are larger for the former. The ratio k(propargyl)/k(allyl) at 298 K equals 10.5 in water and decreases through the series, reaching 1.3 in tert-butyl alcohol. Rate parameters for several other scavengers are also reported. (author)

A Liquid Inorganic Electrolyte Showing an Unusually High Lithium Ion Transference Number: A Concentrated Solution of LiAlCl4 in Sulfur Dioxide

Directory of Open Access Journals (Sweden)

Martin Winter

2013-08-01

Full Text Available We report on studies of an inorganic electrolyte: LiAlCl4 in liquid sulfur dioxide. Concentrated solutions show a very high conductivity when compared with typical electrolytes for lithium ion batteries that are based on organic solvents. Our investigations include conductivity measurements and measurements of transference numbers via nuclear magnetic resonance (NMR and by a classical direct method, Hittorf’s method. For the use of Hittorf’s method, it is necessary to measure the concentration of the electrolyte in a selected cell compartment before and after electrochemical polarization very precisely. This task was finally performed by potentiometric titration after hydrolysis of the salt. The Haven ratio was determined to estimate the association behavior of this very concentrated electrolyte solution. The measured unusually high transference number of the lithium cation of the studied most concentrated solution, a molten solvate LiAlCl4 × 1.6SO2, makes this electrolyte a promising alternative for lithium ion cells with high power ability.

Effects of functional group substitution on electron spectra and solvation dynamics in a family of ionic liquids

International Nuclear Information System (INIS)

Wishart, James F.; Lall-Ramnarine, Sharon I.; Raju, Ravinder; Scumpia, Alexander; Bellevue, Sherly; Ragbir, Revans; Engel, Robert

2005-01-01

Ionic liquids containing ether-, alcohol- and alkyl-functionalized quaternary ammonium dications were studied by pulse radiolysis. Spectra on nanosecond timescales revealed that solvation of the excess electron is particularly slow in the case of the alcohol-derivatized ionic liquids. The blue shift of the electron spectrum to the customary 650 nm peak takes 25-40 ns at 21 deg. C. Comparison with the relaxation dynamics observed in viscous 1,2,6-trihydroxyhexane reveals the hindering effect of the ionic liquid lattice on hydroxypropyl side chain reorientation

Enthalpies of solvation of ethylene oxide oligomers CH{sub 3}O(CH{sub 2}CH{sub 2}O){sub n}CH{sub 3} (n = 1 to 4) in different H-bonding solvents: Methanol, chloroform, and water. Group contribution method as applied to the polar oligomers

Energy Technology Data Exchange (ETDEWEB)

Barannikov, Vladimir P., E-mail: vpb@isc-ras.ru [Institute of Solution Chemistry, Russian Academy of Sciences, Academicheskaya Str. 1, Ivanovo 153045 (Russian Federation); Guseynov, Sabir S.; Vyugin, Anatoliy I. [Institute of Solution Chemistry, Russian Academy of Sciences, Academicheskaya Str. 1, Ivanovo 153045 (Russian Federation)

2011-12-15

Highlights: > Solvation enthalpy is found for ethylene oxide oligomers in chloroform and methanol. > Coefficients of solute-solute interaction are determined for oligomers in methanol. > Enthalpies of hydrogen bonding of oligomers with chloroform and water are estimated. > Additivity scheme is developed for describing enthalpies of solvation of oligomers. - Abstract: The enthalpies of solution and solvation of ethylene oxide oligomers CH{sub 3}O(CH{sub 2}CH{sub 2}O){sub n}CH{sub 3} (n = 1 to 4) in methanol and chloroform have been determined from calorimetric measurements at T = 298.15 K. The enthalpic coefficients of pairwise solute-solute interaction for methanol solutions have been calculated. The enthalpic characteristics of the oligomers in methanol, chloroform, water and tetrachloromethane have been compared. The hydrogen bonding of the oligomers with chloroform and water molecules is exhibited in the values of solvation enthalpy and coefficient of solute-solute interaction. This effect is not observed for methanol solvent. The thermochemical data evidence an existence of multi-centred hydrogen bonds in associates of polyethers with the solvent molecules. Enthalpies of hydrogen bonding of the oligomers with chloroform and water have been estimated. The additivity scheme has been developed to describe the enthalpies of solvation of ethylene oxide oligomers, unbranched monoethers and n-alkanes in chloroform, methanol, water, and tetrachloromethane. The correction parameters for contribution of repeated polar groups and correction term for methoxy-compounds have been introduced. The obtained group contributions permit to describe the enthalpies of solvation of unbranched monoethers and ethylene oxide oligomers in the solvents with standard deviation up to 0.6 kJ . mol{sup -1}. The values of group contributions and corrections are strongly influenced by solvent properties.

Excess Volumes of Mixing of Cl – and Br – with Na + and K + at ...

African Journals Online (AJOL)

Data are dependent on the nature of the common ion and do not support the cross square rule (CSR). The deviation from the CSR increased with increasing ionic strength and is considered to arise from the appreciable contribution of triplet interactions and preferential solvation of the ions and ion-clusters in the mixed ...

Cluster Formation of Polyphilic Molecules Solvated in a DPPC Bilayer

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Xiang-Yang Guo

2017-10-01

Full Text Available We analyse the initial stages of cluster formation of polyphilic additive molecules which are solvated in a dipalmitoylphosphatidylcholine (DPPC lipid bilayer. Our polyphilic molecules comprise an aromatic (trans-bilayer core domain with (out-of-bilayer glycerol terminations, complemented with a fluorophilic and an alkyl side chain, both of which are confined within the aliphatic segment of the bilayer. Large-scale molecular dynamics simulations (1 μ s total duration of a set of six of such polyphilic additives reveal the initial steps towards supramolecular aggregation induced by the specific philicity properties of the molecules. For our intermediate system size of six polyphiles, the transient but recurrent formation of a trimer is observed on a characteristic timescale of about 100 ns. The alkane/perfluoroalkane side chains show a very distinct conformational distribution inside the bilayer thanks to their different philicity, despite their identical anchoring in the trans-bilayer segment of the polyphile. The diffusive mobility of the polyphilic additives is about the same as that of the surrounding lipids, although it crosses both bilayer leaflets and tends to self-associate.

Structure and reaction of electrolytic solution. Denkaishitsu yoeki no kozo to hanno

Energy Technology Data Exchange (ETDEWEB)

Otaki, H. (Okazaki National Research Inst., Aichi (Japan))

1990-07-05

An electrolytic solution has been recognized as an ion transporting system since the oldest time in the history of electrochemistry, and the chemistry related thereto forms the most basic field of electrochemistry. In this article, the progress of chemistry concerning electrolytic solutions since M. Faraday is briefly stated, and in view of very scanty structural knowledge available on other solutions in comparison with the structure of water on which extensive studies have been made, the respective structures of such non-aqueous solutions as the mixed solvent of N,N-dimethylformamide (DMF)-acetonitrile (AN) and the mixed solvent of dimethylsulfoxide (DMSO)-2,2,2-triphloroethanol (TFE) are studied. In addition, concerning the solvation when ions exist in such a non-aqueous solvent mixed system, the selective solvation of Cu {sup 2+} ions in the DMF-AN and Cu {sup 2+} as well as Cl {sup {minus}} ions in the DMSO-TFE is respectively explained, and the solvent effect, etc. of Cu {sup 2+} ions and Cl {sup {minus}} ions on the complex forming reaction are discussed. 17 refs., 8 figs., 2 tabs.

The SAMPL5 challenge for embedded-cluster integral equation theory: solvation free energies, aqueous p$K_a$, and cyclohexane–water log D

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Tielker, Nicolas; Heil, Jochen; Kloss, Thomas; Ehrhart, Sebastian; Güssregen, Stefan; Schmidt, K. Friedemann; Kast, Stefan M.

2016-01-01

We predict cyclohexane–water distribution coefficients (log D7.4) for drug-like molecules taken from the SAMPL5 blind prediction challenge by the “embedded cluster reference interaction site model” (EC-RISM) integral equation theory. This task involves the coupled problem of predicting both partition coefficients (log P) of neutral species between the solvents and aqueous acidity constants (pKa) in order to account for a change of protonation states. The first issue is addressed by calibrating an EC-RISM-based model for solvation free energies derived from the “Minnesota Solvation Database” (MNSOL) for both water and cyclohexane utilizing a correction based on the partial molar volume, yielding a root mean square error (RMSE) of 2.4 kcal mol−1 for water and 0.8–0.9 kcal mol−1 for cyclohexane depending on the parametrization. The second one is treated by employing on one hand an empirical pKa model (MoKa) and, on the other hand, an EC-RISM-derived regression of published acidity constants (RMSE...

A simple model for solvation in mixed solvents. Applications to the stabilization and destabilization of macromolecular structures.

Science.gov (United States)

Schellman, J A

1990-08-31

The properties of a simple model for solvation in mixed solvents are explored in this paper. The model is based on the supposition that solvent replacement is a simple one-for-one substitution reaction at macromolecular sites which are independent of one another. This leads to a new form for the binding polynomial in which all terms are associated with ligand interchange rather than ligand addition. The principal solvent acts as one of the ligands. Thermodynamic analysis then shows that thermodynamic binding (i.e., selective interaction) depends on the properties of K'-1, whereas stoichiometric binding (site occupation) depends on K'. K' is a 'practical' interchange equilibrium constant given by (f3/f1)K, where K is the true equilibrium constant for the interchange of components 3 and 1 on the site and f3 and f4 denote their respective activity coefficients on the mole fraction scale. Values of K' less than unity lead to negative selective interaction. It is selective interaction and not occupation number which determines the thermodynamic effects of solvation. When K' greater than 100 on the mole fraction scale or K' greater than 2 on the molality scale (in water), the differences between stoichiometric binding and selective interaction become less than 1%. The theory of this paper is therefore necessary only for very weak binding constants. When K'-1 is small, large concentrations of the added solvent component are required to produce a thermodynamic effect. Under these circumstances the isotherms for the selective interaction and for the excess (or transfer) free energy are strongly dependent on the behavior of the activity coefficients of both solvent components. Two classes of behavior are described depending on whether the components display positive or negative deviations from Raoult's law. Examples which are discussed are aqueous solutions of urea and guanidinium chloride for positive deviations and of sucrose and glucose for negative deviations

Untitled

Indian Academy of Sciences (India)

counter ion tends to be solvated and mobile in the polymer phase, imparting it a property of ion exchange membrane. Here we briefly summarize the influence of anion on properties and electrochemical behaviour of polyaniline and polypyrrole. Keywords. Anion; polyaniline; processibility; intractable; protonation. 1.

Ab initio joint density-functional theory of solvated electrodes, with model and explicit solvation

Science.gov (United States)

Arias, Tomas

2015-03-01

the electrochemical context and how it is needed for realistic description of solvated electrode systems [], and how simple ``implicit'' polarized continuum methods fail radically in this context. Finally, we shall present a series of results relevant to battery, supercapacitor, and solar-fuel systems, one of which has led to a recent invention disclosure for improving battery cycle lifetimes. Supported as a part of the Energy Materials Center at Cornell, an Energy Frontier Research Center funded by DOE/BES (award de-sc0001086) and by the New York State Division of Science, Technology and Innovation (NYSTAR, award 60923).

The solvation reaction field for a hydrogen atom in a dielectric continuum

International Nuclear Information System (INIS)

Chipman, D.M.

1996-01-01

A reaction field exists even for a nonpolar solute embedded in a spherical cavity within a surrounding homogeneous dielectric continuum. This arises from the tail of the electronic wave function that penetrates beyond the cavity boundary into the dielectric region. This effect, which is neglected or treated only in cursory fashion in most reaction field implementations, is examined in detail for the simple case of a ground state hydrogen atom, where very accurate solutions of the relevant equations can be obtained. Properties considered include the penetration of the electron outside the cavity, the electronic density at the nucleus, the electron binding energy, the electrostatic free energy of solvation, the polarizability, and the vertical 1s→2p excitation energy. Also, the effect of the common approximation of neglecting the volume polarization and treating only the surface polarization contribution to the reaction field is critically evaluated. copyright 1996 American Institute of Physics

Solvated electron: criticism of a suggested correlation of chemical potential with optical absorption energy

International Nuclear Information System (INIS)

Farhataziz, M.

1984-01-01

A recent theoretical treatment of the absorption spectrum of the solvated electron, e - sub(s), maintains that rigorously μ 0 >= -0.75 Esub(av), which gives empirical relationship, μ 0 >= -(0.93 +- 0.02)Esub(max). For e - sub(s) in a particular solvent at a temperature and pressure, μ 0 , Esub(av) and Esub(max) are standard chemical potential, average energy of the absorption spectrum and the energy at the absorption maximum respectively. The temperature and pressure effects on the absorption spectrum of e - sub(s) in water and liquid ammonia do not support the equality sign in the above cited relationships. The implications of inequality expressed above are discussed for e - sub(s) in water and liquid ammonia. (author)

A non-solvated form of [(Z-O-methyl-N-(2-methylphenylthiocarbamato-κS](triphenylphosphane-κPgold(I: crystal structure and Hirshfeld surface analysis

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Chien Ing Yeo

2016-10-01

Full Text Available The title compound, [Au(C9H10NOS(C18H15P], features a near linear P—Au—S arrangement defined by phosphane P and thiolate S atoms with the minor distortion from the ideal [P—Au—S is 177.61 (2°] being traced in part to the close intramolecular approach of an O atom [Au...O = 3.040 (2 Å]. The packing features supramolecular layers lying parallel to (011 sustained by a combination of C—H...π and π–π [inter-centroid distance = 3.8033 (17 Å] interactions. The molecular structure and packing are compared with those determined for a previously reported hemi-methanol solvate [Kuan et al. (2008. CrystEngComm, 10, 548–564]. Relatively minor differences are noted in the conformations of the rings in the Au-containing molecules. A Hirshfeld surface analysis confirms the similarity in the packing with the most notable differences relating to the formation of C—H...S contacts between the constituents of the solvate.

Radiation and Photochemistry Section annual report, October 1990--September 1991

International Nuclear Information System (INIS)

1991-12-01

This report describes the radiation chemistry and photochemistry of reactive intermediates in the condensed phase. The section on the chemistry of ions treats condensed-phase reactions of radical cations, radical cations in zeolite matrices, high energy chemistry, ions and excited states in radiolysis, and photochemistry of the polymer imaging systems. The section on the role of solvent in chemical reactivity describes a study of atomic hydrogen and deuterium in water radiolysis, solvated electron thermodynamics and transport properties, solvent relaxation dynamics, and solvation of an excess electron in an aqueous solution of LiCl. A separate section outlines activities at the 20-MeV linac and the 3-MeV Van de Graaff accelerator

Structural and dynamical properties of solvated electrons; a study of kinetic spectroscopy using pulse radiolysis

International Nuclear Information System (INIS)

Huis, C. van

1977-01-01

In this thesis the pulse radiolysis experiments of hexamethyl-phosphortriamide (HMPA), propanol-1, 3-methylpentane and mixtures of propanol-1 and 3-methylpentane are reported. In the pulse radiolysis of HMPA, carried out at room temperature, the high yield of esub(s) - (G=2) and the very high wavelength of the maximum absorption (max= 2200 nm) in the esub(s) - absorption spectrum are explained by considering the aprotic nature and the molecular structure of this compound. In the experiment with propanol-1 (temperature range 93deg-123degK) a temporal shift to lower wavelengths in the time range of 10 s-10 ms is observed. In further experiments biphenyl was used as electron scavenger. It was concluded that after the electron pulse the following sequence of events takes place: 1) electron redistribution in times shorter than 1 s; 2) dipole reorientation during 10 s-10 ms; 3) recombination of a part of the solvated electrons; 4) a reaction of the solvated electrons with the neighbouring propanol-1 molecules. In the experiments with 3-methylpentane at 103deg-113degK an esub(s) - absorption band with third order decay kinetics was observed. This is attributed to geminate recombination. The activation energy of the recombination process was 0.4 eV. The experiments with mixtures of propanol-1 and 3-methylpentane were carried out at 103degK. At low propanol-1 concentrations the build-up at 500 nm obeys first order kinetics, whereas at high concentrations this build-up can be split up into three first order components, as was measured in pure propanol-1. The half-lives of the three components were in the ratio of 1:10:100. In the last chapter theoretical models for the electron redistribution and the matric relaxation are discussed and compared with the experiments

Association of ionic liquids in solution: a combined dielectric and conductivity study of [bmim][Cl] in water and in acetonitrile.

Science.gov (United States)

Bešter-Rogač, Marija; Stoppa, Alexander; Hunger, Johannes; Hefter, Glenn; Buchner, Richard

2011-10-21

Ion association of the ionic liquid [bmim][Cl] in acetonitrile and in water was studied by dielectric spectroscopy for salt concentrations c ≤ 1.3 M at 298.15 K and by measurement of molar electrical conductivities, Λ, of dilute solutions (c ≤ 0.006 M) in the temperature range 273.15 ≲ T/K ≤ 313.15. Whilst acetonitrile solutions of [bmim][Cl] exhibit moderate ion pairing, with an association constant of K°(A) ≈ 60 M(-1) and increasing with temperature, [bmim][Cl] is only weakly associated in water (K°(A) ≈ 6 M(-1)) and ion pairing decreases with rising temperature. Only contact ion pairs were detected in both solvents. Standard-state enthalpy, entropy and heat capacity changes of ion association were derived, as well as the activation enthalpy of charge transport and the limiting conductivity of the cation, λ(∞) ([bmim](+)). These data, in conjunction with effective solvation numbers obtained from the dielectric spectra, suggest that the solvation of [bmim](+) is much weaker in water than in acetonitrile. This journal is © the Owner Societies 2011

Hydration structure of Ti(III) and Cr(III): Monte Carlo simulation ...

African Journals Online (AJOL)

Classical Monte Carlo simulations were performed to investigate the solvation structures of Ti(III) and Cr(III) ions in water with only ion-water pair interaction potential and by including three-body correction terms. The hydration structures were evaluated in terms of radial distribution functions, coordination numbers and ...

Excess Volumes of Mixing of Cl– and Br– with Na+ and K+ at 308.15 ...

African Journals Online (AJOL)

NJD

cross square rule (CSR). The deviation from the CSR increased with increasing ionic strength and is considered to arise from the appreciable contribution of triplet interactions and preferential solvation of the ions and ion-clusters in the mixed solvent system. KEYWORDS. Excess volumes of mixing, Friedman model, Pitzer ...

Probing the role of interfacial waters in protein-DNA recognition using a hybrid implicit/explicit solvation model

Science.gov (United States)

Li, Shen; Bradley, Philip

2013-01-01

When proteins bind to their DNA target sites, ordered water molecules are often present at the protein-DNA interface bridging protein and DNA through hydrogen bonds. What is the role of these ordered interfacial waters? Are they important determinants of the specificity of DNA sequence recognition, or do they act in binding in a primarily non-specific manner, by improving packing of the interface, shielding unfavorable electrostatic interactions, and solvating unsatisfied polar groups that are inaccessible to bulk solvent? When modeling details of structure and binding preferences, can fully implicit solvent models be fruitfully applied to protein-DNA interfaces, or must the individualistic properties of these interfacial waters be accounted for? To address these questions, we have developed a hybrid implicit/explicit solvation model that specifically accounts for the locations and orientations of small numbers of DNA-bound water molecules while treating the majority of the solvent implicitly. Comparing the performance of this model to its fully implicit counterpart, we find that explicit treatment of interfacial waters results in a modest but significant improvement in protein sidechain placement and DNA sequence recovery. Base-by-base comparison of the performance of the two models highlights DNA sequence positions whose recognition may be dependent on interfacial water. Our study offers large-scale statistical evidence for the role of ordered water for protein DNA recognition, together with detailed examination of several well-characterized systems. In addition, our approach provides a template for modeling explicit water molecules at interfaces that should be extensible to other systems. PMID:23444044

The isobutylene-isobutane alkylation process in liquid HF revisited.

Science.gov (United States)

Esteves, P M; Araújo, C L; Horta, B A C; Alvarez, L J; Zicovich-Wilson, C M; Ramírez-Solís, A

2005-07-07

Details on the mechanism of HF catalyzed isobutylene-isobutane alkylation were investigated. On the basis of available experimental data and high-level quantum chemical calculations, a detailed reaction mechanism is proposed taking into account solvation effects of the medium. On the basis of our computational results, we explain why the density of the liquid media and stirring rates are the most important parameters to achieve maximum yield of alkylate, in agreement with experimental findings. The ab initio Car-Parrinello molecular dynamics calculations show that isobutylene is irreversibly protonated in the liquid HF medium at higher densities, leading to the ion pair formation, which is shown to be a minimum on the potential energy surface after optimization using periodic boundary conditions. The HF medium solvates preferentially the fluoride anion, which is found as solvated [FHF](-) or solvated F(-.)(HF)(3). On the other hand, the tert-butyl cation is weakly solvated, where the closest HF molecules appear at a distance of about 2.9 Angstrom with the fluorine termination of an HF chain.

Quantum Chemical Benchmarking, Validation, and Prediction of Acidity Constants for Substituted Pyridinium Ions and Pyridinyl Radicals.

Science.gov (United States)

Keith, John A; Carter, Emily A

2012-09-11

Sensibly modeling (photo)electrocatalytic reactions involving proton and electron transfer with computational quantum chemistry requires accurate descriptions of protonated, deprotonated, and radical species in solution. Procedures to do this are generally nontrivial, especially in cases that involve radical anions that are unstable in the gas phase. Recently, pyridinium and the corresponding reduced neutral radical have been postulated as key catalysts in the reduction of CO2 to methanol. To assess practical methodologies to describe the acid/base chemistry of these species, we employed density functional theory (DFT) in tandem with implicit solvation models to calculate acidity constants for 22 substituted pyridinium cations and their corresponding pyridinyl radicals in water solvent. We first benchmarked our calculations against experimental pyridinium deprotonation energies in both gas and aqueous phases. DFT with hybrid exchange-correlation functionals provide chemical accuracy for gas-phase data and allow absolute prediction of experimental pKas with unsigned errors under 1 pKa unit. The accuracy of this economical pKa calculation approach was further verified by benchmarking against highly accurate (but very expensive) CCSD(T)-F12 calculations. We compare the relative importance and sensitivity of these energies to selection of solvation model, solvation energy definitions, implicit solvation cavity definition, basis sets, electron densities, model geometries, and mixed implicit/explicit models. After determining the most accurate model to reproduce experimentally-known pKas from first principles, we apply the same approach to predict pKas for radical pyridinyl species that have been proposed relevant under electrochemical conditions. This work provides considerable insight into the pitfalls using continuum solvation models, particularly when used for radical species.

Constants and thermodynamics of the acid-base equilibria of triglycine in water-ethanol solutions containing sodium perchlorate at 298 K

Science.gov (United States)

Pham Tkhi, L.; Usacheva, T. R.; Tukumova, N. V.; Koryshev, N. E.; Khrenova, T. M.; Sharnin, V. A.

2016-02-01

The acid-base equilibrium constants for glycyl-glycyl-glycine (triglycine) in water-ethanol solvents containing 0.0, 0.1, 0.3, and 0.5 mole fractions of ethanol are determined by potentiometric titration at 298.15 K and an ionic strength of 0.1, maintained with sodium perchlorate. It is established that an increase in the ethanol content in the solvent reduces the dissociation constant of the carboxyl group of triglycine (increases p K 1) and increases the dissociation constant of the amino group of triglycine (decreases p K 2). It is noted that the weakening of the acidic properties of a triglycinium ion upon an increase of the ethanol content in the solvent is due to the attenuation of the solvation shell of the zwitterionic form of triglycine, and to the increased solvation of triglycinium ions. It is concluded that the acid strength of triglycine increases along with a rise in the EtOH content in the solvent, due to the desolvation of the tripeptide zwitterion and the enhanced solvation of protons.

Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

Energy Technology Data Exchange (ETDEWEB)

Grodkowski, J; Bobrowski, K; Mehnert, R; Brede, O

1989-01-01

The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl/sub 4/ and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN/sup +radical/) and the former to the known carbonium ion of malachite green dye (MG/sup +/). Observation of the consecutive charge transfer via the schemes: DCE/sup +radical/ -> BPh/sup +radical/ -> MGCN/sup +radical/ and DCE/sup +radical/ -> MGCN/sup +radical/ -> TMPD/sup +radical/, allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV < Ip/sub MGCN/ < 8.27 eV. Presented results and literature data suggest that positive charge in MGCN/sup +radical/ radical cation is located in the ''aniline'' part of the molecule. (author).

Determination of the active site and mechanism for alkene isomerization in Cu(II) exchnaged Y-type zeolite

Energy Technology Data Exchange (ETDEWEB)

John, C S; Leach, H F

1977-01-01

An ESR study of 1-butene isomerization at 315/sup 0/-375/sup 0/C, 3,3-dimethyl-1-butene isomerization to 2,3-dimethyl-1- and -2-butene at 293/sup 0/K, and deuterium redistribution in 3,3-dideuteriopropene at 363/sup 0/-396/sup 0/K showed the presence of two copper(II) species in different environments, which reacted with the olefins at different rates. Although activation energies for the three reactions differed and only dideuteriopropene showed an induction period, a similar mechanism is proposed in all cases, involving preliminary reduction of copper(II), with the rates of reduction and isomerization differing from olefin to olefin. Apparently, the active site for the isomerization is a Broensted acid generated by the reduction, and the isomerization follows an associative (proton addition-elimination) mechanism with a carbonium ion intermediate. Spectra, graphs, diagram, and 12 references.

Resonant Pump-dump Quantum Control of Solvated Dye Molecules with Phase Jumps

Science.gov (United States)

Konar, Arkaprabha; Lozovoy, Vadim; Dantus, Marcos

2014-03-01

Quantum coherent control of two photon and multiphoton excitation processes in atomic and condensed phase systems employing phase jumps has been well studied and understood. Here we demonstrate coherent quantum control of a two photon resonant pump-dump process in a complex solvated dye molecule. Phase jump in the frequency domain via a pulse shaper is employed to coherently enhance the stimulated emission by an order of magnitude when compared to transform limited pulses. Red shifted stimulated emission from successive low energy Stokes shifted excited states leading to narrowband emission are observed upon scanning the pi step across the excitation spectrum. A binary search space routine was also employed to investigate the effects of other types of phase jumps on stimulated emission and to determine the optimum phase that maximizes the emission. Understanding the underlying mechanism of this kind of enhancement will guide us in designing pulse shapes for enhancing stimulated emission, which can be further applied in the field of imaging.

One barbiturate and two solvated thiobarbiturates containing the triply hydrogen-bonded ADA/DAD synthon, plus one ansolvate and three solvates of their coformer 2,4-diaminopyrimidine.