Solvation effects on reaction profiles by the polarizable continuum model coupled with the Gaussian density functional method

An efficient version of the polarizable continuum model for solvation has been implemented in the Gaussian density‐functional‐based code called deMon. Solvation free energies of representative compounds have been calculated as a preliminary test. The hydration effects on the reaction profile of the Cl−+CH3Cl→ClCH3+Cl− reaction and the thermodynamics of the Menschutkin reaction have also been investigated. Finally, the conformational behavior of the 1,2‐diazene cis–trans isomerization process in water was examined. Comparisons between the results obtained and the available experimental data and previous theoretical computations have been made. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 290–299, 1998

[1]  Minoru Sakurai,et al.  Medium effects on the molecular electronic structure. I. The formulation of a theory for the estimation of a molecular electronic structure surrounded by an anisotropic medium , 1987 .

[2]  T. Russo,et al.  Solvation Free Energy Calculations Using a Continuum Dielectric Model for the Solvent and Gradient-Corrected Density Functional Theory for the Solute , 1996 .

[3]  Jacopo Tomasi,et al.  Molecular Interactions in Solution: An Overview of Methods Based on Continuous Distributions of the Solvent , 1994 .

[4]  Donald G. Truhlar,et al.  Ab initio calculations of the transition-state geometry and vibrational frequencies of the SN2 reaction of chloride with chloromethane , 1989 .

[5]  W. Hase,et al.  A direct mechanism for SN2 nucleophilic substitution enhanced by mode selective vibrational excitation , 1989 .

[6]  Jacopo Tomasi,et al.  Nonequilibrium solvation: An ab initio quantum‐mechanical method in the continuum cavity model approximation , 1993 .

[7]  Stephan E. Barlow,et al.  The gas-phase displacement reaction of chloride ion with methyl chloride as a function of kinetic energy , 1988 .

[8]  Miquel Solà,et al.  Analysis of Solvent Effects on the Menshutkin Reaction , 1991 .

[9]  Peter Politzer,et al.  Quantitative treatments of solute/solvent interactions , 1994 .

[10]  M. Mckee.  Catalyzed cis/trans isomerization of diazene. A computational study in the gas and aqueous phases , 1993 .

[11]  Jiali Gao,et al.  A priori computation of a solvent-enhanced SN2 reaction profile in water : the Menshutkin reaction , 1991 .

[12]  Jiali Gao,et al.  A two-dimensional energy surface for a type II SN2 reaction in aqueous solution , 1993 .

[13]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[14]  Tom Ziegler,et al.  Potential Energy Surfaces of the Gas-Phase SN2 Reactions X- + CH3X = XCH3 + X- (X = F, Cl, Br, I): A Comparative Study by Density Functional Theory and ab Initio Methods , 1994 .

[15]  H. Ågren,et al.  Theory of solvent effects on electronic spectra , 1991 .

[16]  Dennis R. Salahub,et al.  Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation , 1992 .

[17]  J. Perdew,et al.  Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation. , 1986, Physical review. B, Condensed matter.

[18]  W. J. Albery,et al.  The Application of the Marcus Relation to Reactions in Solution , 1980 .

[19]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[20]  R. Back.  The preparation, properties and reactions of diimide , 1985 .

[21]  Pierre Claverie,et al.  On the Conformational Varieties of Acetylcholine in the Crystals of its Halides , 1978 .

[22]  D. Truhlar,et al.  A Six-Body Potential Energy Surface for the SN2 Reaction ClN-(g) + CH3Cl(g) and a Variational Transition-State-Theory Calculation of the Rate Constant , 1990 .

[23]  Roberto Cammi,et al.  Analytical first derivatives of molecular surfaces with respect to nuclear coordinates , 1996, J. Comput. Chem..

[24]  David A. Case,et al.  Incorporating solvation effects into density functional electronic structure calculations , 1994 .

[25]  Jacopo Tomasi,et al.  Electron correlation and solvation effects. I, Basic formulation and preliminary attempt to include the electron correlation in the quantum mechanical polarizable continuum model so as to study solvation phenomena , 1991 .

[26]  Self consistent reaction field theory of solvent effects in the framework of Gaussian density functional method , 1995 .

[27]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[28]  J. Kirkwood.  The Dielectric Polarization of Polar Liquids , 1939 .

[29]  W. D. Allen,et al.  The SN2 identity exchange reaction ClCH2CN + Cl- .fwdarw. Cl- + ClCH2CN: experiment and theory , 1992 .

[30]  D. Shanno.  Conditioning of Quasi-Newton Methods for Function Minimization , 1970 .

[31]  D. Stanbury,et al.  Direct Detection of Aqueous Diazene: Its UV Spectrum and Concerted Dismutation , 1994 .

[32]  J. Tomasi,et al.  Importance of water in aldol condensation reactions of acetaldehyde , 1994 .

[33]  Ralph G. Pearson,et al.  Ionization potentials and electron affinities in aqueous solution , 1986 .

[34]  J. Tomasi,et al.  The implementation of density functional theory within the polarizable continuum model for solvation , 1994 .

[35]  J. Tomasi,et al.  Dispersion and repulsion contributions to the solvation energy: Refinements to a simple computational model in the continuum approximation , 1991 .

[36]  T. Mcmahon,et al.  Fluoride and chloride affinities of main group oxides, fluorides, oxofluorides, and alkyls. Quantitative scales of Lewis acidities from ion cyclotron resonance halide-exchange equilibria , 1985 .

[37]  J. Tomasi,et al.  Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects , 1981 .

[38]  A. Bondi.  van der Waals Volumes and Radii , 1964 .

[39]  Heather A. Carlson,et al.  Accuracy of free energies of hydration for organic molecules from 6‐31g*‐derived partial charges , 1993, J. Comput. Chem..

[40]  D. Ramsay,et al.  The Near-ultraviolet Absorption Spectrum of Diimide Vapor , 1974 .

[41]  Richard J. Hall,et al.  Modelling the reaction OH- + CO2 → HCO- 3 in the gas phase and in aqueous solution: a combined density functional continuum approach , 1994 .

[42]  Jacopo Tomasi,et al.  Evaluation of the dispersion contribution to the solvation energy. A simple computational model in the continuum approximation , 1989 .

[43]  Minoru Sakurai,et al.  Medium effects on the molecular electronic structure: Part 2. The application of the theory of medium effects in the framework of the CNDO and INDO methods , 1988 .

[44]  L. Onsager.  Electric Moments of Molecules in Liquids , 1936 .

[45]  R. Pierotti,et al.  A scaled particle theory of aqueous and nonaqueous solutions , 1976 .

[46]  R. C. Weast.  Handbook of chemistry and physics , 1973 .

[47]  W. J. Albery.  Methyl transfer reactions , 1979 .

[48]  J. Tomasi,et al.  Ab initio study of solvated molecules: A new implementation of the polarizable continuum model , 1996 .

[49]  Iñaki Tuñón,et al.  GEPOL: An improved description of molecular surfaces. III. A new algorithm for the computation of a solvent‐excluding surface , 1994, J. Comput. Chem..

[50]  Thanh N. Truong,et al.  Hydration effects on reaction profiles: an ab initio dielectric continuum study of the SN2 Cl- + CH3Cl reaction , 1995 .