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

Abstract In this paper we present a formulation of the Polarizable Continuum Model including the consideration of the electron correlation. Three levels of complexity in the method are considered, the first two introducing a partial decoupling of solvation and correlation effects. Third order calculations show a clear influence of electron correlation on the solvation energy and parallel influence of solvent polarization effects on the correlation energy. The analysis has been performed over a representative set of solutes, also taking into consideration the most significant observables.

[1]  M. Aguilar,et al.  Solute-solvent interactions. Adaptation of the cavity size as a function of the basis set , 1988 .

[2]  J. J. Maraver,et al.  Electrostatic interactions as a factor in the determination of the HOMO in the liquid state , 1986 .

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

[4]  B. Brandow.  Linked-Cluster Expansions for the Nuclear Many-Body Problem , 1967 .

[5]  M. Abraham,et al.  Calculations on Ionic Solvation. VII* The Free Energy of Solvation of Ions Calculated from Various Local Solvent Dielectric Constant-Distance Functions , 1982 .

[6]  C. Felder,et al.  Energies of solute molecules from an atom charge–dipole interaction model with a surrounding dielectric: Application to Gibbs energies of proton transfer between carboxylic acids in water , 1981 .

[7]  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 .

[8]  M. Aguilar,et al.  Solute-solvent interactions. a simple procedure for constructing the solvent cavity for retaining a molecular solute , 1989 .

[9]  J. Kirkwood,et al.  Theory of Solutions of Molecules Containing Widely Separated Charges with Special Application to Zwitterions , 1934 .

[10]  M. R. Hoffmann.  A Full Coupled-Cluster Singles, Doubles, and Triples Model for the Description of Electron Correlation , 1984 .

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

[12]  Alexander A. Rashin,et al.  A simple method for the calculation of hydration enthalpies of polar molecules with arbitrary shapes , 1987 .

[13]  Toru Nakagawa,et al.  Band contour analysis of the nu1 and nu5 fundamentals of formaldehyde , 1971 .

[14]  Orlando Tapia,et al.  Self-consistent reaction field theory of solvent effects , 1975 .

[15]  Jacopo Tomasi,et al.  Conformational energy of glycine in aqueous solutions and relative stability of the zwitterionic and neutral forms. An ab initio study , 1984 .

[16]  R. Lees.  Torsion‐Vibration‐Rotation Interactions in Methanol. II. Microwave Spectrum of CD3OD , 1972 .

[17]  P. Claverie,et al.  Improvements of the continuum model. 1. Application to the calculation of the vaporization thermodynamic quantities of nonassociated liquids , 1988 .

[18]  Arieh Warshel,et al.  Calculations of chemical processes in solutions , 1979 .

[19]  Rodney J. Bartlett,et al.  Fifth-Order Many-Body Perturbation Theory and Its Relationship to Various Coupled-Cluster Approaches* , 1986 .

[20]  Jean-Louis Rivail,et al.  A quantum chemical approach to dielectric solvent effects in molecular liquids , 1976 .

[21]  Manuel F. Ruiz-López,et al.  Ab initio SCF calculations on electrostatically solvated molecules using a deformable three axes ellipsoidal cavity , 1983 .

[22]  Jacopo Tomasi,et al.  Introduction of solvent effects in the electrostatic recognition of biological receptors , 1988 .

[23]  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 .

[24]  Jacopo Tomasi,et al.  Appraisal of solvation effects on chemical functional groups: amides and esters in terms of transferable subgroup contributions , 1989 .

[25]  D. Rinaldi,et al.  Influence of dispersion forces on the electronic structure of a solvated molecule , 1986 .

[26]  F.J.Olivares del Valle,et al.  A computation procedure for the dispersion component of the interaction energy in continuum solute-solvent models , 1989 .

[27]  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 .

[28]  H. Ågren,et al.  A self-consistent reaction field approach to liquid photoionization , 1987 .

[29]  Kurt V. Mikkelsen,et al.  Self‐consistent reaction field calculations of photoelectron binding energies for solvated molecules , 1989 .

[30]  G. Karlstroem,et al.  Proton transport in water modeled by a quantum chemical dielectric cavity model , 1988 .

[31]  R. Lees,et al.  Microwave Spectra of Molecules of Astrophysical Interest: III. Methanol , 1973 .

[32]  Jacopo Tomasi,et al.  Theoretical determination of the gibbs energy of solution and transfer between immiscible solvents, with comments on the dynamics of phase transfer , 1990 .

[33]  H. Padé.  Sur la représentation approchée d'une fonction par des fractions rationnelles , 1892 .

[34]  S. Miertus,et al.  Approximate methods for solvent effects calculations on biomolecules , 1989 .

[35]  J. Rivail,et al.  Variational calculation of electronic multipole molecular polarizabilities , 1978 .

[36]  R. Lees.  Torsion‐Vibration‐Rotation Interactions in Methanol. IV. Microwave Spectrum of CH3OH in the Excited CO Stretching State , 1972 .

[37]  M. Huron,et al.  Calculation of the interaction energy of one molecule with its whole surrounding. II. Method of calculating electrostatic energy , 1974 .

[38]  R. Bartlett.  Many-Body Perturbation Theory and Coupled Cluster Theory for Electron Correlation in Molecules , 1981 .

[39]  Jacopo Tomasi,et al.  An appraisal of solvation effects on chemical functional groups: The amidic and the esteric linkages , 1990 .

[40]  Malcolm L. J. Drummond,et al.  A supertensor formalism for solute–continuum solvent interactions with an arbitrarily shaped cavity. I. Theory and implementation , 1988 .

[41]  G. W. Schnuelle,et al.  Free energy of a charge distribution in concentric dielectric continua , 1975 .

[42]  B. Zwolinski,et al.  Thermodynamic properties of normal and deuterated methanols , 1977 .

[43]  G. Herzberg,et al.  On the Structure of CH2 in its Triplet Ground State , 1971 .

[44]  I. Shavitt,et al.  Ab initio SCF and CI studies on the ground state of the water molecule. I. Comparison of CGTO and STO basis sets near the Hartree-Fock limit , 1975 .

[45]  G. Karlstroem.  A new approach to the modeling of dielectric media effects in ab initio quantum chemical calculations , 1988 .

[46]  R. Lees,et al.  Torsion–Vibration–Rotation Interactions in Methanol. I. Millimeter Wave Spectrum , 1968 .

[47]  Jacopo Tomasi,et al.  Electrostatic interaction of a solute with a continuum. Improved description of the cavity and of the surface cavity bound charge distribution. , 1987 .

[48]  J. Rullmann,et al.  Analysis of discrete and continuum dielectric models : Application to the calculation of protonation energies in solution , 1987 .

[49]  M. Born.  Volumen und Hydratationswärme der Ionen , 1920 .

[50]  R. Bonaccorsi,et al.  Ab initio evaluation of absorption and emission transitions for molecular solutes, including separate consideration of orientational and inductive solvent effects , 1983 .

[51]  S. Ehrenson.  Boundary continuity and analytical potentials in continuum solvent models. Implications for the Born model , 1987 .

[52]  R. Constanciel,et al.  On the theory of solvent effects , 1978 .