Polarizable dielectric model of solvation with inclusion of charge penetration effects

An approximate method, recently proposed to include in continuum solvation models the effects of electronic charge lying outside the solute cavity, has been adapted and implemented in the framework of the polarizable continuum model (PCM). This formulation exploits all the features already developed for the other PCM versions; it provides molecular free energies, gradients and second derivatives with respect to nuclear coordinates. The performances of this method have been tested in comparison with other PCM versions, in particular, we examined the reliability of this technique to reproduce actual volume charge distribution effects, compared to traditional procedures based on Gauss’ Law.

[1]  Jacopo Tomasi,et al.  A new definition of cavities for the computation of solvation free energies by the polarizable continuum model , 1997 .

[2]  Timothy Clark,et al.  Efficient diffuse function‐augmented basis sets for anion calculations. III. The 3‐21+G basis set for first‐row elements, Li–F , 1983 .

[3]  K. Wiberg,et al.  Solvent Effects. 5. Influence of Cavity Shape, Truncation of Electrostatics, and Electron Correlation on ab Initio Reaction Field Calculations , 1996 .

[4]  V. Barone,et al.  Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model , 1998 .

[5]  D. D. Yue,et al.  Theory of Electric Polarization , 1974 .

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

[7]  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..

[8]  A. Klamt,et al.  COSMO : a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient , 1993 .

[9]  D. Chipman.  Reaction field treatment of charge penetration , 2000 .

[10]  Jacopo Tomasi,et al.  Evaluation of Solvent Effects in Isotropic and Anisotropic Dielectrics and in Ionic Solutions with a Unified Integral Equation Method: Theoretical Bases, Computational Implementation, and Numerical Applications , 1997 .

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

[12]  Enrico O. Purisima,et al.  Fast summation boundary element method for calculating solvation free energies of macromolecules , 1998 .

[13]  A. Klamt,et al.  Refinement and Parametrization of COSMO-RS , 1998 .

[14]  B. Mennucci,et al.  Linear response theory for the polarizable continuum model , 1999 .

[15]  Jacopo Tomasi,et al.  Second-Order Møller-Plesset Analytical Derivatives for the Polarizable Continuum Model Using the Relaxed Density Approach , 1999 .

[16]  Jacopo Tomasi,et al.  Correction of cavity‐induced errors in polarization charges of continuum solvation models , 1998 .

[17]  Jacopo Tomasi,et al.  Geometry optimization of molecular structures in solution by the polarizable continuum model , 1998 .

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

[19]  Andreas Klamt,et al.  Treatment of the outlying charge in continuum solvation models , 1996 .

[20]  Jacopo Tomasi,et al.  Analytical free energy second derivatives with respect to nuclear coordinates: Complete formulation for electrostatic continuum solvation models , 1999 .

[21]  Vincenzo Barone,et al.  Quantum Mechanical Conformational Analysis of β-Alanine Zwitterion in Aqueous Solution , 2000 .

[22]  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 .

[23]  D. Chipman.  The solvation reaction field for a hydrogen atom in a dielectric continuum , 1996 .

[24]  Tom Ziegler,et al.  An implementation of the conductor-like screening model of solvation within the Amsterdam density functional package , 1999 .

[25]  V. Barone,et al.  Analytical second derivatives of the free energy in solution by polarizable continuum models , 1998 .

[26]  Jacopo Tomasi,et al.  Remarks on the use of the apparent surface charges (ASC) methods in solvation problems: Iterative versus matrix‐inversion procedures and the renormalization of the apparent charges , 1995, J. Comput. Chem..

[27]  C. Cramer,et al.  Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics. , 1999, Chemical reviews.

[28]  Christian Silvio Pomelli,et al.  Recent Advances in the Description of Solvent Effects with the Polarizable Continuum Model , 1998 .

[29]  V. Barone,et al.  A direct procedure for the evaluation of solvent effects in MC-SCF calculations , 1999 .