New developments in the polarizable continuum model for quantum mechanical and classical calculations on molecules in solution

The polarizable continuum model (PCM), used for the calculation of molecular energies, structures, and properties in liquid solution has been deeply revised, in order to extend its range of applications and to improve its accuracy. The main changes effect the definition of solute cavities, of solvation charges and of the PCM operator added to the molecular Hamiltonian, as well as the calculation of energy gradients, to be used in geometry optimizations. The procedure can be equally applied to quantum mechanical and to classical calculations; as shown also with a number of numerical tests, this PCM formulation is very efficient and reliable. It can also be applied to very large solutes, since all the bottlenecks have been eliminated to obtain a procedure whose time and memory requirements scale linearly with solute size. The present procedure can be used to compute solvent effects at a number of different levels of theory on almost all the chemical systems which can be studied in vacuo.

[1]  K. Morokuma,et al.  A NEW ONIOM IMPLEMENTATION IN GAUSSIAN98. PART I. THE CALCULATION OF ENERGIES, GRADIENTS, VIBRATIONAL FREQUENCIES AND ELECTRIC FIELD DERIVATIVES , 1999 .

[2]  Vincenzo Barone,et al.  Improving performance of polarizable continuum model for study of large molecules in solution , 1999 .

[3]  Jacopo Tomasi,et al.  Excited states and solvatochromic shifts within a nonequilibrium solvation approach: A new formulation of the integral equation formalism method at the self-consistent field, configuration interaction, and multiconfiguration self-consistent field level , 1998 .

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

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

[6]  Christian Silvio Pomelli,et al.  An improved iterative solution to solve the electrostatic problem in the polarizable continuum model , 2001 .

[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]  R. Constanciel.  Theoretical basis of the empirical reaction field approximations through continuum model , 1986 .

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

[10]  J. Tomasi,et al.  Ab initio study of ionic solutions by a polarizable continuum dielectric model , 1998 .

[11]  Jacopo Tomasi,et al.  A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics , 1997 .

[12]  Donald G. Truhlar,et al.  A Universal Solvation Model Based on Class IV Charges and the Intermediate Neglect of Differential Overlap for the Spectroscopy Molecular Orbital Method , 2000 .

[13]  V. Barone,et al.  Toward reliable density functional methods without adjustable parameters: The PBE0 model , 1999 .

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

[15]  Thanh N. Truong,et al.  A new method for incorporating solvent effect into the classical, ab initio molecular orbital and density functional theory frameworks for arbitrary shape cavity , 1995 .

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

[17]  M. Tissandier,et al.  The Proton's Absolute Aqueous Enthalpy and Gibbs Free Energy of Solvation from Cluster-Ion Solvation Data , 1998 .

[18]  Orlando Tapia,et al.  Solvent effects and chemical reactivity , 2002 .

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

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

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

[22]  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 .

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

[24]  Jeffrey R. Reimers,et al.  Solvent effects on molecular spectra. III. Absorption to and emission from the lowest singlet (n,π*) state of dilute pyrimidine in water , 1993 .

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

[26]  Leif A. Eriksson,et al.  Theoretical Biochemistry: Processes and Properties of Biological Systems , 2001 .

[27]  Vincenzo Barone,et al.  Solvent effect on vertical electronic transitions by the polarizable continuum model , 2000 .

[28]  W. Goddard,et al.  UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations , 1992 .

[29]  C. Reichardt.  Solvents and Solvent Effects in Organic Chemistry , 1988 .

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

[31]  S. Canuto,et al.  Solvent effects in emission spectroscopy: A Monte Carlo quantum mechanics study of the n←π* shift of formaldehyde in water , 2000 .

[32]  K. Morokuma,et al.  ONIOM: A Multilayered Integrated MO + MM Method for Geometry Optimizations and Single Point Energy Predictions. A Test for Diels−Alder Reactions and Pt(P(t-Bu)3)2 + H2 Oxidative Addition , 1996 .

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

[34]  Giovanni Scalmani,et al.  Polarizable dielectric model of solvation with inclusion of charge penetration effects , 2001 .

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

[36]  Benedetta Mennucci,et al.  Analytical derivatives for geometry optimization in solvation continuum models. I. Theory , 1998 .

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

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

[39]  M. Aguilar.  Separation of the Electric Polarization into Fast and Slow Components: A Comparison of Two Partition Schemes , 2001 .

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

[41]  D. B. Chesnut,et al.  A study of NMR chemical shielding in water clusters derived from molecular dynamics simulations , 1994 .

[42]  János G. Ángyán,et al.  Common theoretical framework for quantum chemical solvent effect theories , 1992 .