Towards improved force fields: III. Polarization through modified atomic charges

A method of modeling polarization by representing an atomic‐centered induced dipole as a set of induced charges on the atom and its immediate neighbors is presented. The method is based on earlier work on deriving atomic charges from a distributed multipole analysis (P. J. Winn et al., J Phys Chem A 1997, 101, 5437; G. G. Ferenczy, J Comput Chem 1991, 12, 913). The method has been applied to the water dimer, water trimers, formaldehyde–water complexes, methanol complexes, and DNA basepairs. It was found that the induced charges described the various cooperative and anticooperative hydrogen bonding systems well, both qualitatively and quantitatively (as compared with Hartree–Fock calculations). Importantly, it has been shown that, when an induced charge (or induced dipole) model is used for larger molecules, a correction term is required for the underlying electrostatics. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 704–712, 1999

[1]  Jonathan W. Essex,et al.  Atomic charges for variable molecular conformations , 1992 .

[2]  C. Reynolds,et al.  Toward Improved Force Fields. 1. Multipole-Derived Atomic Charges , 1997 .

[3]  G. W. Robinson,et al.  A flexible/polarizable simple point charge water model , 1991 .

[4]  Pavel Hobza,et al.  Intermolecular interactions between medium-sized systems. Nonempirical and empirical calculations of interaction energies. Successes and failures , 1988 .

[5]  J. Stewart.  Optimization of parameters for semiempirical methods II. Applications , 1989 .

[6]  Bruce J. Berne,et al.  Dynamical Fluctuating Charge Force Fields: The Aqueous Solvation of Amides , 1996 .

[7]  Michiel Sprik,et al.  COMPUTER-SIMULATION OF THE DYNAMICS OF INDUCED POLARIZATION FLUCTUATIONS IN WATER , 1991 .

[8]  M. Symons.  Anticooperativity in solvation , 1993 .

[9]  Uwe Koch,et al.  Conformational dependence of atomic multipole moments , 1995 .

[10]  S J Wodak,et al.  Calculations of electrostatic properties in proteins. Analysis of contributions from induced protein dipoles. , 1987, Journal of molecular biology.

[11]  W. Goddard,et al.  Charge equilibration for molecular dynamics simulations , 1991 .

[12]  Anthony J. Stone,et al.  Distributed multipole analysis, or how to describe a molecular charge distribution , 1981 .

[13]  György G. Ferenczy,et al.  Transferable net atomic charges from a distributed multipole analysis for the description of electrostatic properties: a case study of saturated hydrocarbons , 1993 .

[14]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[15]  Methods for determining the reliability of semiempirical electrostatic potentials and potential derived charges , 1992 .

[16]  György G. Ferenczy,et al.  Toward Improved Force Fields. 2. Effective Distributed Multipoles , 1997 .

[17]  Peter A. Kollman,et al.  Implementation of nonadditive intermolecular potentials by use of molecular dynamics: development of a water-water potential and water-ion cluster interactions , 1990 .

[18]  Kenneth J. Miller,et al.  Additions and Corrections - A New Empirical Method to Calculate Average Molecular Polarizabilities , 1979 .

[19]  György G. Ferenczy.  Charges derived from distributed multipole series , 1991 .

[20]  J. Pople,et al.  Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions , 1980 .

[21]  P. C. Hariharan,et al.  The influence of polarization functions on molecular orbital hydrogenation energies , 1973 .

[22]  Anders Wallqvist,et al.  A molecular dynamics study of polarizable water , 1989 .