Reviews in Computational Chemistry Volume 18

CHAPTER 3
Potentials and Algorithms for
Incorporating Polarizability in
Computer Simulations
Steven W. Rick* and Steven J. Stuart y
*Department of Chemistry, University of New Orleans,
New Orleans, Louisiana 70148 and Chemistry Department,
Southern University of New Orleans, New Orleans, Louisiana
70126, and y Department of Chemistry, Clemson University,
Clemson, South Carolina 29634
INTRODUCTION
Reviews in Computational Chemistry, Volume 18
E dited by K enny B. L ipkowitz and D onald B. Boyd
Copyr ight © 2002 John Wiley & Sons, I nc.
ISBN: 0-471-21576-7
Polarization refers to the redistribution of a particle’s electron density
due to an electric field. In terms of molecular interactions, polarization leads
to nonadditivity, since a molecule polarized by another molecule will interact
differently with a third molecule than it would if it were not polarized. The
change in the electron density can be characterized by changes in the monopole
charges, dipole moments, or higher order moments. Methods for treating
polarizability in molecular dynamics or Monte Carlo simulations achieve this
goal through inducible dipole moments (the polarizable point dipole and shell
models) or through fluctuating charges (the electronegativity equalization and
semiempirical models). This chapter describes these models, with a focus on
those methods that have been developed for molecular dynamics and Monte
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