A New Approach to Reactive Potentials with Fluctuating Charges: Quadratic Valence-Bond Model

Jorge Morales, Todd J. Martínez

Research output: Contribution to journalArticle

31 Scopus citations

Abstract

Chemical potential equilibration models have proven to be a promising approach for describing charge transfer and polarization in the context of classical force fields. These have generally been justified in an ad hoc manner and are known to behave incorrectly in certain cases, presenting a stumbling block to widespread application. In this paper, we present a new wave function-based derivation of a CPE-like model, shedding some light on the nature of the approximations that are made. The concept of a pairwise hardness arises naturally from this derivation, leading us to suggest a model that employs a pairwise electronegativity. We show that this leads to a CPE-like model that dissociates correctly for a diatomic and furthermore predicts charges in agreement with ab initio methods for a simple diatomic.

Original languageEnglish
Pages (from-to)3076-3084
Number of pages9
JournalJournal of Physical Chemistry A
Volume108
Issue number15
DOIs
StatePublished - Apr 15 2004

Fingerprint Dive into the research topics of 'A New Approach to Reactive Potentials with Fluctuating Charges: Quadratic Valence-Bond Model'. Together they form a unique fingerprint.

Cite this