Molecule-specific determination of atomic polarizabilities with the polarizable atomic multipole model

作者：Kim Hyun Woo^*; Rhee Young Min

来源：Journal of Computational Chemistry, 2012, 33(20): 1662-1672.

DOI：10.1002/jcc.22985

• molecular dynamics
• polarizable model
• force field
• atomic polarizability
• atomic multipole

Recently, many polarizable force fields have been devised to describe induction effects between molecules. In popular polarizable models based on induced dipole moments, atomic polarizabilities are the essential parameters and should be derived carefully. Here, we present a parameterization scheme for atomic polarizabilities using a minimization target function containing both molecular and atomic information. The main idea is to adopt reference data only from quantum chemical calculations, to perform atomic polarizability parameterizations even when relevant experimental data are scarce as in the case of electronically excited molecules. Specifically, our scheme assigns the atomic polarizabilities of any given molecule in such a way that its molecular polarizability tensor is well reproduced. We show that our scheme successfully works for various molecules in mimicking dipole responses not only in ground states but also in valence excited states. The electrostatic potential around a molecule with an externally perturbing nearby charge also exhibits a near-quantitative agreement with the reference data from quantum chemical calculations. The limitation of the model with isotropic atoms is also discussed to examine the scope of its applicability.

• 出版日期2012-7-30