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A finite field method for calculating molecular polarizability tensors for arbitrary multipole rank
Author(s) -
Elking Dennis M.,
Perera Lalith,
Duke Robert,
Darden Thomas,
Pedersen Lee G.
Publication year - 2011
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21914
Subject(s) - polarizability , multipole expansion , chemistry , fast multipole method , tensor (intrinsic definition) , ab initio , ab initio quantum chemistry methods , polarization (electrochemistry) , anisotropy , coupled cluster , perturbation theory (quantum mechanics) , physics , intermolecular force , computational chemistry , spherical multipole moments , molecular physics , atomic physics , quantum mechanics , molecule , geometry , mathematics
A finite field method for calculating spherical tensor molecular polarizability tensors α lm ; l ′ m ′ = ∂Δ lm /∂ϕ l ′ m ′ * by numerical derivatives of induced molecular multipole Δ lm with respect to gradients of electrostatic potential ϕ l ′ m ′ * is described for arbitrary multipole ranks l and l ′. Interconversion formulae for transforming multipole moments and polarizability tensors between spherical and traceless Cartesian tensor conventions are derived. As an example, molecular polarizability tensors up to the hexadecapole–hexadecapole level are calculated for water using the following ab initio methods: Hartree–Fock (HF), Becke three‐parameter Lee‐Yang‐Parr exchange‐correlation functional (B3LYP), Møller–Plesset perturbation theory up to second order (MP2), and Coupled Cluster theory with single and double excitations (CCSD). In addition, intermolecular electrostatic and polarization energies calculated by molecular multipoles and polarizability tensors are compared with ab initio reference values calculated by the Reduced Variation Space method for several randomly oriented small molecule dimers separated by a large distance. It is discussed how higher order molecular polarizability tensors can be used as a tool for testing and developing new polarization models for future force fields. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011