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Numerical study on the partitioning of the molecular polarizability into fluctuating charge and induced atomic dipole contributions.

ABSTRACT: In order to carry out a detailed analysis of the molecular static polarizability, which is the response of the molecule to a uniform external electric field, the molecular polarizability was computed using the finite-difference method for 21 small molecules, using density functional theory. Within nine charge population schemes (Löwdin, Mulliken, Becke, Hirshfeld, CM5, Hirshfeld-I, NPA, CHELPG, MK-ESP) in common use, the charge fluctuation contribution is found to dominate the molecular polarizability, with its ratio ranging from 59.9% with the Hirshfeld or CM5 scheme to 96.2% with the Mulliken scheme. The Hirshfeld-I scheme is also used to compute the other contribution to the molecular polarizability coming from the induced atomic dipoles, and the atomic polarizabilities in eight small molecules and water pentamer are found to be highly anisotropic for most atoms. Overall, the results suggest that (a) more emphasis probably should be placed on the charge fluctuation terms in future polarizable force field development and (b) an anisotropic polarizability might be more suitable than an isotropic one in polarizable force fields based entirely or partially on the induced atomic dipoles.

SUBMITTER: Mei Y

PROVIDER: S-EPMC4521410 | biostudies-literature | 2015 Jun

REPOSITORIES: biostudies-literature

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Numerical study on the partitioning of the molecular polarizability into fluctuating charge and induced atomic dipole contributions.

Mei Ye Y Simmonett Andrew C AC Pickard Frank C FC DiStasio Robert A RA Brooks Bernard R BR Shao Yihan Y

The journal of physical chemistry. A 20150518 22

In order to carry out a detailed analysis of the molecular static polarizability, which is the response of the molecule to a uniform external electric field, the molecular polarizability was computed using the finite-difference method for 21 small molecules, using density functional theory. Within nine charge population schemes (Löwdin, Mulliken, Becke, Hirshfeld, CM5, Hirshfeld-I, NPA, CHELPG, MK-ESP) in common use, the charge fluctuation contribution is found to dominate the molecular polariza ...[more]

PMID: 25945749

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Project description:A set of atomic polarizability parameters for a new polarizable Gaussian model (pGM) has been developed with the goal to accurately reproduce the polarizability anisotropy, taking advantage of its ability to attenuate all short-range electrostatic interactions, by fitting the ab initio molecular polarizability tensors ( A pq) calculated at the B3LYP/aug-cc-pVTZ level. For comparison, we also rederived the parameters for three Thole models in which the 1-2 (bonded), 1-3 (separated by two bonds), and 1-4 (separated by three bonds) interactions are fully included. The average percent errors (APEs) of molecular polarizability tensors for 4842 molecules or dimers are 2.98, 3.76, 3.28, and 3.82% for the pGM, Thole linear, Thole exponential, and Thole Amoeba models, respectively, with atom-type independent, universal screening factors (USF). The APEs are reduced further to 2.30, 2.69, 2.25, and 2.48% for the four corresponding polarizable models with atom-type dependent, variable screening factors (VSF). It is encouraging that the pGM with variable screening factors achieved APEs of 1.83 for 1155 amino acid analogs, dipeptides, and tetrapeptides, 1.39 for 28 nucleic acid bases, 0.708 for 1464 water clusters, and 1.99 for 85 dimers of water and biological building blocks. Compared to the new set of models, the APEs of the old Thole models that were fitted to isotropic molecular polarizabilities are 8.7% for set A (without the 1-2 and 1-3 interactions) and 6.3% for set D (with the 1-2 and 1-3 interactions) models, respectively. MPAD, a metric of molecular polarization anisotropy difference based on the diagonal terms of molecular polarizability tensors was defined and applied to assess the polarizable models in reproducing the ab initio molecular polarization anisotropy. The MPADs are 3.71, 4.70, 4.11, and 4.77% for the pGM, Thole linear, Thole exponential, and Thole Amoeba USF models, respectively. The APEs are reduced further to 2.85, 3.58, 2.90, and 3.15% for the four corresponding VSF models. Thus, the new pGM and Thole models notably improve molecular polarization anisotropy. Since pGM attenuates all short-range electrostatic interactions, its application is expected to improve stability in charge fitting, energy, and force calculations and the accuracy of multibody polarization.

Dataset Information

Numerical study on the partitioning of the molecular polarizability into fluctuating charge and induced atomic dipole contributions.

Publications

Numerical study on the partitioning of the molecular polarizability into fluctuating charge and induced atomic dipole contributions.

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