East China Normal Univ., Shanghai (China); NYU Shanghai, Shanghai (China); National Institutes of Health, National Heart, Lung and Blood Institute, Rockville, MD (United States); Office of Scientific and Technical Information (OSTI)
National Institutes of Health, National Heart, Lung and Blood Institute, Rockville, MD (United States)
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 in this study using the finite-difference method for 21 small molecules, using density functional theory. Within nine charge population schemes (Lowdin, 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. In conclusion, the overall 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.
Mei, Ye, et al. "Numerical study on the partitioning of the molecular polarizability into fluctuating charge and induced atomic dipole contributions." Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, vol. 119, no. 22, May. 2015. https://doi.org/10.1021/acs.jpca.5b03159
Mei, Ye, Simmonett, Andrew C., Pickard, IV, Frank C., DiStasio, Jr., Robert A., Brooks, Bernard R., & Shao, Yihan (2015). Numerical study on the partitioning of the molecular polarizability into fluctuating charge and induced atomic dipole contributions. Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, 119(22). https://doi.org/10.1021/acs.jpca.5b03159
Mei, Ye, Simmonett, Andrew C., Pickard, IV, Frank C., et al., "Numerical study on the partitioning of the molecular polarizability into fluctuating charge and induced atomic dipole contributions," Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory 119, no. 22 (2015), https://doi.org/10.1021/acs.jpca.5b03159
@article{osti_1344918,
author = {Mei, Ye and Simmonett, Andrew C. and Pickard, IV, Frank C. and DiStasio, Jr., Robert A. and Brooks, Bernard R. and Shao, Yihan},
title = {Numerical study on the partitioning of the molecular polarizability into fluctuating charge and induced atomic dipole contributions},
annote = {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 in this study using the finite-difference method for 21 small molecules, using density functional theory. Within nine charge population schemes (Lowdin, 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. In conclusion, the overall 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.},
doi = {10.1021/acs.jpca.5b03159},
url = {https://www.osti.gov/biblio/1344918},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {ISSN 1089-5639},
number = {22},
volume = {119},
place = {United States},
publisher = {American Chemical Society},
year = {2015},
month = {05}}
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 22 Vol. 119; ISSN 1089-5639