Self-consistent electrostatic embedding for liquid phase polarization
نویسندگان
چکیده
While it is well known that molecules can be strongly polarized when transferred from the gas phase to a polar liquid, quantifying polarization effects explicitly using either experiment or theory has remained elusive. In this paper, we present new QM/MM method involving self-consistent calculation of liquid state dipole moments, able yield realistic, accurate estimates multipole moments in state. As proof-of-concept, apply our Self-Consistent Electrostatic Embedding (SCEE) widely studied system pure water. The gives molecular are significantly enhanced with respect isolated gas-phase molecule and consistent best current experimental estimate property. previous calculations on same systematically underestimate moment, those predictions become own several shortcomings accounted for an approximate way. Furthermore, sampling configurations (but not all) fixed-charge force fields yields results classical polarizable model. We then extract contributions energy (i.e. change transferring phase) show distortion correction cancelled out by purely electronic contribution energy. This insight very important point view force-field development, since allows us unequivocally quantify two missing terms non-polarizable models. provides way improve phase-change energies (e.g. enthalpy vaporization, hydration free energies) such force-fields correcting effects.
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ژورنال
عنوان ژورنال: Journal of Molecular Liquids
سال: 2021
ISSN: ['0167-7322', '1873-3166']
DOI: https://doi.org/10.1016/j.molliq.2020.114550