Calculation of the Vibrational Stark Effect Using a First-Principles QM/MM Approach.

ABSTRACT: The proper description of the electric environment of condensed phases is a critical challenge for force field methods. To test and validate the ability of the CHARMM additive force field to describe the electric environment in aqueous solution combined QM/MM calculations have been used to calculate the vibrational Stark effect (VSE). We utilized a first principles methodology using correlated electronic structure techniques to compute the Stark shift between the gas phase and solvent environments and between two different solvent environments of three VSE probes containing acetonitrile or fluorine functionalities which have been well-characterized experimentally. Reasonable agreement with the experimentally determined Stark shifts is obtained when the MM atoms are described by the CHARMM

SUBMITTER: Ringer AL 

PROVIDER: S-EPMC3058488 | biostudies-literature | 2011 Feb

REPOSITORIES: biostudies-literature