Modeling Charge Flux by Interpolating Atomic Partial Charges.

Abstract

Although the charge flux effect or the geometric dependence of the atomic partial charges have been known for a long time, how it can be effectively handled is not yet established. Here, we present a charge interpolation scheme as a new general tool for representing the charge flux in an analytically well-defined manner. By applying it to the anionic GFP chromophore with the diabatically represented atomic charges, we show that the charge interpolation provides a substantial improvement on the accuracy of the geometry-dependent changes in the molecular dipole moments in the gas phase. We also test the scheme toward describing the electrostatic term in the solvation energy in the aqueous environment and observe that it is also improved but that the extent of the improvement is somewhat limited. We show that the remaining errors can be largely corrected by introducing atomic polarizabilities. Overall, our results show that charge interpolation is an amenable approach for describing the charge flux effect and that its description in the condensed phase should be accompanied by proper treatments of polarization effects.