Quantum mechanical/molecular mechanical/continuum style solvation model: Linear response theory, variational treatment, and nuclear gradients

Hui Li, University of Nebraska - Lincoln

Document Type Article

Published in THE JOURNAL OF CHEMICAL PHYSICS 131, 184103 (2009). Copyright © 2009 American Institute of Physics. Used by Permission

Abstract

Linear response and variational treatment are formulated for Hartree–Fock (HF) and Kohn–Sham density functional theory (DFT) methods and combined discrete-continuum solvation models that incorporate self-consistently induced dipoles and charges. Due to the variational treatment, analytic nuclear gradients can be evaluated efficiently for these discrete and continuum solvation models. The forces and torques on the induced point dipoles and point charges can be evaluated using simple electrostatic formulas as for permanent point dipoles and point charges, in accordance with the electrostatic nature of these methods. Implementation and tests using the effective fragment potential (EFP, a polarizable force field method and the conductorlike polarizable continuum model (CPCM) show that the nuclear gradients are as accurate as those in the gas phase HF and DFT methods. Using B3LYP/EFP/CPCM and time-dependent-B3LYP/EFP/CPCM methods, acetone S₀→S₁ excitation in aqueous solution is studied. The results are close to those from full B3LYP/CPCM calculations.