A smooth, nonsingular, and faithful discretization scheme for polarizable continuum models: the switching/Gaussian approach.
作者： Adrian W. Lange , John M. Herbert
DOI: 10.1063/1.3511297
关键词: Gaussian 、 Continuum (topology) 、 Solvent models 、 Classical mechanics 、 Molecular dynamics 、 Potential energy surface 、 Statistical physics 、 Gravitational singularity 、 Discretization 、 Physics 、 Invertible matrix
摘要: Polarizable continuum models (PCMs) are a widely used family of implicit solvent based on reaction-field theory and boundary-element discretization the solute/continuum interface. An often overlooked aspect these theories is that interface typically does not afford continuous potential energy surface for solute. In addition, we show can lead to numerical singularities violations exact variational conditions. To fix problems, introduce switching/Gaussian (SWIG) method, scheme overcomes several longstanding problems with PCMs. Our approach generalizes procedure introduced by York Karplus [J. Phys. Chem. A 103, 11060 (1999)], extending it beyond conductor-like screening model. Comparison other purportedly smooth PCM implementations reveals certain artifacts in alternative approaches, which avoided using SWIG methodology. The versatility our demonstrated via geometry optimizations, vibrational frequency calculations, molecular dynamics simulations, solutes described quantum mechanics mechanics.
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