On analytical derivatives for geometry optimization in the polarizable continuum model

摘要

The present paper is dedicated to the analytical computation of shape derivatives in the polarizable continuum model. We derive expressions for the interaction energy’s sensitivity with respect to variations of the cavity’s shape by means of the Hadamard representation of the shape gradient. In particular, by using the adjoint approach, the shape gradient depends only on two solutions of the underlying electrostatic problem. We further formulate boundary integral equations to compute the involved quantities.