Efficient Evaluation of Molecular Electrostatic Potential in Large Systems

Abstract

An algorithm for the efficient computation of molecular electrostatic potential is reported. It is based on the partition/expansion of density into (pseudo) atomic fragments with the method of Deformed Atoms in Molecules, which allows to compute the potential as a sum of atomic contributions. These contributions are expressed as a series of irregular spherical harmonics times effective multipole moments and inverse multipole moments, including short-range terms. The problem is split into two steps. The first one consists of the partition/expansion of density accompanied by the computation of multipole moments, and its cost depends on the size of the basis set used in the computation of electron density within the Linear Combination of Atomic Orbitals framework. The second one is the actual computation of the electrostatic potential from the quantities calculated in the first step, and its cost depends on the number of computation points. For a precision in the electrostatic potential of six decimal figures, the algorithm leads to a dramatic reduction of the computation time with respect to the calculation from electron density matrix and integrals involving basis set functions.