Electrostatically Embedded Many-Body Expansion for Large Systems, with Applications to Water Clusters

Abstract

The use of background molecular charge to incorporate environmental effects on a molecule or active site is widely employed in quantum chemistry. In the present article we employ this practice in conjunction with many-body expansions. In particular, we present electrostatically embedded two-body and three-body expansions for calculating the energies of molecular clusters. The system is divided into fragments, and dimers or trimers of fragments are calculated in a field of point charges representing the electrostatic potential of the other fragments. We find that including environmental point charges can lower the errors in the electrostatically embedded pairwise additive (EE-PA) energies for a series of water clusters by as much as a factor of 10 when compared to the traditional pairwise additive approximation and that for the electrostatically embedded three-body (EE-3B) method the average mean unsigned error over nine different levels of theory for a set of six tetramers and one pentamer is only 0.05 kcal/mol, which is only 0.4% of the mean unsigned net interaction energy. We also test the accuracy of the EE-PA and EE-3B methods for a cluster of 21 water molecules and find that the errors relative to a full MP2/aug'-cc-pVTZ calculation to be only 2.97 and 0.38 kcal/mol, respectively, which are only 1.5% and 0.2%, respectively, of the net interaction energy. This method offers the advantage over some other fragment-based methods in that it does not use an iterative method to determine the charges and thus provides substantial savings for large clusters. The method is convenient to adapt to a variety of electronic structure methods and program packages, it has N(2) or N(3) computational scaling for large systems (where N is the number of fragments), it is easily converted to an O(N) method, and its linearity allows for convenient analytic gradients.