Stochastic Formulation of the Resolution of Identity: Application to Second Order Møller–Plesset Perturbation Theory

Citation:

Takeshita, T. Y. ; de Jong, W. A. ; Neuhauser, D. ; Baer, R. ; Rabani, E. Stochastic Formulation of the Resolution of Identity: Application to Second Order Møller–Plesset Perturbation Theory. J. Chem. Theory Comput. 2017, 13, 4605.

Abstract:

A stochastic orbital approach to the resolution of identity (RI) approximation for 4 index electron repulsion integrals (ERIs) is presented. The stochastic RI-ERIs are then applied to second order Møller-Plesset perturbation theory (MP2) utilizing a multiple stochastic orbital approach. The introduction of multiple stochastic orbitals results in an O(N_AO^3 ) scaling for both the stochastic RI-ERIs and stochastic RI-MP2, NAO being the number of basis functions. For a range of water clusters we demonstrate that this method exhibits a small prefactor and observed scalings of O(Ne^2.4) for total energies and O(Ne^3.1) for forces (Ne being the number of correlated electrons), outperforming MP2 for clusters with as few as 21 water molecules.

Notes:

PMID: 28914534 RBaer-Publication

Publisher's Version

Last updated on 11/16/2017