Tensor Hypercontraction Second-Order Møller-Plesset Perturbation Theory: Grid Optimization and Reaction Energies

Sara I L Kokkila Schumacher; Edward G Hohenstein; Robert M Parrish; Lee-Ping Wang; Todd J Martínez

doi:10.1021/acs.jctc.5b00272

Tensor Hypercontraction Second-Order Møller-Plesset Perturbation Theory: Grid Optimization and Reaction Energies

J Chem Theory Comput. 2015 Jul 14;11(7):3042-52. doi: 10.1021/acs.jctc.5b00272.

Authors

Sara I L Kokkila Schumacher^{1

2}, Edward G Hohenstein^{1

2

3}, Robert M Parrish⁴, Lee-Ping Wang^{1

2}, Todd J Martínez^{1

2}

Affiliations

¹ Department of Chemistry and the PULSE Institute, Stanford University , Stanford, California 94305, United States.
² SLAC National Accelerator Laboratory , Menlo Park, California 94025, United States.
³ Department of Chemistry and Biochemistry, City College of New York , New York, New York 10031, United States.
⁴ Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.

PMID: 26575741
DOI: 10.1021/acs.jctc.5b00272

Abstract

We have recently introduced the tensor hypercontraction (THC) method for electronic structure, including MP2. Here, we present an algorithm for THC-MP2 that lowers the memory requirements as well as the prefactor while maintaining the formal quartic scaling that we demonstrated previously. We also describe a procedure to optimize quadrature grids used in grid-based least-squares (LS) THC-MP2. We apply this algorithm to generate grids for first-row atoms with less than 100 points/atom while incurring negligible errors in the computed energies. We benchmark the LS-THC-MP2 method using optimized grids for a wide variety of tests sets including conformational energies and reaction barriers in both the cc-pVDZ and cc-pVTZ basis sets. These tests demonstrate that the THC methodology is not limited to small basis sets and that it incurs negligible errors in both absolute and relative energies.