Tensor factorizations of local second-order Møller Plesset theory

Abstract

Efficient electronic structure methods can be built around efficient tensor representations of the wavefunction. Here we describe a general view of tensor factorization for the compact representation of electronic wavefunctions. We use these ideas to construct low-complexity representations of the doubles amplitudes in local second order Møller-Plesset perturbation theory. We introduce two approximations - the direct orbital specific virtual approximation and the full orbital specific virtual approximation. In these approximations, each occupied orbital is associated with a small set of correlating virtual orbitals. Conceptually, the representation lies between the projected atomic orbital representation in Pulay-Saebø local correlation theories and pair natural orbital correlation theories. We have tested the orbital specific virtual approximations on a variety of systems and properties including total energies, reaction energies, and potential energy curves. Compared to the Pulay-Saebø ansatz, we find that these approximations exhibit favourable accuracy and computational times, while yielding smooth potential energy curves.