Communication: Tensor hypercontraction. III. Least-squares tensor hypercontraction for the determination of correlated wavefunctions

Abstract

The manipulation of the rank-four tensor of double excitation amplitudes represents a challenge to the efficient implementation of many electronic structure methods. We present a proof of concept for the approximation of doubles amplitudes in the tensor hypercontraction (THC) representation. In particular, we show how THC can be used to both reduce the scaling with respect to molecular size of coupled cluster singles and doubles (CCSD) (and related methods) by two orders from O(N6) to O(N4) and remove the memory bottleneck associated with storage of the doubles amplitudes. The accuracy of correlated methods as integral and amplitude approximations are introduced is examined. For a set of 20 small molecules, single and double-excitation configuration interaction (CISD), quadratic CISD (QCISD), and CCSD correlation energies could be reproduced with millihartree accuracy after the introduction of these approximations. Our approach exploits otherwise hidden factorizable tensor structure in both the electron repulsion integrals and the wavefunction coefficients and should be applicable with suitable modifications to many methods in electronic structure theory. © 2012 American Institute of Physics.