Multireference Perturbation Theory with Cholesky Decomposition for the Density Matrix Renormalization Group

J Chem Theory Comput. 2017 Feb 14;13(2):451-459. doi: 10.1021/acs.jctc.6b00778. Epub 2017 Feb 2.

Abstract

We present a second-order N-electron valence state perturbation theory (NEVPT2) based on a density matrix renormalization group (DMRG) reference wave function that exploits a Cholesky decomposition of the two-electron repulsion integrals (CD-DMRG-NEVPT2). With a parameter-free multireference perturbation theory approach at hand, the latter allows us to efficiently describe static and dynamic correlation in large molecular systems. We demonstrate the applicability of CD-DMRG-NEVPT2 for spin-state energetics of spin-crossover complexes involving calculations with more than 1000 atomic basis functions. We first assess, in a study of a heme model, the accuracy of the strongly and partially contracted variant of CD-DMRG-NEVPT2 before embarking on resolving a controversy about the spin ground state of a cobalt tropocoronand complex.