Externally-Contracted Multireference Configuration Interaction Method Using a DMRG Reference Wave Function.

Abstract

The recent development of the density matrix renormalization group (DMRG) method in multireference quantum chemistry makes it practical to evaluate static correlation in a large active space, while dynamic correlation provides a critical correction to the DMRG reference for strong-correlated systems and is usually obtained using multireference perturbation (MRPT) or configuration interaction (MRCI) methods with internal contraction (ic) approximation. These methods can use an active space scalable to relatively larger size references than has previously been possible. However, they are still hardly applicable to systems with an active space larger than 30 orbitals and/or a large basis set because of high computation and storage costs of high-order reduced density matrices (RDMs) and the crucial dependence of the MRCI Hamiltonian dimension on the number of virtual orbitals. In this work, we propose a new effective implementation of DMRG-MRCI, in which we use reconstructed CASCI-type configurations from DMRG wave function via the entropy-driving genetic algorithm (EDGA) [ Luo et al. J. Chem. Theory Comput. 2017 , 13 , 4699 - 4710 . ] and integrate it with MRCI by an external contraction (ec) scheme. This bypasses the bottleneck of computing high-order RDMs in traditional DMRG dynamic correlation methods with ic approximation, and the number of MRCI configurations is not dependent on the number of virtual orbitals. Therefore, the DMRG-ec-MRCI method is promising for dealing with a larger active space than 30 orbitals and large basis sets. We demonstrate the capability of our DMRG-ec-MRCI method in several benchmark applications, including the evaluation of the potential energy curve of Cr2, single-triplet gaps of higher n-acene molecules, and the energy of the Eu-BTBP(NO3)3 complex.