Multi-reference Epstein–Nesbet perturbation theory with density matrix renormalization group reference wavefunction

Abstract

The accurate electronic structure calculation for strongly correlated chemical systems requires an adequate description for both static and dynamic electron correlation, and is a persistent challenge for quantum chemistry. In order to account for static and dynamic electron correlations accurately and efficiently, in this work we propose a new method by integrating the density matrix renormalization group (DMRG) method and multi-reference second-order Epstein–Nesbet perturbation theory (ENPT2) with a selected configuration interaction (SCI) approximation. Compared with previous DMRG-based dynamic correlation methods, the DMRG-ENPT2 method extends the range of applicability, allowing us to efficiently calculate systems with very large active space beyond 30 orbitals. We demonstrate this by performing calculations on H2S with an active space of (16e, 15o), hexacene with an active space of (26e, 26o) and 2D H64 square lattice with an active space of (42e, 42o).