Multireference electron correlation methods with density matrix renormalisation group reference functions

Abstract

Recent advances in quantum chemical density matrix renormalisation group (DMRG) theory are presented. The DMRG, originally devised as an alternative to the exact diagonalisation in condensed matter physics, has become a powerful quantum chemical method for molecular systems that exhibit a multireference character, e.g., excited states, π-conjugated systems, transition metal complexes, and in particular for large systems by combining it with conventional multireference electron correlation methods. The capability of the current quantum chemical DMRG is demonstrated for an application involving the potential energy curve of the chromium dimer, which is one of the most demanding multireference systems and thus requires the best electronic structure treatment for non-dynamical and dynamical correlation as well as large basis sets.

Keywords:

• electronic structure theory
• electron correlation
• density matrix renormalisation group
• transition metal complex

Acknowledgements

The author acknowledges T. Yanai for many valuable discussions and support. This work was supported in part by a Grant-in-Aid for Scientific Research (C) (grant no. 25410030) from MEXT, Japan.