How to select active space for multiconfigurational quantum chemistry?

Abstract

Björn Roos is one of the pioneers in the development and usage of multiconfigurational methods, in particular, the complete active space self‐consistent field method and the perturbational complete active space perturbation theory through second order. To perform multiconfigurational calculations using these methods, a set of active orbitals must be selected, and the success of the methods depends on the choice of this set. This is not only sometimes easy but also sometimes difficult, especially for use of the more recent RASSCF and RASPT2 methods (which use a “restricted active space” rather than the complete one). Although an automated procedure for selecting the active orbitals would be a preferable solution, this does not seem feasible yet. An account of the problem is given, with examples and some approaches that usually work. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111:3329–3338, 2011