title: Explicitly correlated multireference configuration interaction with multiple reference functions: avoided crossings and conical intersections.
abstract: We develop an explicitly correlated multireference configuration interaction method (MRCI-F12) with multiple reference functions. It can be routinely applied to nearly degenerate molecular electronic structures near conical intersections and avoided crossings, where the reference functions are strongly mixed in the correlated wave function. This work is a generalization of the MRCI-F12 method for electronic ground states, reported earlier by Shiozaki et al. [J. Chem. Phys. 134, 034113 (2011)]. The so-called F12b approximation is used to arrive at computationally efficient formulas. The doubly external part of the wave function is expanded in terms of internally contracted configurations generated from all the reference functions. In addition, we introduce a singles correction to the CASSCF reference energies, which is applicable to multi-state calculations. As examples, we present numerical results for the avoided crossing of LiF, excited states of ozone, and the H(2) + OH (A(2)Σ(+)) reaction.
authors.affiliation: Institut für Theoretische Chemie, Universität Stuttgart, Stuttgart, Germany.
authors.forename: Toru
authors.initials: T
authors.lastname: Shiozaki
authors.forename: Hans-Joachim
authors.initials: HJ
authors.lastname: Werner