Diabatization around Conical Intersections with a New Phase-Corrected Valence-Bond-Based Compression Approach.

In the present work, the valence-bond-based compression approach for diabatization (VBCAD), previously presented in the literature [J. Phys. Chem. Lett. 2020, 11, 5295-5301] in the case of avoided crossings, is extended to the more general situation of conical intersections and their vicinity. A pointwise phase-correction scheme for diabatic states is proposed, based on the explicit use of the peculiarities of the nonorthogonality of ab initio valence bond (VB) theory. Rather than fitting or propagating nonadiabatic couplings, it allows us to determine the phase of diabatic states consistently and automatically at each geometry point. Moreover, it is shown that the undetermination of degenerate states around a conical intersection can be fixed naturally from a straightforward classical VB picture. These are illustrated with two prototypical symmetry-induced (Jahn-Teller) conical intersection models.