Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 12, Issue 7, Pages 1885-1892Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.0c03506
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Funding
- National Natural Science Foundation of China [21733008, 21973077]
- 111 Project [B17027]
- New Century Excellent Talents in Fujian Province University
- Fundamental Research Funds for the Central Universities [20720190046]
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This study extends the valence-bond-based compression approach for diabatization to the more general situation of conical intersections and introduces a pointwise phase-correction scheme for diabatic states. The undetermination of degenerate states around a conical intersection can be fixed naturally from a classical VB picture.
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.
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