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A simple quasi-diabatization scheme suitable for spectroscopic problems based on one-electron properties of interacting states

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4940426· OSTI ID:22493711

We present a simple quasi-diabatization scheme applicable to spectroscopic studies that can be applied using any wavefunction for which one-electron properties and transition properties can be calculated. The method is based on rotation of a pair (or set) of adiabatic states to minimize the difference between the given transition property at a reference geometry of high symmetry (where the quasi-diabatic states and adiabatic states coincide) and points of lower symmetry where quasi-diabatic quantities are desired. Compared to other quasi-diabatization techniques, the method requires no special coding, facilitates direct comparison between quasi-diabatic quantities calculated using different types of wavefunctions, and is free of any selection of configurations in the definition of the quasi-diabatic states. On the other hand, the method appears to be sensitive to multi-state issues, unlike recent methods we have developed that use a configurational definition of quasi-diabatic states. Results are presented and compared with two other recently developed quasi-diabatization techniques.

OSTI ID:
22493711
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 144; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English

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