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On the consequences of nonremovable derivative couplings. I. The geometric phase and quasidiabatic states: A numerical study

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.472972· OSTI ID:397446
 [1]
  1. Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218 (United States)
Conical intersections complicate the computational treatment of nuclear dynamics in the adiabatic state basis through the geometric phase effect and singularities in the derivative couplings. The diabatic representation seeks to eliminate these difficulties. However, the adiabatic to diabatic state transformation is necessarily approximate in a polyatomic molecule since the derivative couplings cannot be rigorously removed. This point is rarely considered when constructing approximate diabatic states. The nonremovable part of the derivative couplings is investigated by considering the integral of the derivative coupling along closed loops in the vicinity of the 1{sup 2}{ital A}{prime}{endash}2{sup 2}{ital A}{prime} seam of conical intersections in H{sub 3}. {copyright} {ital 1996 American Institute of Physics.}
DOE Contract Number:
FG02-91ER14189
OSTI ID:
397446
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 105; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English