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Existence of strictly diabatic basis sets for the two‐state problem
Author(s) -
Kryachko Eugene S.,
Varandas António J. C.
Publication year - 2002
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.10297
Subject(s) - diabatic , basis (linear algebra) , orthogonality , coupling (piping) , basis set , transverse plane , state (computer science) , quantum mechanics , physics , gauge (firearms) , mathematical physics , theoretical physics , mathematics , adiabatic process , geometry , molecule , materials science , metallurgy , engineering , structural engineering , algorithm
Some new properties of the nonadiabatic coupling elements are derived, in particular the orthogonality and gauge invariance of their longitudinal and transverse components. A method for constructing a strictly diabatic basis set that makes both the transverse and longitudinal components of the nonadiabatic coupling elements of the two‐state problem vanish identically and is based on introducing overlap between the electronic states in the vicinity of the crossing seam is proposed. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002