Energies and derivative couplings in the vicinity of a conical intersection 3. The 'most' diabatic basis
Titel:
Energies and derivative couplings in the vicinity of a conical intersection 3. The 'most' diabatic basis
Auteur:
MATSUNAGA, NIKITA YARKONY, DAVID R.
Verschenen in:
Molecular physics
Paginering:
Jaargang 93 (1998) nr. 1 pagina's 79-84
Jaar:
1998-01-01
Inhoud:
It is shown that in the immediate vicinity of an arbitrary conical intersection at Rx all the derivative coupling, except for the small part due to the finiteness of the basis sets, is removable by the orthogonal transformation generated by the angle α(ρ, θ, z) = λ(θ)/2 + ρmp(θ)/q(θ) + zmz(θ)/q(θ), where ρ, θ,z are cylindrical polar coordinates centred at Rx. Expressions for λ(θ), q(θ), mp (θ) and mz (θ) are given. The implications of this result for numerical studies that (i) determine the 'most' diabatic basis using Poisson's equation and (ii) assess approximate diabatization schemes are discussed.
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