On the form of the adiabatic and diabatic representation and the validity of the adiabatic approximation for X3 Jahn-Teller systems

Todd C. Thompson, Donald G Truhlar, C. Alden Mead

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Abstract

Starting with an expansion previously obtained for the adiabatic potential energy surfaces and derivative couplings for an X3 system in the vicinity of a D3h conical intersection, with the potential energy truncated at the second order in the distance from the intersection, and the derivative coupling carried to the highest order consistent with the existence of the "strictly diabatic" representation, we obtain the rigorous functional form to the same order of approximation for the diabatic representation of the same system. This diabatic representation is then applied to the reinterpretation of the recently observed laser-induced fluorescence spectrum of Cu3. In a more general context, the same functional form is used to estimate quantitatively the validity of the electronic adiabatic approximation, as a function of a unitless scale parameter, over a range of this parameter corresponding to several metal trimer systems. Some of the methods and results of this study are more general than the X3 systems to which most of the paper is addressed; we briefly indicate the possible extensions and implications for other systems.

Original languageEnglish (US)
Pages (from-to)2392-2407
Number of pages16
JournalThe Journal of chemical physics
Volume82
Issue number5
DOIs
StatePublished - Jan 1 1985

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