D matrix analysis of the Renner-Teller effect: An accurate three-state diabatization for NH2

G. J. Halász*, Á Vibók, R. Baer, M. Baer

*Corresponding author for this work

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Some time ago we published our first article on the Renner-Teller (RT) model to treat the electronic interaction for a triatomic molecule [J. Chem. Phys. 124, 081106 (2006)]. The main purpose of that Communication was to suggest considering the RT phenomenon as a topological effect, just like the Jahn-Teller phenomenon. However, whereas in the first publication we just summarized a few basic features to support that idea, here in the present article, we extend the topological approach and show that all the expected features that characterize a three (multi) state RT-type'3 system of a triatomic molecule can be studied and analyzed within the framework of that approach. This, among other things, enables us to employ the topological D matrix [Phys. Rev. A 62, 032506 (2000)] to determine, a priori, under what conditions a three-state system can be diabatized. The theoretical presentation is accompanied by a detailed numerical study as carried out for the HNH system. The D-matrix analysis shows that the two original electronic states 2A1 and 2B1 (evolving from the collinear degenerate II doublet), frequently used to study this Renner-Teller-type system, are insufficient for diabatization. This is true, in particular, for the stable ground-state configurations of the HNH molecule. However, by including just one additional electronic state - a B state (originating from a collinear ∑ state) - it is found that a rigorous, meaningful three-state diabatization can be carried out for large regions of configuration space, particularly for those, near the stable configuration of NH2. This opens the way for an accurate study of this important molecule even where the electronic angular momentum deviates significantly from an integer value.

Original languageAmerican English
Article number094102
JournalJournal of Chemical Physics
Issue number9
StatePublished - 2006

Bibliographical note

Funding Information:
Three of the authors (M.B., Á.V., and G.J.H) acknowledge the US-Israel Bi-national Science Foundation for partly supporting this study. One of the authors (Á.V.) acknowledges the OTKA Grant Nos. T037994 and M041537 and the computational resources provided by the John-von-Neumann Institute, Research Centre Juelich (Project ID ehu01).


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