Renner-Teller/Jahn-Teller intersections along the collinear axes of polyatomic molecules: C2H2+ as a case study

TitleRenner-Teller/Jahn-Teller intersections along the collinear axes of polyatomic molecules: C2H2+ as a case study
Publication TypeJournal Article
Year of Publication2007
AuthorsHalasz GJ, Vibok A, Hoffman DK, Kouri DJ, Baer M
Journal TitleJournal of Chemical Physics
Volume126
Pages154309
Date PublishedApr
Type of ArticleArticle
ISBN Number0021-9606
Accession NumberISI:000245870900022
KeywordsANGULAR-MOMENTUM, COLLISIONS, DEGENERATE, DIABATIC REPRESENTATIONS, ELECTRONIC-STATE, GEOMETRIC PHASES, H+H-2 SYSTEM, NONADIABATIC COUPLING TERMS, ORBITAL, POTENTIAL-ENERGY SURFACES, TRIATOMIC-MOLECULES
Abstract

Recently we discussed the Renner-Teller effect in triatomic molecules [J. Chem. Phys. 125, 094102 (2006)]. In that article the main message is that the Renner-Teller phenomenon, just like the Jahn-Teller phenomenon, is a topological effect. Now we extend this study to a tetra-atomic system, namely, the C2H2+ ion, for which topological effects are revealed when one atom surrounds the triatom axis or when two atoms surround (at a time) the two-atom axis. The present study not only supports the findings of the previous study, in particular, the crucial role played by the topological D matrix for diabatization, but it also reveals new features which are expected to be more and more pronounced the larger the original collinear molecule. As already implied, shifting away two atoms from the collinear molecular axis does not necessarily abolish the ability of the remaining two atoms to form topological effects. Moreover, the study indicates that when the two hydrogens are shifted away, the CC axis produces two kinds of topological effects: (1) a Renner-Teller effect (characterized by a topological phase of 2 pi) which is revealed when the two hydrogens surround, rigidly, this axis (as mentioned above), and (2) a Jahn-Teller effect (characterized by a topological phase of pi) which is revealed when one of the hydrogens surrounds this axis while the other hydrogen is clamped to its position. (c) 2007 American Institute of Physics.

DOI10.1063/1.2717934
Alternate JournalJ. Chem. Phys.