Show simple item record

dc.creatorNagesh, Jayashreeen_US
dc.creatorSibert, E. L., IIIen_US
dc.date.accessioned2010-07-12T14:18:25Z
dc.date.available2010-07-12T14:18:25Z
dc.date.issued2010en_US
dc.identifier2010-RJ-04en_US
dc.identifier.urihttp://hdl.handle.net/1811/46306
dc.descriptionAuthor Institution: Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin-Madison, WI 53706en_US
dc.description.abstractThe Jahn-Teller type of degeneracy in electronic states in polyatomic molecules greatly affects its vibrational dynamics. The methoxy free radical possesses $C_{3v}$ symmetry at the Jahn-Teller conical intersection ($\tilde{X}^{2}E$) and provides an ideal system for understanding how the Jahn-Teller phenomenon affects the dynamics. Despite many efforts to clearly elucidate the dynamics, calculation of the potential hypersurface and vibronic states in the molecule remains a theoretical challenge. We adopt a diabatic framework to describe the 9-dimensional hypersurface, which allows us to treat the dynamics in a more straightforward manner. A 9-dimensional force field is calculated for both the $\tilde{A}^{2}A_{1}$ and $\tilde{X}^{2}E$ surfaces using various levels of theory and basis sets. Quartic and quadratic force fields, expressed in internal coordinates, are obtained for the ground and excited states, respectively. The least squares fit was obtained solely using points with $C_s$ symmetry, yet is shown to agree well with {\it ab initio} points obtained at lower symmetry. The Hamiltonian is shown to take on a particularly simple form when expressed in terms of circular raising and lowering operators for both the electronic and vibrational degrees of freedom. The variational calculation in the diabatic representation is carried out in a series of prediagonalization steps, adding vibrational degrees of freedom in a systematic manner. Theoretical and experimental fundamental frequencies are shown to be in good agreement.en_US
dc.language.isoenen_US
dc.publisherOhio State Universityen_US
dc.titleNINE DIMENSIONAL THEORETICAL STUDIES ON METHOXY FREE RADICALen_US
dc.typeArticleen_US


Files in this item

Thumbnail

Items in Knowledge Bank are protected by copyright, with all rights reserved, unless otherwise indicated.

This item appears in the following Collection(s)

Show simple item record