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Molecular Eigensolution Symmetry Analysis and Fine Structure
Department of Physics, University of Arkansas, Fayetteville, AR 72701, USA
Intel Corporation, Santa Clara, CA 95054, USA
* Author to whom correspondence should be addressed.
Received: 3 September 2012; in revised form: 26 November 2012 / Accepted: 27 November 2012 / Published: 4 January 2013
Abstract: Spectra of high-symmetry molecules contain fine and superfine level cluster structure related to J-tunneling between hills and valleys on rovibronic energy surfaces (RES). Such graphic visualizations help disentangle multi-level dynamics, selection rules, and state mixing effects including widespread violation of nuclear spin symmetry species. A review of RES analysis compares it to that of potential energy surfaces (PES) used in Born-Oppenheimer approximations. Both take advantage of adiabatic coupling in order to visualize Hamiltonian eigensolutions. RES of symmetric and D2 asymmetric top rank-2-tensor Hamiltonians are compared with Oh spherical top rank-4-tensor fine-structure clusters of 6-fold and 8-fold tunneling multiplets. Then extreme 12-fold and 24-fold multiplets are analyzed by RES plots of higher rank tensor Hamiltonians. Such extreme clustering is rare in fundamental bands but prevalent in hot bands, and analysis of its superfine structure requires more efficient labeling and a more powerful group theory. This is introduced using elementary examples involving two groups of order-6 (C6 and D3~C3v), then applied to families of Oh clusters in SF6 spectra and to extreme clusters.
Keywords: symmetry; molecular dynamics; tunneling; level clusters
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MDPI and ACS Style
Harter, W.G.; Mitchell, J.C. Molecular Eigensolution Symmetry Analysis and Fine Structure. Int. J. Mol. Sci. 2013, 14, 714-806.
Harter WG, Mitchell JC. Molecular Eigensolution Symmetry Analysis and Fine Structure. International Journal of Molecular Sciences. 2013; 14(1):714-806.
Harter, William G.; Mitchell, Justin C. 2013. "Molecular Eigensolution Symmetry Analysis and Fine Structure." Int. J. Mol. Sci. 14, no. 1: 714-806.