Analysis of the Jahn-Teller Effect on the Spectrum and Structure of the NO3 Radical
Loading...
Date
2016-05
Authors
Journal Title
Journal ISSN
Volume Title
Publisher
The Ohio State University
Abstract
The magnitude of the Jahn-Teller effect in NO3 has been a large topic of research world-wide. The rotational structure of the perpendicular bands in the X <- A electronic spectrum of NO3 has been previously suggested to exhibit asymmetric top behavior. A rovibronic Hamiltonian has been developed to describe an oblate symmetric top under the influence of Jahn-Teller distortions, coriolis coupling, spin-rotation coupling, and spin-orbit coupling. The rotationally resolved, perpendicular transitions in the X <- A spectrum have been fit using this model and the results indicate that negligible to no Jahn-Teller distortions are observed in the rotational structure, inconsistent with the ab-initio analysis. The previous vibronic fit was also inconsistent with ab-initio results. In that analysis, the fit Hamiltonian includes up to second order Jahn-Teller coupling, whereas the ab-initio analysis considers up to quartic Jahn-Teller coupling. To pursue the vibronic discrepancy further, hypothetical spectra calculated from the ab-initio Hamiltonian have been fit using the quadratic Hamiltonian to determine the effects of higher order coupling terms in the fit parameters of the lower order model. The potentials of NO3 and Li3 were analyzed using this method. Extending upon this analysis, the effect of experimental error on fit parameters was analyzed by varying a set of computed levels in a way that mimics experimental error and fitting these levels. The distribution of fit parameters was studied.
Description
2015 Barry M. Goldwater Scholarship
2016 Denman Undergraduate Research Forum - Third Place, Mathematical and Physical Sciences
2016 Denman Undergraduate Research Forum - Third Place, Mathematical and Physical Sciences
Keywords
spectroscopy, Jahn-Teller, NO3, quantum mechanics, molecular structure, non-adiabatic