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Variations in Duschinsky rotations in m-fluorotoluene and m-chlorotoluene during excitation and ionization

Davies, Alexander R.; Kemp, David J.; Warner, Lewis G.; Fryer, Elizabeth F.; Rees, Alan; Wright, Timothy G.

Variations in Duschinsky rotations in m-fluorotoluene and m-chlorotoluene during excitation and ionization Thumbnail


Authors

Alexander R. Davies

David J. Kemp

Lewis G. Warner

Elizabeth F. Fryer

Alan Rees

Timothy G. Wright



Abstract

We investigate Duschinsky rotation/mixing between three vibrations for both m-fluorotoluene (mFT) and m-chlorotoluene (mClT), during electronic excitation and ionization. In the case of mFT, we investigate both the S1 → S0 electronic transition and the D0+ ← S1 ionization, by two-dimensional laser-induced fluorescence (2D-LIF) and zero-electron-kinetic energy (ZEKE) spectroscopy, respectively; for mClT, only the D0+ ← S1 ionization was investigated, by ZEKE spectroscopy. The Duschinsky mixings are different in the two molecules, owing to shifts in vibrational wavenumber and variations in the form of the fundamental vibrations between the different electronic states. There is a very unusual behavior for two of the mFT vibrations, where apparently different conclusions for the identity of two S1 vibrations arise from the 2D-LIF and ZEKE spectra. We compare the experimental observations to the calculated Duschinsky matrices, finding that these successfully pick up the key geometric changes associated with each electronic transition and so are successful in qualitatively explaining the vibrational activity in the spectra. Experimental values for a number of vibrations across the S0, S1, and D0+ states are reported and found to compare well to those calculated. Assignments are made for the observed vibration-torsion (“vibtor”) bands, and the effect of vibrational motion on the torsional potential is briefly discussed.

Citation

Davies, A. R., Kemp, D. J., Warner, L. G., Fryer, E. F., Rees, A., & Wright, T. G. (2020). Variations in Duschinsky rotations in m-fluorotoluene and m-chlorotoluene during excitation and ionization. Journal of Chemical Physics, 152(21), Article 214303. https://doi.org/10.1063/5.0009391

Journal Article Type Article
Acceptance Date May 12, 2020
Online Publication Date Jun 1, 2020
Publication Date Jun 7, 2020
Deposit Date Jun 3, 2020
Publicly Available Date Jun 4, 2020
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 152
Issue 21
Article Number 214303
DOI https://doi.org/10.1063/5.0009391
Keywords Physical and Theoretical Chemistry; General Physics and Astronomy
Public URL https://nottingham-repository.worktribe.com/output/4569857
Publisher URL https://aip.scitation.org/doi/10.1063/5.0009391
Additional Information This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Journal of Chemical Physics and may be found at https://doi.org/10.1063/5.0009391

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