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A combined time-resolved infrared and density functional theory study of the lowest excited states of 9-fluorenone and 2-naphthaldehyde

Abstract

A combined experimental and theoretical study of the infrared (IR) spectra of 2naphthaldehyde and 9-fluorenone in their ground and first excited singlet and triplet electronic states is presented. IR studies have also been carried out using supercritical krypton (scKr) as a solvent to measure spectra in the ground and triplet excited states. This solvent provides a weakly interacting environment that is closer to the gas phase and allows a direct comparison with the calculated spectra for a single molecule. The IR spectra for the three different states are computed with Kohn-Sham density functional theory. For the first excited singlet state it is necessary to use an overlap procedure that allows the excited state to be studied by preventing variational collapse to the ground state. This allows the excited singlet state to be studied in an analogous approach to the ground and excited triplet state, in contrast to using time-dependent density functional theory. The good agreement between the calculated excited state spectra and the experiment provides insight into the nature of the excited states. For the ground and excited triplet state the anharmonic vibrational frequencies are computed using the transition optimized shifted Hermite method, and for these molecules the hybrid B97-1 functional is found to provide the closest agreement with experiment in the ground state.

Journal Article Type Article
Publication Date Aug 17, 2018
Journal Chemical Physics
Print ISSN 0301-0104
Publisher Elsevier
Peer Reviewed Peer Reviewed
Volume 512
Pages 44-52
Institution Citation Hanson-Heine, M. W., Calladine, J. A., Yang, J., Towrie, M., Horvath, R., Besley, N. A., & George, M. W. (2018). A combined time-resolved infrared and density functional theory study of the lowest excited states of 9-fluorenone and 2-naphthaldehyde. Chemical Physics, 512, 44-52. doi:10.1016/j.chemphys.2018.04.014
DOI https://doi.org/10.1016/j.chemphys.2018.04.014
Keywords Physical and Theoretical Chemistry; General Physics and Astronomy
Publisher URL https://www.sciencedirect.com/science/article/pii/S0301010418300065
Additional Information This article is maintained by: Elsevier; Article Title: A combined time-resolved infrared and density functional theory study of the lowest excited states of 9-fluorenone and 2-naphthaldehyde; Journal Title: Chemical Physics; CrossRef DOI link to publisher maintained version: https://doi.org/10.1016/j.chemphys.2018.04.014; Content Type: article; Copyright: © 2018 Published by Elsevier B.V.

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