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Electronic spectra of azaindole and its excited state mixing: A symmetry-adapted cluster configuration interaction study

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Title: Electronic spectra of azaindole and its excited state mixing: A symmetry-adapted cluster configuration interaction study
Authors: Arulmozhiraja, Sundaram Browse this author
Coote, Michelle L. Browse this author
Hasegawa, Jun-ya Browse this author
Issue Date: 28-Nov-2015
Publisher: American Institute of Physics (AIP)
Journal Title: Journal of chemical physics
Volume: 143
Issue: 20
Start Page: 204304-1
End Page: 204304-8
Publisher DOI: 10.1063/1.4935578
PMID: 26627956
Abstract: Electronic structures of azaindole were studied using symmetry-adapted cluster configuration interaction theory utilizing Dunning's cc-pVTZ basis set augmented with appropriate Rydberg spd functions on carbon and nitrogen atoms. The results obtained in the present study show good agreement with the available experimental values. Importantly, and contrary to previous theoretical studies, the excitation energy calculated for the important n-pi* state agrees well with the experimental value. A recent study by Pratt and co-workers concluded that significant mixing of pi-pi* and n-pi* states leads to major change in the magnitude and direction of the dipole moment of the upper state vibrational level in the 0,0 + 280 cm(-1) band in the S-1 <- S-0 transition when compared to that of the zero-point level of the S-1 state. The present study, however, shows that all the four lowest lying excited states, (1)Lb pi-pi*, La-1 pi-pi*, n-pi*, and pi-sigma*, cross each other in one way or another, and hence, significant state mixing between them is likely. The upper state vibrational level in the 0,0 + 280 cm(-1) band in the S-1 <- S-0 transition benefits from this four-state mixing and this can explain the change in magnitude and direction of the dipole moment of the S1 excited vibrational level. This multistate mixing, and especially the involvement of pi-sigma* state in mixing, could also provide a route for hydrogen atom detachment reactions. The electronic spectra of benzimidazole, a closely related system, were also investigated in the present study.
Rights: Copyright 2015 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 143, 204304 (2015) and may be found at http://scitation.aip.org/content/aip/journal/jcp/143/20/10.1063/1.4935578
Type: article
URI: http://hdl.handle.net/2115/60625
Appears in Collections:触媒科学研究所 (Institute for Catalysis) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 長谷川 淳也

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