Ab initio quantum dynamical study of photoinduced ring opening in furan

• Verfasst von: Gromov, Evgeniy [VerfasserIn]
• Verfasst von: Lévêque, C. [VerfasserIn]
• Verfasst von: Gatti, F. [VerfasserIn]
• Verfasst von: Burghardt, I. [VerfasserIn]
• Verfasst von: Köppel, Horst [VerfasserIn]
• Titel: Ab initio quantum dynamical study of photoinduced ring opening in furan
• Verf.angabe: E. V. Gromov, C. Lévêque, F. Gatti, I. Burghardt, and H. Köppel
• E-Jahr: 2011
• Jahr: 26 October 2011
• Umfang: 11 S.
• Fussnoten: Gesehen am 11.07.2022
• Titel Quelle: Enthalten in: The journal of chemical physics
• Ort Quelle: Melville, NY : American Institute of Physics, 1933
• Jahr Quelle: 2011
• Band/Heft Quelle: 135(2011), 16, Artikel-ID 164305, Seite 1-11
• ISSN Quelle: 1089-7690
• DOI: doi:10.1063/1.3653792
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1809790530

Abstract

The nonadiabatic photoinduced ring opening occurring in the two lowest excited singlet states of furan is investigated theoretically, using wave-packet propagation techniques. The underlying multidimensional potential energy surfaces (PESs) are obtained from ab initio computations, using the equation-of-motion coupled cluster method restricted to single and double excitations (EOM-CCSD), reported in earlier recent work [E. V. Gromov, A. B. Trofimov, F. Gatti, and H. Köppel, J. Chem. Phys. 133, 164309 (2010) https://doi.org/10.1063/1.3493451.]. Up to five nuclear degrees of freedom are considered in the quantum dynamical treatment. Four of them represent in-plane motion for which the electronic states in question (correlating with the valence 1B2(V) and Rydberg 1A2(3s) states at the C2v ground-state molecular configuration) have different symmetries, A′ and A′′, respectively. The fifth mode, representing out-of-plane bending of the oxygen atom against the carbon-atom plane, leads to an interaction of these states, as is crucial for the photoreaction. The nonadiabatic coupling and conical intersection cause an electronic population transfer on the order of ∼10 fs. Its main features, and that of the wave-packet motion, are interpreted in terms of properties of the PES. The lifetime due to the ring-opening process has been estimated to be around 2 ps. The dependence of this estimate on the nuclear degrees of freedom retained in the computations is discussed.