Photoinduced quantum dynamics of ortho- and para-fulvene: Hindered photoisomerization due to mode selective fast radiationless decay via a conical intersection
- Faculty of Pharmacy, Al-Quds University, POB 20002, Palestine (Country Unknown)
- Institut fuer Chemie und Biochemie, Freie Universitaet Berlin, 14195 Berlin (Germany)
- Department of Physical Chemistry and the Farkas Center for Light Induced Processes, The Hebrew University of Jerusalem, 91904 Jerusalem (Israel)
In this study, we investigate the photoinduced nonadiabatic dynamics of para- and ortho-fulvene by a combination of quantum chemical ab initio calculations and quantum dynamical simulations. We explore the competition between two different pathways, the photoisomerization and radiationless decay via a conical intersection (CI) at planar configuration. For this purpose, we extend a previous two-dimensional model which included the molecular torsion and the antisymmetric stretch as a coupling mode [Grohmann et al., Chem. Phys. 338, 252 (2007)] to a three-dimensional model, taking into account also the symmetric stretch as additional vibrational mode. Quantum dynamical simulations show that upon excitation with a single short laser pulse, the mode selective motion along the symmetric stretch drives the system to the CI, followed by radiationless decay before photoisomerization of fulvene can take place, thus confirming previous semiclassical calculations [Bearpark et al., J. Am. Chem. Soc. 118, 5253 (1996)]. Moreover, we show that the competition between photoisomerization and radiationless decay at a planar geometry depends on the nonadiabatic coupling strength.
- OSTI ID:
- 21255545
- Journal Information:
- Journal of Chemical Physics, Vol. 130, Issue 12; Other Information: DOI: 10.1063/1.3089546; (c) 2009 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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