Experimental and theoretical study of the photodissociation of bromo-3-fluorobenzene
- Department of Photochemistry and Molecular Science, Uppsala University, Box 523, SE-75120 Uppsala (Sweden)
The UV photodissociation of bromo-3-fluorobenzene under collisionless conditions has been studied as a function of the excitation wavelength between 255 and 265 nm. The experiments were performed using ultrafast pump-probe laser spectroscopy. To aid in the interpretation of the results, it was necessary to extend the theoretical framework substantially compared to previous studies, to also include quantum dynamical simulations employing a two-dimensional nuclear Hamiltonian. The nonadiabatic potential energy surfaces (PES) were parameterized against high-level MS-CASTP2 quantum chemical calculations, using both the C-Br distance and the out-of-plane bending of the bromine as nuclear parameters. We show that the wavelength dependence of the photodissociation via the S{sub 0}{yields}{sup 1}{pi}{pi}*{yields}{sup 1}{pi}{sigma}* channel, accessible with a {approx}260 nm pulse, is captured in this model. We thereby present the first correlation between experiments and theory within the quantitative regime.
- OSTI ID:
- 21024640
- Journal Information:
- Journal of Chemical Physics, Vol. 128, Issue 3; Other Information: DOI: 10.1063/1.2819093; (c) 2008 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Ultrafast absorption spectroscopy of photodissociated CF sub 2 Br sub 2 : Details of the reaction mechanism and evidence for anomalously slow intramolecular vibrational redistribution within the CF sub 2 Br intermediate
Dynamical insights into {sup 1}{pi}{sigma}* state mediated photodissociation of aniline