Laser control of the radiationless decay in pyrazine using the dynamic Stark effect
- Laboratoire Interdisciplinaire Carnot de Bourgogne UMR 6303 CNRS, Université de Bourgogne, BP 47870, F-21078 Dijon (France)
- CTMM, Institut Charles Gerhardt UMR 5253 CNRS, CC 15001, Université Montpellier 2, F-34095 Montpellier (France)
The laser control of the radiationless decay between the B{sub 3u}(nπ*) and B{sub 2u}(ππ*) states of pyrazine using the dynamic Stark effect has been investigated. A vibronic coupling model Hamiltonian in diabatic representation, including potential energy, transition dipole, and static polarizability surfaces as a function of the four most important vibrational modes of the molecule has been parametrized using multi-reference electronic structure calculations. The interaction of the molecule with a strong non-resonant laser pulse has been analyzed in terms of dressed potential energy surfaces. Because of the large polarizability difference between the vibronically coupled B{sub 3u}(nπ*) and B{sub 2u}(ππ*) states, the Stark effect induced by the non-resonant laser pulse shifts the conical intersection away from the Franck-Condon region. We have shown, by solving the time-dependent Schrödinger equation for the molecule interacting with a relatively weak pump pulse driving the electronic excitation from the ground state to the B{sub 2u}(ππ*) state, and a strong non-resonant control pulse, that this control mechanism can be used to trap the wavepacket on the B{sub 2u}(ππ*) potential energy surface for a much longer time than the natural B{sub 2u}(ππ*) lifetime.
- OSTI ID:
- 22254852
- Journal Information:
- Journal of Chemical Physics, Vol. 140, Issue 19; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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