6533b7d4fe1ef96bd1262973

RESEARCH PRODUCT

Full-dimensional control of the radiationless decay in pyrazine using the dynamic Stark effect

Benjamin LasorneStéphane GuérinMohamad SaabFabien GattiMatthieu Sala

subject

010304 chemical physicsChemistryWave packetDiabaticGeneral Physics and AstronomyHartree010402 general chemistry01 natural sciencesPotential energy0104 chemical sciences[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistryVibronic couplingsymbols.namesakeStark effectQuantum mechanicsExcited state[ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry0103 physical sciencesPotential energy surfacesymbolsPhysics::Atomic PhysicsPhysics::Chemical PhysicsPhysical and Theoretical ChemistryAtomic physicsComputingMilieux_MISCELLANEOUS

description

We present a full quantum-mechanical study of the laser control of the radiationless decay between the B3u(nπ(*)) and B2u(ππ(*)) states of pyrazine using the dynamic Stark effect. In contrast to our previous study [Sala et al., J. Chem. Phys. 140, 194309 (2014)], where a four-dimensional model was used, all the 24 degrees of freedom are now included in order to test the robustness of the strategy of control. Using a vibronic coupling Hamiltonian model in a diabatic representation, the multi-layer version of the multi-configuration time-dependent Hartree method is exploited to propagate the corresponding wave packets. We still observe a trapping of the wavepacket on the B2u(ππ(*)) potential energy surface due to the Stark effect for a longer time than the "non-resonant field-free" B2u(ππ(*)) lifetime.

https://doi.org/10.1063/1.4896938