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

Abstract

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.