On the preservation of coherence in the electronic wavepacket of a neutral and rigid polyatomic molecule

Abstract

We present various types of reduced models including five vibrational modes and three electronic states for the pyrazine molecule in order to investigate the lifetime of electronic coherence in a rigid and neutral system. Using an ultrafast optical pumping in the ground state (1 1 Ag), we prepare a coherent superposition of two bright excited states, 1 1 B2u and 1 1 B1u, and reveal the effect of the nuclear motion on the preservation of the electronic coherence induced by the laser pulse. More specifically, two aspects are considered: the anharmonicity of the potential energy surfaces and the dependence of the transition dipole moments (TDMs) with respect to the nuclear coordinates. To this end, we define an ideal model by making three approximations: (i) only the five totally symmetric modes move, (ii) which correspond to uncoupled harmonic oscillators, and (iii) the TDMs from the ground electronic state to the two bright states are constant (Franck-Condon approximation). We then lift the second and third approximations by considering, first, the effect of anharmonicity, second, the effect of coordinate-dependence of the TDMs (first-order Herzberg-Teller contribution), third, both. Our detailed numerical study with quantum dynamics confirms long-term revivals of the electronic coherence even for the most realistic model.