Molecular dynamics of pyrazine after excitation to the S2 electronic state using a realistic 24-mode model Hamiltonian

TLDR: In this article, a realistic model Hamiltonian including all 24 vibrational modes of the pyrazine molecule was presented, which determined the potential energy surfaces of the lowest two excited states, S1 and S2, which are strongly coupled to each other.

Abstract: The molecular dynamics of pyrazine after excitation to the S2 electronic state is investigated using the S2 absorption spectrum as a benchmark. We first present a realistic model Hamiltonian including all 24 vibrational modes of the pyrazine molecule. Using this model, we determined the potential energy surfaces of the lowest two excited states, S1 and S2, which are strongly coupled to each other. We then treated the nuclear motion of all 24 vibrational modes using the multiconfiguration time-dependent Hartree (MCTDH) wave packet propagation method. This method obtains results of good accuracy with acceptable computational effort for such a large system. The calculated spectrum is in good agreement with the experimental one. Furthermore, our results shed light on the role of the 20 modes which are only weakly coupled to the system, and demonstrate that essential physical features, such as symmetries, have to be considered when one wants to treat the molecular dynamics of pyrazine realistically.