All mode dynamics at the conical intersection of an octa-atomic molecule: Multi-configuration time-dependent Hartree (MCTDH) investigation on the butatriene cation

The ground state and the first excited electronic states of the octa-atomic butatriene cation (C4H4+) exhibit a multidimensional conical intersection. This intersection is energetically low lying and is located in the vicinity of the Franck-Condon region of the neutral molecule's ground state. The conical intersection thus dominates the nuclear dynamics in ionization processes of this molecule. This is a particularly interesting example of vibronic coupling, introducing what appears to be a new, structured band into the energy spectrum. In this work, the potential energy surfaces and their intersection are investigated by ab initio methods. A diabatic model Hamiltonian including all possible linear, quadratic and bilinear vibronic coupling terms is introduced, with coupling constants determined by a fit to the ab initio data. The nuclear dynamics of all 18 vibrational modes is then evaluated by propagating the wave packet using the multi-configuration time-dependent Hartree method. Finally, the photoelectron spectrum of butatriene is computed and compared with the experimental one. (C) 2001 American Institute of Physics.