Detailed Mechanism for Photoinduced Cytosine Dimerization: A Semiclassical Dynamics Simulation

Semiclassical dynamics simulation is used to study dimerization of two stacked cytosine molecules following excitation by ultrashort laser pulses (25 fs fwhm, Gaussian, 4.1 eV photon energy). The initial excited state was found to form an ultrashort exciton state, which eventually leads to the formation of an excimer state by charge transfer. When the interbase distance, defined as an average value of C-5-C-5' and C-6-C-6' CZ, becomes less than 3 angstrom, charge recombination occurs due to strong intermolecular interaction, eventually leading to an avoided crossing within 20-30 is. Geometries at the avoided crossing, with average intermolecular distance of about 2.1 angstrom, are in accord with CASSCF/CASPT2 calculations. Results indicate that the C-2-N-1-C-6-C-5 and C-2'-N-1'-C-6'-C-5' dihedral angles' bending vibrations play a significant role in the vibronic coupling between the HOMO and LUMO, which leads to a nonadiabatic transition to the electronic ground state.