CONTROL OF ISOMERIZATIONS BY SERIES OF ULTRAFAST INFRARED-LASER PULSES - MODEL SIMULATIONS FOR SEMIBULLVALENES

Model simulations of laser-driven Cope rearrangements of non-degenerate semibullvalene isotopomers are carried out by fast Fourier transform propagations of representative wavepackets. High selectivities for the isomerization reactions, with reaction probabilities > 80% for specific isotopomers, are achieved by series of picosecond IR laser pulses with analytical (Gaussian) shapes. The laser-induced reaction proceeds in a shallow double-well potential representing the electronic ground state, from the vibrational ground state of the reactant isomer via a delocalized state with energy close to the potential barrier towards a vibrationally excited product state.