High-level ab initio electronic structure calculations are used to interpret the fragmentation dynamics of , following excitation with an intense ultrafast laser pulse. The potential energy surfaces of the ground and excited cationic states along the dissociative bond have been calculated using multireference second order perturbation theory methods. The calculations confirm the existence of a charge transfer resonance during the evolution of a dissociative wave packet on the ground state potential energy surface of the molecular cation and yield a detailed picture of the dissociation dynamics observed in earlier work. Comparisons of the ionic spectrum for two similar molecules support a general picture in which molecules are influenced by dynamic resonances in the cation during dissociation.
Interpreting ultrafast molecular fragmentation dynamics with ab initio electronic structure calculations
Carlos Trallero, Brett J. Pearson, Thomas Weinacht, Kandis Gilliard, Spiridoula Matsika; Interpreting ultrafast molecular fragmentation dynamics with ab initio electronic structure calculations. J. Chem. Phys. 28 March 2008; 128 (12): 124107. https://doi.org/10.1063/1.2850524
Download citation file: