title: Dissociation of H2NCH dication in a strong laser field.
abstract: Ab initio classical molecular dynamics calculations have been used to simulate the dissociation of H(2)NCH(2+) in a strong laser field. The frequencies of the continuous oscillating electric field were chosen to be ω = 0.02, 0.06, and 0.18 au (2280, 760, and 253 nm, respectively). The field had a maximum strength of 0.03 au (3.2 × 10(13) W cm(-2)) and was aligned with the CN bond. Trajectories were started with 100 kcal/mol of vibrational energy above zero point and were integrated for up to 600 fs at the B3LYP/6-311G(d,p) level of theory. A total of 200 trajectories were calculated for each of the three different frequencies and without a field. Two dissociation channels are observed: HNCH(+) + H(+) and H(2)NC(+) + H(+). About one-half to two-thirds of the H(+) dissociations occurred directly, while the remaining indirect dissociations occurred at a slower rate with extensive migration of H(+) between C and N. The laser field increased the initial dissociation rate by a factor of ca. 1.4 and decreased the half-life by a factor of ca. 0.75. The effects were similar at each of the three frequencies. The HNCH(+) to H(2)NC(+) branching ratio decreased from 10.6:1 in the absence of the field to an average of 8.4:1 in the laser field. The changes in the rates and branching ratios can be attributed to the laser field lowering the reaction barriers as a result of a difference in polarizability of the reactant and transition states.
authors.affiliation: Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA.
authors.forename: Jia
authors.initials: J
authors.lastname: Zhou
authors.forename: H Bernhard
authors.initials: HB
authors.lastname: Schlegel