Exchange reactions in intense infrared laser fields
We examine the role of the dipole moment induced by an intense nonresonant infrared laser field on exchange reactions of the type A + BC→AB + C. This is compared to previous work which included the effect of the permanent dipole moment and its variation along the reaction coordinate. The formalism for laser-molecule interaction is developed for the cases where the reciprocal laser frequency is comparable to or much shorter than the time required for the system to cross the transition state. It is predicted that the induced dipole moment will both lower the electronic barrier to reaction and also create bound states along the reaction path. Results of classical trajectory calculations are presented for the collinear H + H2→H2+H reaction, using ab initio dipole moment and polarizability surfaces. It is found that the collisional energy threshold for reaction is lowered significantly, and that the effects of the induced dipole moment dominate over those of the permanent dipole moment. A time-dependent analysis of the reaction shows that the fluctuating barrier can occasionally be very low when the transition state is approached, allowing trajectories to be reactive with very low collision energies.
|Journal||Physical Review A - Atomic, Molecular, and Optical Physics|
Ivanov, M.Yu., Matusek, D.R., & Wright, J.S. (1996). Exchange reactions in intense infrared laser fields. Physical Review A - Atomic, Molecular, and Optical Physics, 54(6), 5159–5170. doi:10.1103/PhysRevA.54.5159