Journal of Physical Chemistry A, Vol.104, No.21, 4882-4888, 2000
Competitive local laser control of photodissociation reaction HCo(CO)(4)-> HCo(CO)(3)+CO in electronic ground state
The performance of locally generated driving fields in the case of strong mode competition in two-dimensional models of the title reaction is investigated. The simulations are based on an all-Cartesian reaction surface Hamiltonian derived from ab initio quantum chemistry data. Here the one-dimensional reaction coordinate is defined by the Co-CO distance and motions of the HCo(CO)(3) fragment are described in the harmonic approximation. The influence of two substrate normal modes is investigated in detail. First, we consider the high-frequency H-Co stretching vibration, whose presence is shown to give no problem for driving the reaction coordinate. Second, we focus on a low-frequency umbrella-type mode involving the equatorial carbonyls. This mode provides a challenge to the method because of resonance and dipole gradient effects.