Theoretical investigation of intramolecular vibrational energy redistribution in HFCO and DFCO induced by an external field.

ABSTRACT

The present paper is devoted to a full quantum mechanical study of the intramolecular vibrational energy redistribution in HFCO and DFCO. In contrast to our previous studies [Pasin et al., J. Chem. Phys. 124, 194304 (2006) and 126, 024302 (2007)], the dynamics is now performed in the presence of an external time-dependent field. This more closely reflects the experimental conditions. A six-dimensional dipole surface is computed. The multiconfiguration time-dependent Hartree method is exploited to propagate the corresponding six-dimensional wave packets. Special emphasis is placed on the excitation of the out-of-plane bending vibration and on the dissociation of the molecule. In the case of DFCO, we predict that it is possible to excite the out-of-plane bending mode of vibration and to drive the dissociation to DF+CO with only one laser pulse with a fixed frequency and without excitation of an electronic state.