Effect of Vibrational Pre-Excitation on the Dissociation Dynamics of HOD(2+)

Preferential breaking of chemical bonds using few-cycle, intense laser pulse to obtain desired products offer a formidable challenge in understanding ultrafast chemical reactivity. In a recent study [J. Chem. Phys. 2015, 143, 244310], it was found that carrier-envelope phase influences the bond-selective fragmentation in HOD with up to 3-fold enhancement. We present a detailed theoretical study to understand the influence of initial vibrational states governing the dissociation dynamics. We have carried out a time-dependent quantum mechanical wave packet study on the ground electronic state (X̃ (3)B1) of HOD(2+). Analytical potential energy surface for the ground electronic states of both the neutral molecule and dication has been developed at multireference configuration interaction level of theory with aug-cc-pVQZ basis set. Branching ratio is computed from the accumulated flux in H(+) + OD(+) and D(+) + OH(+) dissociation channels. Our investigation demonstrate a strong dependency on the initial conditions, and thereby preferential cleavage of bonds can be achieved. We have also compared our results with experimental and other theoretical studies.