Selective bond breaking mediated by state specific vibrational excitation in model HOD molecule through optimized femtosecond IR pulse: A simulated annealing based approach

TLDR: The selective control of O-H/O-D bond dissociation in reduced dimensionality model of HOD molecule has been explored through IR+UV femtosecond pulses and selectivity of the bond breaking by UV pulse (if required, optimized) together with optimized IR one is encouraging compared to the normal pulses.

Abstract: The selective control of O–H/O–D bond dissociation in reduced dimensionality model of HOD molecule has been explored through IR+UV femtosecond pulses. The IR pulse has been optimized using simulated annealing stochastic approach to maximize population of a desired low quanta vibrational state. Since those vibrational wavefunctions of the ground electronic states are preferentially localized either along the O–H or O–D mode, the femtosecond UV pulse is used only to transfer vibrationally excited molecule to the repulsive upper surface to cleave specific bond, O–H or O–D. While transferring from the ground electronic state to the repulsive one, the optimization of the UV pulse is not necessarily required except specific case. The results so obtained are analyzed with respect to time integrated flux along with contours of time evolution of probability density on excited potential energy surface. After preferential excitation from |0, 0⟩ (|m, n⟩ stands for the state having m and n quanta of excitations in O–H and O–D mode, respectively) vibrational level of the ground electronic state to its specific low quanta vibrational state (|1, 0⟩ or |0, 1⟩ or |2, 0⟩ or |0, 2⟩) by using optimized IR pulse, the dissociation of O–D or O–H bond through the excited potential energy surface by UV laser pulse appears quite high namely, 88% (O–H ; |1, 0⟩) or 58% (O–D ; |0, 1⟩) or 85% (O–H ; |2, 0⟩) or 59% (O–D ; |0, 2⟩). Such selectivity of the bond breaking by UV pulse (if required, optimized) together with optimized IR one is encouraging compared to the normal pulses.