Picosecond laser control of bond-selective dissociation and clockwise and anticlockwise rotation of the dissociation fragments: applications to a three-dimensional model of HONO 2 in the ground electronic state

Abstract

Quantum dynamical simulations within the Schrödinger wave-function formalism have been performed for a three-dimensional (3-D) model of HONO 2 in the ground electronic state excited by linearly polarized shaped infrared (IR) laser pulses of picosecond (ps) and subpicosecond duration. The OH and the ON single bond stretches are explicitly treated together with the bending angle between them on the basis of the respective, ab initio defined, 3-D potential-energy surface and dipole function. Selective breaking of the ON single bond by optimally shaped IR laser pulses with more than 97% probability is demonstrated. Selective preparation of the clockwise and anticlockwise rotating OH fragments after the breakage of the ON single bond in HONO 2 by optimally designed subpicosecond IR laser pulses is demonstrated as well, with the respective branching ratio ranging from about 2.35 to 7.04. It is also demonstrated that optimally designed strong and short IR laser pulses can compete against intramolecular vibrational-enegry redistribution (IVR) and prepare a desirable molecular state.