Controlling the strong field fragmentation of ClCHO+ using two laser pulses -an ab initio molecular dynamics simulation.

ABSTRACT

For a single, intense 7 µm linearly polarized laser pulse, we found that the branching ratio for the fragmentation of ClCHO+ → Cl + HCO+ , H + ClCO+ , HCl+ +CO depended strongly on the orientation of the molecule (J. Phys. Chem. Lett. 2012, 3 2541). The present study explores the possibility of controlling the branching ratio for fragmentation by using two independent pulses with different frequencies, alignment and delay. Born-Oppenheimer molecular dynamics simulations in the laser field were carried out with the B3LYP/6-311G(d,p) level of theory using combinations of 3.5, 7 and 10.5 µm sine squared pulses with field strengths of 0.03 au (peak intensity of 3.15×1013 W/cm2 ) and lengths of 560 fs. A 3.5 µm pulse aligned with the C-H bond and a 10.5 µm pulse perpendicular to the C-H bond produced a larger branching ratio for HCl+ +CO than a comparable single 7 µm pulse. When the 10.5 µm pulse was delayed by one quarter of the pulse envelope, the branching ratio for the high energy product, (HCl+ +CO 73%) was a factor of three larger than the low energy product (Cl + HCO+ , 25%). By contrast, when the 3.5 µm pulse was delayed by one quarter of the pulse envelope, the branching ratio was reversed (HCl+ +CO 38%; Cl + HCO+ , 60%). Continuous wavelet analysis was used to follow the interaction of the laser with the various vibrational modes as a function of time. © 2018 Wiley Periodicals, Inc.