Laser-induced alignment dynamics of gas phase CS2 dimers

Rotational dynamics of gas phase carbon disulfide (CS2) dimers were induced by a moderately intense, circularly polarized alignment laser pulse and measured as a function of time by Coulomb explosion imaging with an intense fs probe pulse. For the alignment pulse, two different temporal intensity profiles were used: a truncated pulse with a 150 ps turn-on and a 8 ps turn-off or a ‘kick’ pulse with a duration of 1.3 ps. For both types of pulses, rich rotational dynamics with characteristic full and fractional revivals were recorded, showing that the intermolecular carbon-carbon axis periodically aligns along the propagation direction of the laser pulses. The truncated pulse gave the strongest alignment, which we rationalize as being due to a flat relative phase between the components in the rotational wave packet generated. Fourier analysis of the alignment dynamics gave well-spaced peaks which were fit to determine the rotational constant, B, and the centrifugal constant, DJ, for the ground state of the dimer. Our results agree with values from high-resolution IR spectroscopy. Numerical simulations of the alignment accurately reproduced the experimental dynamics when the truncated pulse or a low intensity kick pulse was used, but failed to reproduce the dynamics induced by a high intensity kick pulse. We posit that the discrepancy is due to excitation of the intermolecular torsional motion by the kick pulse.