Invariants of the dynamics of molecular vibrational wave packets in phase modulation

Abstract

An exact analytic solution was obtained for the correlation function of the motion of a phase-modulated Gauss wave packet in an anharmonic potential. The solution is expressed through the theta-function with the parameters depending on both the potential and phase modulation of the initial wave packet. Changes in both linear and quadratic chirps result in an invariant correlation function time shift in a weakly anharmonic potential with the conservation of all the total and fractional revivals. At a strong potential anharmonicity, translational invariance with respect to a quadratic chirp is preserved in certain instances, whereas the dynamics of packets experiences qualitative changes depending on linear phase modulation. This approach can be used to qualitatively analyze intramolecular dynamics if the potential energy surface is not known exactly, which is especially useful for quantum control of large molecules, in particular, photochromes.