Femtosecond Dynamics of Optically Induced Anisotropy of Complex Molecules in the Gas Phase

The evolution of optically induced anisotropy in an equilibrium ensemble of free asymmetric tops under collisionless conditions has been investigated theoretically and experimentally. The dynamics of the orientation correlation functions has been studied, the results of femtosecond experiments on measurement of relaxation of the optically induced anisotropy for perylene in the gas phase are presented, and their interpretation within the framework of the theory developed is given. It is shown that in contrast to stationary anisotropy, its time kinetics has more complete characteristic information about the dynamics of vector correlations in a molecular ensemble.