On the calculation of rotational anisotropy decay, as measured by ultrafast polarization-resolved vibrational pump-probe experiments.

Polarization-resolved vibrational pump-probe experiments are useful for measuring the dynamics of molecular reorientation. The rotational anisotropy observable is usually modeled by the second-Legendre-polynomial time-correlation function of the appropriate molecule-fixed unit vector. On the other hand, more elaborate calculations that include non-Condon effects, excited-state absorption, and spectral diffusion, can be performed using the infrastructure of the nonlinear response formalism. In this paper we present "exact" (within the impulsive limit) results from the nonlinear response formalism, and also a series of approximations that ultimately recover the traditional result mentioned above. To ascertain the importance of these effects not included in the traditional approach, we consider the specific case of dilute HOD in H(2)O. We find that for the frequency-integrated anisotropy decay, it is important to include non-Condon effects. For the frequency-resolved anisotropy decay, non-Condon effects, excited-state absorption, and spectral diffusion are all important. We compare our results with recent experiments.