Angular momentum dependent friction slows down rotational relaxation under nonequilibrium conditions

It has recently been shown that relaxation of the rotational energy of hot nonequilibrium photofragments (i) slows down significantly with the increase of their initial rotational temperature and (ii) differs dramatically from the relaxation of the equilibrium rotational energy correlation function, manifesting thereby the breakdown of the linear response description [ A. C. Moskun et al., Science 311, 1907 (2006) ]. We demonstrate that this phenomenon may be caused by the angular momentum dependence of rotational friction. We have developed the generalized Fokker–Planck equation whose rotational friction depends upon angular momentum algebraically. The calculated rotational correlation functions correspond well to their counterparts obtained via molecular dynamics simulations in a broad range of initial nonequilibrium conditions. It is suggested that the angular momentum dependence of friction should be taken into account while describing rotational relaxation far from equilibrium