Real-time probing of vectorial properties of ultra-fast photodissociations in liquids

Angular momentum dependent friction slows down rotational relaxation under nonequilibrium conditions

“…By combining the obtained dimensionless values of τ S at equilibrium (T ne = T = 120K) and at a certain temperature T ne > T we have used Eq. (19) to calculate the corresponding parameters ξ and b for N = 1, 2. The results of these calculations are summed up in Table 1.…”

“…Traditionally, polarization photodissociation experiments (both in the steady state and in the time domain) have been performed in the gas phase under collision-free conditions. 1,2 Recently, a number of "real time" measurements 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22 and computer simulations 23,24,25,26,27 has been reported, where the anisotropy decay of diatomic photoproducts was studied in the condensed phase. Both classical 28,29 and quantum 30 models of the anisotropy decay in the dissipative ensemble of photofragments have also been developed.…”

Manifestation of nonequilibrium initial conditions in molecular rotation: The generalized J-diffusion model

“…[27][28][29][30] In our previous paper, 26 we have demonstrated how the angular-momentum dependent friction can be incorporated into the rotational Fokker-Planck equation. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Third, we demonstrate how the use of standard "equilibrium" approaches may lead to quantitatively and even qualitatively wrong results, if they are applied to describe nonequilibrium molecular rotation. First, we investigate how the angular momentum dependent rates manifest themselves in relaxations of initial nonequilibrium distributions and in behaviors of rotational and orientational correlation functions ͑CFs͒.…”

“…for the interpretation of photofragment anisotropy decays. 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 Third, we demonstrate how the use of standard "equilibrium" approaches may lead to quantitatively and even qualitatively wrong results, if they are applied to describe nonequilibrium molecular rotation.…”

“…There have been collected many evidences (due to polarization time-resolved experiments, 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 computer simulations, 16,17,18,19,20,21 and model studies 21,22,23 ) which indicate that rotational and orientational relaxations of molecules in liquids under equilibrium and (highly) nonequilibrium conditions differ significantly. The studies of nonequilibrium rotational relaxation have recently culminated in papers.…”