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

TL;DR

This paper extends the J-diffusion model to include angular momentum dependence, revealing that nonequilibrium initial conditions cause slower decay of rotational correlation functions and coherent behavior in molecular rotation.

Contribution

The authors introduce a generalized J-diffusion model accounting for nonequilibrium conditions, highlighting significant differences from standard models in rotational dynamics predictions.

Findings

Rotational correlation functions decay slower far from equilibrium.

Hot molecules exhibit persistent coherent orientational behavior.

Rotational relaxation times follow Arrhenius energy dependence.

Abstract

In order to adequately describe molecular rotation far from equilibrium, we have generalized the J-diffusion model by allowing the rotational relaxation rate to be angular momentum dependent. The calculated nonequilibrium rotational correlation functions (CFs) are shown to decay much slower than their equilibrium counterparts, and orientational CFs of hot molecules exhibit coherent behavior, which persists for several rotational periods. As distinct from the results of standard theories, rotational and orientational CFs are found to dependent strongly on the nonequilibrium preparation of the molecular ensemble. We predict the Arrhenius energy dependence of rotational relaxation times and violation of the Hubbard relations for orientational relaxation times. The standard and generalized J-diffusion models are shown to be almost indistinguishable under equilibrium conditions. Far from equilibrium, their predictions may differ dramatically.