Re-examining Einstein's $B$ coefficient and rate equations with the Rabi model

Abstract

Starting from the Rabi Hamiltonian, which is useful in arriving at non-perturbative results within the rotating wave approximation, we have found Einstein's $B$ coefficient to be time-dependent: $B(t)\propto|J_0(\omega_\gamma t)|$ for a two-level system (atom or molecule) in thermal radiation field. Here $\omega_\gamma$ is the corresponding Rabi flopping (angular) frequency and $J_0$ is the zeroth order Bessel function of the first kind. The resulting oscillations in the $B$ coefficient---even for very small $\omega_\gamma$---drives the system away from thermodynamic equilibrium at any finite temperature contrary to Einstein's assumption. The time-dependent generalized $B$ coefficient facilitates a path to go beyond Pauli's formalism of non-equilibrium statistical mechanics involving the quantum statistical Boltzmann (master) equation. In this context, we have obtained entropy production of the two-level system by revising Einstein's rate equations, while considering the $A$ coefficient to be the original time-independent one and the $B$ coefficient to be time-dependent.