Microscopic reversibility and probability matrices for molecular collisions

An information theoretic procedure for the prediction of collision probability matrices subject to a dynamic constraint is derived, discussed and illustrated by an example. The novel point in the derivation is the imposition of the symmetry of time-reversal invariance as a rigorous kinematic constraint in the process of minimizing the entropy deficiency. The resulting probability matrix is thereby guaranteed to be strictly symmetric. The structure of the probability matrix, as derived here, relates the energy requirements and energy disposal of the same reaction.