Symmetry relations in chemical kinetics arising from microscopic reversibility

摘要

It is shown that the kinetics of time-reversible chemical reactions havingthe same equilibrium constant but different initial conditions are closelyrelated to one another by a directly measurable symmetry relation analogous tochemical detailed balance. In contrast to detailed balance, however, thisrelation does not require knowledge of the elementary steps that underlie thereaction, and remains valid in regimes where the concept of rate constants isill-defined, such as at very short times and in the presence of low activationbarriers. Numerical simulations of a model of isomerization in solution areprovided to illustrate the symmetry under such conditions, and potentialapplications in protein folding-unfolding are pointed out.