Summary: Three-dimensional simulations of reversible bimolecular reactions.
III. The pseudo-unimolecular ABCD reaction
Alexander V. Popova)
and Noam Agmonb)
Department of Physical Chemistry and the Fritz Haber Research Center, The Hebrew University,
Jerusalem 91904, Israel
Received 22 January 2003; accepted 7 March 2003
We report a microscopic simulation for the reversible A B C D reaction in its
pseudo-unimolecular limit. The simulations are used to assess the validity of various approximate
theories for the time dependence of the approach to equilibrium, up to its long-time asymptotic
behavior. To available theories we have added a new theory, the generalized multiparticle kernel 1
GMPK1 theory. It is shown to be in very good agreement with our simulations than all other
theories. The asymptotic behavior of both simulations and GMPK1 agrees with that derived by
Gopich and Szabo Chem. Phys. 284, 91 2002 . © 2003 American Institute of Physics.
In the kinetics of reversible reactions, competition be-
tween particles couples their motion and renders the problem
difficult. Yet rapid recent advance in theoretical methods and
simulation techniques is making such problems trackable.