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Three-dimensional simulations of reversible bimolecular reactions. II. The excited-state target problem with different lifetimes
 

Summary: Three-dimensional simulations of reversible bimolecular reactions.
II. The excited-state target problem with different lifetimes
Alexander V. Popova)
and Noam Agmonb)
Department of Physical Chemistry and the Fritz Haber Research Center, The Hebrew University,
Jerusalem 91904, Israel
Received 20 March 2002; accepted 4 June 2002
We report a first microscopic simulation for the diffusional kinetics of a reversible excited-state
reaction, A B AB, where A and AB have different lifetimes and the B-particles are in excess.
When the excited species equilibrate fast compared with the excited-state lifetimes, one obtains the
pre-equilibrium approximation. The full time-dependence in this case is approximated by a shifted
infinite-lifetime expression, and this allows us to derive an analytic expression for the asymptotic
exponent. Multiplying this exponential is a t 3/2
term. When the excited-state decay of AB is fast,
we obtain the quasistationary approximation. Quantitative comparison between various theories and
simulation is presented. 2002 American Institute of Physics. DOI: 10.1063/1.1496455
I. INTRODUCTION
Bimolecular reactivity in solution is more complex than
most chemists care to admit. The chemical rate equations1
describe a special limit when diffusion is very fast as com-

  

Source: Agmon, Noam - Institute of Chemistry, Hebrew University of Jerusalem

 

Collections: Chemistry