A Brownian dynamics (BD) simulation for a pseudo-first-order diffusion-influenced reversible association–dissociation reaction of a target system in three dimensions with spherical symmetry is presented. The exact Green function for a reversible geminate dissociation that we obtained recently is utilized in the simulation. We compare the results of simulation with two successful theoretical predictions, the enhanced version of the superposition approximation approach (SA) and the more rigorous kinetic theoretical approach (KT). The KT predicts the correct power law behavior of ∼t−3/2 with a slightly higher amplitude in the long-time region, but it is in good agreement with the BD result in the transient region. On the other hand, a faster relaxation is observed in the transient region for the SA, but the correct power law behavior with numerically exact amplitude is predicted for the exact target system. An interesting interplay between the mobility of the system and the dynamic correlation effect incorporated with many-body problems is also revealed.
Dynamic correlation effect in reversible diffusion-influenced reactions: Brownian dynamics simulation in three dimensionsExcited-state diffusion-influenced reversible reaction, A*ϩB C*, is investigated in three dimensions by suitably modifying the Brownian dynamics simulation algorithm of Edelstein and Agmon ͓J. Chem. Phys. 99, 5396 ͑1993͔͒ which requires the exact Green functions of the geminate system. The proposed simulation algorithm is based on using the mixed look-up tables. For the excited bound state, the unimolecular decay is coupled to the reactive movement and its trajectory can be calculated with the aid of the excited-state look-up table. On the other hand, the unimolecular decay of the excited unbound state is assumed to be independent of the reactive movement and its trajectory is calculated with the ground-state look-up table. The optimum size of the time step is found by fitting simulations performed for the geminate case to the analytic result. The simulation results with varying concentration of B particles as well as the ratio of unimolecular decay constants are in excellent agreement with the kinetic theoretical predictions of Kwac et al. ͓J. Chem. Phys. 114, 3883 ͑2001͔͒.
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