Comment on ‘‘Non-Rice–Ramsperger–Kassel–Marcus dynamics and the statistics of reaction rates in chaotic systems’’ [J. Chem. Phys. 9 8, 7898 (1993)

Abstract

Results from chaos theory on the scarring of wave functions are applied to the problem of analyzing semiclassical reaction rates. Specifically, we show that uniform support of an eigenstate over the energy surface yields a Rice–Ramsperger–Kassel–Marcus (RRKM) estimate of the rate, while scarring of an eigenstate results in corrections to the RRKM rate due to periodic trajectories which recross the transition state. Non-RRKM behavior is also demonstrated for strongly averaged rates where recrossing effects are negligible.