Modified Kramers formulas for the decay rate in agreement with dynamical modeling
AbstractAccuracy of the Kramers approximate formulas for the thermal decay rate of the metastable state is studied for the anharmonic shapes of the potential pocket and the barrier. This is done by the comparison with the quasistationary rate resulting from the dynamical modeling. Disagreement between the Kramers rate and the dynamical one is shown to reach 15% in the cases when much better agreement is expected. Corrections to the Kramers formulas accounting for the higher derivatives of the potential are obtained. The small parameters are the ratios of the thermal energy to the stiffnesses at the extremes of the potential. The distance between the potential barrier and the absorptive border is accounted for as well. This corrected Kramers rate is demonstrated to agree with the dynamical rate typically within 2%. Probably the most interesting result is that despite the corrections are derived in the case of the overdamped Brownian motion, the above 2% agreement holds even in the case of medium friction.
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Bibliographic InfoArticle provided by Elsevier in its journal Physica A: Statistical Mechanics and its Applications.
Volume (Year): 391 (2012)
Issue (Month): 23 ()
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Web page: http://www.journals.elsevier.com/physica-a-statistical-mechpplications/
Metastable system; Decay rate; Kramers rate; Corrections to Kramers formulas;
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- Edholm, O. & Leimar, O., 1979. "The accuracy of Kramers' theory of chemical kinetics," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 98(1), pages 313-324.
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