Deep nuclear resonant tunneling thermal rate constant calculations

Authors

  • Salvatore Mandrà,

    Corresponding author
    1. Dipartimento di Fisica, Università degli Studi di Milano, via Celoria 16, 20133 Milano, Italy
    • Dipartimento di Chimica, Università degli Studi di Milano, via Golgi 19, 20133 Milano, Italy
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  • Stéphanie Valleau,

    1. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138
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  • Michele Ceotto

    Corresponding author
    1. Dipartimento di Chimica, Università degli Studi di Milano, via Golgi 19, 20133 Milano, Italy
    • Dipartimento di Chimica, Università degli Studi di Milano, via Golgi 19, 20133 Milano, Italy
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Abstract

A fast and robust time-independent method to calculate thermal rate constants in the deep resonant tunneling regime for scattering reactions is presented. The method is based on the calculation of the cumulative reaction probability which, once integrated, gives the thermal rate constant. We tested our method with both continuous (single and double Eckart barriers) and discontinuous first derivative potentials (single and double rectangular barriers). Our results show that the presented method is robust enough to deal with extreme resonating conditions such as multiple barrier potentials. Finally, the calculation of the thermal rate constant for double Eckart potentials with several quasi-bound states and the comparison with the time-independent log-derivative method are reported. An implementation of the method using the Mathematica Suite is included in the Supporting Information. © 2013 Wiley Periodicals, Inc.

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