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Kinetics and Dynamics pp 481–500Cite as

Tunneling Transmission Coefficients: Toward More Accurate and Practical Implementations

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Part of the book series: Challenges and Advances in Computational Chemistry and Physics ((COCH,volume 12))

Abstract

The accurate evaluation of quantum effects is of great importance in many reaction processes. Variational transition state theory with multidimensional tunneling is the natural choice for the study of these reactions, because it incorporates quantum effects through a multiplicative transmission coefficient and it can deal with large systems. Currently, the main approximation used for taking into account tunneling is the small-curvature approximation, mainly because the large curvature and the least-action approximations are computationally very demanding and their use it is usually associated to small systems. Here we describe two algorithms based on splines under tension, which allow the evaluation of these two transmission coefficients for large systems. The analysis of kinetic isotope effects on a model reaction show that the least-action transmission coefficient should be used instead of the more inexpensive, but probably less accurate small-curvature transmission coefficient.

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Authors and Affiliations

  1. Faculty of Chemistry, Department of Physical Chemistry, University of Santiago de Compostela, 15706, Santiago de Compostela, Spain

    Rubén Meana-Pañeda & Antonio Fernández-Ramos

Authors
  1. Rubén Meana-Pañeda
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  2. Antonio Fernández-Ramos
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Corresponding author

Correspondence to Antonio Fernández-Ramos .

Editor information

Editors and Affiliations

  1. Inst. Applied Radiation Chemistry, Dept. Chemistry, Technical University of Lodz, Zeromskiego 116, Lodz, 90-924, Poland

    Piotr Paneth

  2. Inst. Applied Radiation Chemistry, Dept. Chemistry, Technical University of Lodz, Zeromskiego 116, Lodz, 90-924, Poland

    Agnieszka Dybala-Defratyka

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Meana-Pañeda, R., Fernández-Ramos, A. (2010). Tunneling Transmission Coefficients: Toward More Accurate and Practical Implementations. In: Paneth, P., Dybala-Defratyka, A. (eds) Kinetics and Dynamics. Challenges and Advances in Computational Chemistry and Physics, vol 12. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-3034-4_18

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