This paper presents the parsctst code, an efficient parallel implementation of the semiclassical transition state theory (SCTST) for reaction rate constant calculations. Parsctst is developed starting from a previously presented approach for the computation of the vibrational density of states of fully coupled anharmonic molecules (Nguyen et al. Chem. Phys. Lett. 2010, 499, 915). The parallel implementation makes it practical to tackle reactions involving more than 100 fully coupled anharmonic vibrational degrees of freedom and also includes multidimensional tunneling effects. After describing the pseudocode and demonstrating its computational efficiency, we apply the new code for estimating the rate constant of the proton transfer isomerization reaction of the 2,4,6-tri-tert-butylphenyl to 3,5-di-tert-butylneophyl. Comparison with both theoretical and experimental results is presented. Parsctst code is user-friendly and provides a significant computational time saving compared to serial calculations. We believe that parsctst can boost the application of SCTST as an alternative to the basic transition state theory for accurate kinetics modeling not only in combustion or atmospheric chemistry, but also in organic synthesis, where bigger reactive systems are encountered.

Parallel Implementation of Semiclassical Transition State Theory / C. Aieta, F. Gabas, M. Ceotto. - In: JOURNAL OF CHEMICAL THEORY AND COMPUTATION. - ISSN 1549-9618. - 15:4(2019 Apr 09), pp. 2142-2153. [10.1021/acs.jctc.8b01286]

Parallel Implementation of Semiclassical Transition State Theory

C. Aieta
Primo
;
F. Gabas
Secondo
;
M. Ceotto
Ultimo
2019

Abstract

This paper presents the parsctst code, an efficient parallel implementation of the semiclassical transition state theory (SCTST) for reaction rate constant calculations. Parsctst is developed starting from a previously presented approach for the computation of the vibrational density of states of fully coupled anharmonic molecules (Nguyen et al. Chem. Phys. Lett. 2010, 499, 915). The parallel implementation makes it practical to tackle reactions involving more than 100 fully coupled anharmonic vibrational degrees of freedom and also includes multidimensional tunneling effects. After describing the pseudocode and demonstrating its computational efficiency, we apply the new code for estimating the rate constant of the proton transfer isomerization reaction of the 2,4,6-tri-tert-butylphenyl to 3,5-di-tert-butylneophyl. Comparison with both theoretical and experimental results is presented. Parsctst code is user-friendly and provides a significant computational time saving compared to serial calculations. We believe that parsctst can boost the application of SCTST as an alternative to the basic transition state theory for accurate kinetics modeling not only in combustion or atmospheric chemistry, but also in organic synthesis, where bigger reactive systems are encountered.
Settore CHIM/02 - Chimica Fisica
9-apr-2019
1-mar-2019
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/651960
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