A recently developed strategy for the computation at affordable cost of reliable barrier heights ruling reactions in the gas phase (junChS, [Barone, V.; et al. J. Chem. Theory Comput. 2021, 17, 4913−4928]) has been extended to the employment of explicitly correlated (F12) methods. A thorough benchmark based on a wide range of prototypical reactions shows that the new model (referred to as junChS-F12), which employs cost-effective revDSD-PBEP86-D3(BJ) reference geometries, has an improved performance with respect to its conventional counterpart and outperforms the most well-known model chemistries without the need of any empirical parameter and at an affordable computa- tional cost. Several benchmarks show that revDSD-PBEP86- D3(BJ) structures and force fields provide zero point energies and thermal contributions, which can be confidently used, together with junChS-F12 electronic energies, for obtaining accurate reaction rates in the framework of the master equation approach based on the ab initio transition-state theory.

Reliable gas phase reaction rates at affordable cost by means of the parameter-free junChS-F12 model chemistry

Barone, Vincenzo
;
Lupi, Jacopo;Salta, Zoi;Tasinato, Nicola
2023

Abstract

A recently developed strategy for the computation at affordable cost of reliable barrier heights ruling reactions in the gas phase (junChS, [Barone, V.; et al. J. Chem. Theory Comput. 2021, 17, 4913−4928]) has been extended to the employment of explicitly correlated (F12) methods. A thorough benchmark based on a wide range of prototypical reactions shows that the new model (referred to as junChS-F12), which employs cost-effective revDSD-PBEP86-D3(BJ) reference geometries, has an improved performance with respect to its conventional counterpart and outperforms the most well-known model chemistries without the need of any empirical parameter and at an affordable computa- tional cost. Several benchmarks show that revDSD-PBEP86- D3(BJ) structures and force fields provide zero point energies and thermal contributions, which can be confidently used, together with junChS-F12 electronic energies, for obtaining accurate reaction rates in the framework of the master equation approach based on the ab initio transition-state theory.
2023
Settore CHIM/02 - Chimica Fisica
Settore CHIM/12 - Chimica dell'Ambiente e dei Beni Culturali
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11384/140684
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