| Autor: |
Barone V; SMART Laboratory, Scuola Normale Superiore di Pisa, Piazza dei Cavalieri 7, 56125 Pisa, Italy., Lupi J; SMART Laboratory, Scuola Normale Superiore di Pisa, Piazza dei Cavalieri 7, 56125 Pisa, Italy., Salta Z; SMART Laboratory, Scuola Normale Superiore di Pisa, Piazza dei Cavalieri 7, 56125 Pisa, Italy., Tasinato N; SMART Laboratory, Scuola Normale Superiore di Pisa, Piazza dei Cavalieri 7, 56125 Pisa, Italy. |
| Abstrakt: |
A recently developed strategy for the computation at affordable cost of reliable barrier heights ruling reactions in the gas phase (junChS, [Barone, V.; 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 computational 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. |
