Heavy Atom Tunneling in Organic Reactions at Coupled Cluster Potential Accuracy with a Parallel Implementation of Anharmonic Constant Calculations and Semiclassical Transition State Theory
Articolo
Data di Pubblicazione:
2022
Citazione:
Heavy Atom Tunneling in Organic Reactions at Coupled Cluster Potential Accuracy with a Parallel Implementation of Anharmonic Constant Calculations and Semiclassical Transition State Theory / G. Mandelli, C.D. Aieta, M. Ceotto. - In: JOURNAL OF CHEMICAL THEORY AND COMPUTATION. - ISSN 1549-9618. - 18:2(2022 Feb 08), pp. 623-637. [10.1021/acs.jctc.1c01143]
Abstract:
We describe and test on some organic reactions a parallel implementation strategy to compute anharmonic constants, which are employed in semiclassical transition state theory reaction rate calculations. Our software can interface with any quantum chemistry code capable of a single point energy estimate, and it is suitable for both minimum and transition state geometry calculations. After testing the accuracy and comparing the efficiency of our implementation against other software, we use it to estimate the semiclassical transition state theory (SCTST) rate constant of three reactions of increasing dimensionality, known as examples of heavy atom tunneling. We show how our method is improved in efficiency with respect to other existing implementations. In conclusion, our approach allows SCTST rates and heavy atom tunneling at a high level of electronic structure theory (up to CCSD(T)) to be evaluated. This work shows how crucial the possibility to perform high level ab initio rate evaluations can be.
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
G. Mandelli, C.D. Aieta, M. Ceotto
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