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Issue 8, 2020
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Benchmark ab initio and dynamical characterization of the stationary points of reactive atom + alkane and SN2 potential energy surfaces

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Abstract

We describe a composite ab initio approach to determine the best technically feasible relative energies of stationary points considering additive contributions of the CCSD(T)/complete-basis-set limit, core and post-CCSD(T) correlation, scalar relativistic and spin–orbit effects, and zero-point energy corrections. The importance and magnitude of the different energy terms are discussed using examples of atom/ion + molecule reactions, such as X + CH4/C2H6 and X + CH3Y/CH3CH2Cl [X, Y = F, Cl, Br, I, OH, etc.]. We test the performance of various ab initio levels and recommend the modern explicitly-correlated CCSD(T)-F12 methods for potential energy surface (PES) developments. We show that the choice of the level of electronic structure theory may significantly affect the reaction dynamics and the CCSD(T)-F12/double-zeta PESs provide nearly converged cross sections. Trajectory orthogonal projection and an Eckart-transformation-based stationary-point assignment technique are proposed to provide dynamical characterization of the stationary points, thereby revealing front-side complex formation in SN2 reactions and transition probabilities between different stationary-point regions.

Graphical abstract: Benchmark ab initio and dynamical characterization of the stationary points of reactive atom + alkane and SN2 potential energy surfaces

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Article information


Submitted
05 Sep 2019
Accepted
06 Dec 2019
First published
06 Dec 2019

This article is Open Access

Phys. Chem. Chem. Phys., 2020,22, 4298-4312
Article type
Perspective

Benchmark ab initio and dynamical characterization of the stationary points of reactive atom + alkane and SN2 potential energy surfaces

G. Czakó, T. Győri, B. Olasz, D. Papp, I. Szabó, V. Tajti and D. A. Tasi, Phys. Chem. Chem. Phys., 2020, 22, 4298
DOI: 10.1039/C9CP04944D

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