An efficient algorithm for capturing quantum effects in classical reactive scattering: application to D + H3+ → H2D+ + H

• Published in: Physical chemistry chemical physics : PCCP Vol. 25; no. 3; pp. 1602 - 1605
• Main Authors: Braunstein, Matthew, Bonnet, Laurent
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 01.01.2023
• Subjects: Algorithms; Chemical reactions; Molecular dynamics; Rate constants; Scattering; Zero point energy
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d2cp05108g

Motivated by a recent semiclassical analysis of chemical reaction thresholds [Bonnet et al., J. Chem. Phys., 2022, 157, 094114], we present an efficient algorithm for including zero-point energy (ZPE) effects in classical reactive scattering. The algorithm is an extension of the quasi-classical trajectory (QCT) Gaussian binning method. We apply it to the astrophysically important D + H3+ reaction, where there are significant quantum effects and where application of other methods is problematic [Braunstein et al., Phys. Chem. Chem. Phys., 2022, 24, 5489]. The rate constants computed with the new, general algorithm closely match recent Ring Polymer Molecular Dynamics (RPMD) [Bulut et al., J. Phys. Chem. A, 2019, 123, 8766] and experimentally derived [Bowen et al., J. Chem. Phys., 2021, 154, 084307] ones spanning ∼4 orders of magnitude from 70 to 1500 K.