A Global Full-Dimensional Potential Energy Surface for the K₂Rb₂ Complex and its Lifetime
A full-dimensional global potential energy surface for the KRb + KRb → K2 + Rb2 reaction is developed from 20 »759 ab initio points calculated using a coupled cluster singles, doubles, and perturbative triples (CCSD(T)) method with effective core potentials, extrapolated to the complete basis set limit. The ab initio points are represented with high fidelity (root-mean-square error of 1.86 cm-1) using the permutation-invariant polynomial-neural network method, which enforces the permutation invariance of the potential with respect to exchange of identical nuclei. The potential energy surface features two D2h minima and one Cs minimum connected by the isomerization saddle points. The Rice-Ramsperger-Kassel-Marcus lifetime of the K2Rb2 reaction intermediate estimated using the potential energy surface is 227 ns, in reasonable agreement with the latest experimental measurement.
D. Yang et al., "A Global Full-Dimensional Potential Energy Surface for the K₂Rb₂ Complex and its Lifetime," Journal of Physical Chemistry Letters, vol. 11, no. 7, pp. 2605-2610, American Chemical Society (ACS), Apr 2020.
The definitive version is available at https://doi.org/10.1021/acs.jpclett.0c00518
Center for High Performance Computing Research
Keywords and Phrases
Binary alloys; Mean square error; Molecular physics; Numerical methods; Potential energy; Potential energy surfaces; Quantum chemistry; Reaction intermediates; Rubidium alloys, Complete basis set limit; Coupled-cluster singles; Effective core potential; Global potential energy surfaces; High-fidelity; Invariant polynomials; Rice-ramsperger-kassel-marcus; Root mean square errors, Potassium alloys, ab initio calculation; article; isomerization; nonhuman; rice
International Standard Serial Number (ISSN)
Article - Journal
© 2020 American Chemical Society (ACS), All rights reserved.
02 Apr 2020