Global Full-Dimensional Potential Energy Surface for the Reaction 23Na87Rb + 23Na87Rb â 23Na2 + 87Rb2 and the Formation Rate and Lifetime of the 23Na287Rb2 Collision Complex.
J Phys Chem A
; 126(48): 9008-9021, 2022 Dec 08.
Article
em En
| MEDLINE
| ID: mdl-36417561
ABSTRACT
A full-dimensional global potential energy surface (PES) for the reaction 23Na87Rb + 23Na87Rb â 23Na2 + 87Rb2 was constructed based on high-level ab initio calculations. The short-range part was expressed as a permutation invariant polynomial-neural network (PIP-NN) fit of 22â¯003 ab initio points calculated using a coupled cluster method with the one-electron basis 5s5p5d2f plus effective core potentials and core polarizability potentials, while the long-range part was represented in an asymptotically correct form based on multipole expansion. The formation rate of the 23Na287Rb2 complex calculated using a quantum statistical method is in good agreement with experiment, while the estimated 19.20 µs lifetime of the complex from Rice-Ramsperger-Kassel-Marcus (RRKM) theory is significantly shorter than the measured millisecond decay rate, signaling either the inadequacy of RRKM theory or a yet unresolved loss mechanism.
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MEDLINE
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2022
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Article