Breakdown of energy transfer gap laws revealed by full-dimensional quantum scattering between HF molecules.

Abstract:

:Inelastic collisions involving molecular species are key to energy transfer in gaseous environments. They are commonly governed by an energy gap law, which dictates that transitions are dominated by those between initial and final states with roughly the same ro-vibrational energy. Transitions involving rotational inelasticity are often further constrained by the rotational angular momentum. Here, we demonstrate using full-dimensional quantum scattering on an ab initio based global potential energy surface (PES) that HF-HF inelastic collisions do not obey the energy and angular momentum gap laws. Detailed analyses attribute the failure of gap laws to the exceedingly strong intermolecular interaction. On the other hand, vibrational state-resolved rate coefficients are in good agreement with existing experimental results, validating the accuracy of the PES. These new and surprising results are expected to extend our understanding of energy transfer and provide a quantitative basis for numerical simulations of hydrogen fluoride chemical lasers.

journal_name

Nat Commun

journal_title

Nature communications

authors

Yang D,Huang J,Hu X,Guo H,Xie D

doi

10.1038/s41467-019-12691-8

subject

Has Abstract

pub_date

2019-10-11 00:00:00

pages

4658

issue

1

issn

2041-1723

pii

10.1038/s41467-019-12691-8

journal_volume

10

pub_type

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