skip to main content

Title: The rate constant for radiative association of HF: Comparing quantum and classical dynamics

Radiative association for the formation of hydrogen fluoride through the A{sup 1}Π → X{sup 1}Σ{sup +} and X{sup 1}Σ{sup +} → X{sup 1}Σ{sup +} transitions is studied using quantum and classical dynamics. The total thermal rate constant is obtained for temperatures from 10 K to 20 000 K. Agreement between semiclassical and quantum approaches is observed for the A{sup 1}Π → X{sup 1}Σ{sup +} rate constant above 2000 K. The agreement is explained by the fact that the corresponding cross section is free of resonances for this system. At temperatures below 2000 K we improve the agreement by implementing a simplified semiclassical expression for the rate constant, which includes a quantum corrected pair distribution. The rate coefficient for the X{sup 1}Σ{sup +} → X{sup 1}Σ{sup +} transition is calculated using Breit–Wigner theory and a classical formula for the resonance and direct contributions, respectively. In comparison with quantum calculations the classical formula appears to overestimate the direct contribution to the rate constant by about 12% for this transition. Below about 450 K the resonance contribution is larger than the direct, and above that temperature the opposite holds. The biggest contribution from resonances is at the lowest temperature in the study, 10 K,more » where it is more than four times larger than the direct. Below 1800 K the radiative association rate constant due to X{sup 1}Σ{sup +} → X{sup 1}Σ{sup +} transitions dominates over A{sup 1}Π → X{sup 1}Σ{sup +}, while above that temperature the situation is the opposite.« less
Authors:
; ;  [1]
  1. Department of Chemistry and Molecular Biology, University of Gothenburg, 41296 Gothenburg (Sweden)
Publication Date:
OSTI Identifier:
22252894
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 18; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPARATIVE EVALUATIONS; CROSS SECTIONS; HYDROGEN FLUORIDES; REACTION KINETICS; RESONANCE; SEMICLASSICAL APPROXIMATION