HCl and DCl: a case study of different approaches for determining photo fractionation constants.
The photoabsorption cross sections of HCl and DCl are calculated using the reflection principle and time dependent wavepacket propagation methods. The absorption cross sections are compared to high precision experimental absorption cross sections from the literature and the different results given by the methods are discussed. The results of the calculations emphasize the important roles that photodissociation dynamics and the change in transition dipole moment with internuclear distance play in isotopic fractionation. The wave number dependent fractionation constants have been determined. The process fractionation constant has been calculated in the Venusian atmosphere where photo-fractionation leads to enrichment in deuterium through loss of hydrogen to space. At an altitude of 70 km the process fractionation constant was found to be epsilon(p) = -344 per thousand and epsilon(p) = -256 per thousand for the experimental and the reflection principle methods, respectively. At the top of the atmosphere the process fractionation constant was evaluated to be epsilon(p) = -32 per thousand, epsilon(p) = -20 per thousand and epsilon(p) = -40 per thousand using the experimental data, the wavepacket and the reflection principle methods, respectively. Using the Rayleigh distillation formula it is concluded that HCl at the top of the Venusian atmosphere is fractionated (enriched in D) relative to the bulk composition prior to photolysis.
Grage
Mette M-L
MM
Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100, Copenhagen Ø, Denmark.
Nyman
Gunnar
G
Johnson
Matthew S
MS
D000042:Absorption; D000465:Algorithms; D001272:Atmosphere / Q000737:chemistry; D003903:Deuterium / Q000737:chemistry*; D005118:Extraterrestrial Environment; D006851:Hydrochloric Acid / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D010777:Photochemistry; D010782:Photolysis; D013057:Spectrum Analysis; D013997:Time Factors
D006859:Hydrogen; D003903:Deuterium; D006851:Hydrochloric Acid