Infrared spectra of diatomic halogen complexes with hydrogen fluoride in solid argon and neon

Rodney D. Hunt, Lester Andrews

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Abstract

Chlorine was condensed at 12 K with HF in excess argon, which produced two 1:1 complexes of the form HF-Cl2 and Cl2-HF on the basis of infrared spectra. Increasing the HF concentration favored secondary 1:2 complexes with both (HF)2-Cl2 and Cl2-(HF)2 arrangements. The HF submolecule stretching frequency for the 1:1 anti-hydrogen-bonded complex was observed at 3902 cm-1; molecular beam electric resonance studies observed only the anti-hydrogen-bonded form, which ab initio studies predict is the more stable arrangement. The 1:1 hydrogen-bonded complex, which is similar to N2-HF, displayed an HF stretching fundamental at 3860 cm-1. With DF the hydrogen-bonded complex population fraction was substantially larger than with HF on the basis of infrared band absorbances. Similar results were obtained for chlorine monofluoride complexes with hydrogen fluoride and deuterium fluoride. In contrast, hydrogen fluoride and fluorine produced only one product complex, with an HF stretching mode at 3915 cm-1. This complex is identified as F2-HF on the basis of ab initio calculations. Photolysis of F2 and HF produced two new radical complexes, F-(HF) and F-(HF)2, with HF stretching modes at 3908 and 3901 cm-1 for HF2 and 3795 cm-1 for H2F3, which are markedly different from those of their anions. Similarly, the HF interaction with bromine and bromine monofluoride formed predominantly the hydrogen-bonded Br2-HF and FBr-HF complexes, respectively.

Original languageEnglish
Pages (from-to)3769-3774
Number of pages6
JournalJournal of Physical Chemistry
Volume92
Issue number13
DOIs
StatePublished - 1988
Externally publishedYes

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