TITLE

Electron spin resonance study on H6+, H5D+, H4D2+, and H2D4+ in solid parahydrogen

AUTHOR(S)
Kumagai, Jun; Inagaki, Hiroki; Kariya, Susumu; Ushida, Takahiro; Shimizu, Yuta; Kumada, Takayuki
PUB. DATE
July 2007
SOURCE
Journal of Chemical Physics;7/14/2007, Vol. 127 Issue 2, p024505
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
We carried out an electron spin resonance (ESR) study on hydrogen ion radicals produced by radiolysis of solid para-H2. In addition to quartet ESR lines proposed to be H2+-core H6+ (D2d) ions in solid para-H2 [T. Kumada et al., Phys. Chem. Chem. Phys. 7, 776 (2005)], we newly observed totally more than 50 resolved lines in γ-ray irradiated solid para-H2–ortho-D2 (1 mol %) and para-H2–HD (1 mol %) mixtures. We assigned these lines to be isotope substituents of H2+-core H6+ ions such as H5D+, H4D2+, and H2D4+ throughout the comparison of their ESR parameters with theoretical results. These results provide a conclusive evidence that H2+-core H6+ ions are generated in irradiated solid hydrogens. Analysis of the EPR spectrum and ab initio calculations predicts D2d symmetry of the H6+ ions, whereas a lowering symmetry (D2d→C2v) induced by asymmetric nuclear wave function is observed in H5D+ and H4D2+. We also observed isotope-substitution reactions such as H6++D2→H4D2++H2 and H6++HD→H5D++H2, which are analogous to the well-known isotope-condensation reactions of H3+ in dark nebula, H3++HD→HD2++H2 and HD2++HD→D3++H2.
ACCESSION #
25800428

 

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