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Structure of N2H4.+ formed in X-irradiated Li(N2H5)SO4 single crystals
Linköping University, The Institute of Technology. Linköping University, Department of Physics, Chemistry and Biology, Chemical Physics .
Department of Physics, University of Oslo, N-0316 Oslo, Norway.
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2000 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 2, no 1, 37-42 p.Article in journal (Refereed) Published
Abstract [en]

X-irradiated Li(N2H5)SO4 single crystals were investigated using ESR and ENDOR spectroscopy at several temperatures. The hydrazine radical cation N2H4.+ was selectively produced by irradiation at room temperature. From the analysis of the orientation dependent ENDOR spectra, the 1H-hfc tensors of the cation radical were precisely obtained and the radical structure was supported by theoretical calculations. It is suggested that the cation radical has a planar p* structure D(2h) (2B(2g)) in the crystal down to 230 K. By using the evaluated 1H-hf tensor the powder ESR line shape was successfully simulated. Concomitant with the radical formation, the N-N bond of N2H4.+ is suggested to reorient so as to optimize hydrogen bond interactions. 1H-ENDOR line splitting for the N2H4.+ radical was observed at temperatures below 230 K. Apparently this splitting is due to a reversible structural change where one of the NH2 moleties in N2H4.+ becomes slightly bent out of the molecular plane, whereas the other one remains planar. This deformation evidently arises from interactions between the cation radical, adjacent H2N-NH3+ molecules and the SO4-LiO4 framework. Interacting N2H5+···N2H4.+···N2H5+ molecules along the c-axis are proposed to explain the deformation mechanism.

Place, publisher, year, edition, pages
2000. Vol. 2, no 1, 37-42 p.
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Engineering and Technology
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URN: urn:nbn:se:liu:diva-47713DOI: 10.1039/a908487hOAI: oai:DiVA.org:liu-47713DiVA: diva2:268609
Available from: 2009-10-11 Created: 2009-10-11 Last updated: 2017-12-13

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Lund, Anders

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