Reflection spectrum of the single crystal of wurster's blue perchlorate.
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概要
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The visible and near-infrared reflection spectrum of the single crystal of Wurster's blue perchlorate was measured at various temperatures over the range of 30–300 K, by using the microspectrophotometric method. The absorption spectra were derived by Kramers-Kronig transformation of the reflection spectra. The intensity ratio of the (0-0) and (0-1) vibronic bands of the local-excitation associated with the π-π<SUP>*</SUP> (<SUP>2</SUP>B<SUB>1u</SUB>←<SUP>2</SUP>B<SUB>2g</SUB>) transition of TMPD<SUP>+</SUP> was found to be anomalous when the spectrum was measured with the light polarized parallel to the b-axis, while not in the spectrum polarized parallel to the a-axis. The Davydov splitting between B<SUB>3u</SUB> and B<SUB>2u</SUB> components of this absorption band was found to be about 400 cm<SUP>−1</SUP>. In the antiferromagnetic (low temperature) phase below 190 K, the charge-transfer band appeared in the a-axis spectrum, showing its absorption maximum at 11.6×10<SUP>3</SUP> cm<SUP>−1</SUP>, and its intensity increased on lowering the temperature. At the same time, a marked temperature dependence was observed in the local-excitation band. These changes are interpreted in terms of the singlet-triplet model of the dimeric interaction of TMPD<SUP>+</SUP> ions in the low-temperature phase.
- 公益社団法人 日本化学会の論文
著者
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Kuroda Haruo
Department of Chemistry, Faculty of Science, The University of Tokyo
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Yakushi Kyuya
Department Of Chemistry Faculty Of Science University Of Tokyo
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Iyechika Yasushi
Department of Chemistry, Faculty of Science, The University of Tokyo
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Kuroda Haruo
Department of Chemistry and Research Center for Spectrochemistry, Faculty of Science, The University of Tokyo
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