Raman and Mid-IR Spectral Analysis of the Atacamite-Structure Hydroxyl/Deuteroxyl Nickel Chlorides Ni2(OH/D)3Cl
LIU Xiao-Dong1,2**, Hagihala Masato1, ZHENG Xu-Guang1,3**, MENG Dong-Dong1,2, GUO Qi-Xin4
1Department of Physics, Graduate School of Science and Engineering, Saga University, Saga 840-8502, Japan 2Department of Physics, College of Science, Tianjin Polytechnic University, Tianjin 300160 3Department of Physics, Faculty of Science and Engineering, Saga University, Saga 840-8502, Japan 4Synchrotron Light Application Center & Department of Electrical and Electronic Engineering, Saga University, Saga 840-8502, Japan
Raman and Mid-IR Spectral Analysis of the Atacamite-Structure Hydroxyl/Deuteroxyl Nickel Chlorides Ni2(OH/D)3Cl
LIU Xiao-Dong1,2**, Hagihala Masato1, ZHENG Xu-Guang1,3**, MENG Dong-Dong1,2, GUO Qi-Xin4
1Department of Physics, Graduate School of Science and Engineering, Saga University, Saga 840-8502, Japan 2Department of Physics, College of Science, Tianjin Polytechnic University, Tianjin 300160 3Department of Physics, Faculty of Science and Engineering, Saga University, Saga 840-8502, Japan 4Synchrotron Light Application Center & Department of Electrical and Electronic Engineering, Saga University, Saga 840-8502, Japan
摘要Vibrational spectra (Raman 4000–95 cm−1 and mid-IR 4000–400 cm−1) of the atacamite-structure Ni2(OH)3Cl, including a rarely reported kind of asymmetric trimetric hydrogen bond, as a member of the geometrically frustrated material series and its deuteride Ni2(OD)3Cl are, to the best of our knowledge, reported for the first time and analyzed at room temperature. Through a comparative study of four spectra according to their crystal structural parameters, we assign OH stretching modes v(OH) in a functional group region (3700–3400 cm−1) and their deformation modes δ(NiOH/D) in the correlation peak region (900–600 cm−1) with the corresponding mode frequency ratios ωv(OD)/ωv(OH)≈73% and ωδ(NiOD)/ωδ(NiOH)≈75%, and further self−consistently suggest Ni-O and Ni-Cl related modes in the fingerprint region (500–200 cm−1 and 200–0 cm−1, respectively) by use of the unified six-ligand NiO5Cl and NiO4Cl2 frames. This report may contribute to the spectral analysis of other hydroxyl transition-metal halides and to the understanding of the fundamental physics of their exotic magnetic geometrical frustration property from the spectral changes around the corresponding low transition temperatures.
Abstract：Vibrational spectra (Raman 4000–95 cm−1 and mid-IR 4000–400 cm−1) of the atacamite-structure Ni2(OH)3Cl, including a rarely reported kind of asymmetric trimetric hydrogen bond, as a member of the geometrically frustrated material series and its deuteride Ni2(OD)3Cl are, to the best of our knowledge, reported for the first time and analyzed at room temperature. Through a comparative study of four spectra according to their crystal structural parameters, we assign OH stretching modes v(OH) in a functional group region (3700–3400 cm−1) and their deformation modes δ(NiOH/D) in the correlation peak region (900–600 cm−1) with the corresponding mode frequency ratios ωv(OD)/ωv(OH)≈73% and ωδ(NiOD)/ωδ(NiOH)≈75%, and further self−consistently suggest Ni-O and Ni-Cl related modes in the fingerprint region (500–200 cm−1 and 200–0 cm−1, respectively) by use of the unified six-ligand NiO5Cl and NiO4Cl2 frames. This report may contribute to the spectral analysis of other hydroxyl transition-metal halides and to the understanding of the fundamental physics of their exotic magnetic geometrical frustration property from the spectral changes around the corresponding low transition temperatures.
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2011, Vol. 28 
