Microstructured hydroxyl environments and Raman spectroscopy in selected basic transition-metal halides

doi:10.1088/1674-1056/20/8/087801

Abstract Raman vibrational spectra of the selected basic (hydroxyl OH and deuteroxyl OD) transition-metal halides, geometrically frustrated material series $\alpha $-, $\beta $-, $\gamma $-Cu$_{2}$(OH)$_{3}$Cl, $\alpha $-Cu$_{2}$(OH)$_{3}$Br, $\beta $-Ni$_{2}$(OH)$_{3}$Cl, $\beta $-Co$_{2}$(OH)$_{3}$Cl, $\beta $-Co$_{2}$(OH)$_{3}$Br, $\gamma $-Cu$_{2}$(OD)$_{3}$Cl, and $\beta $-Co$_{2}$(OD)$_{3}$Cl are measured at room temperature and analysed to investigate the relationship between the microstructured OH environments and their respective Raman spectra. Among these selected samples, the last two are used to determine the OH stretching vibration region (3600 cm$^{-1}$--3300 cm$^{{-}1}$) and OH bending vibration region (1000 cm$^{-1}$--600 cm$^{-1}$) of OH systems in the spectra. Through the comparative analysis of the distances $d$(metal--O), $d$(O--halogen), and $d$(OH), the strong metal--O interaction and trimeric hydrogen bond ($C_{3v}$, $C_{s}$ or $C_{1}$ symmetry) are found in every material, but both determine simultaneously an ultimate $d$(OH), and therefore an OH stretching vibration frequency. According to the approximately linear relationship between the OH stretching vibration frequency and $d$(OH), some unavailable $d$(OH) are guessed and some doubtful $d$(OH) are suggested to be corrected. In addition, it is demonstrated in brief that the OH bending vibration frequency is also of importance to check the more detailed crystal microstructure relating to the OH group.

Keywords: hydroxyl trimeric hydrogen bond Raman spectrum basic transition-metal halide

Received: 24 January 2011
Revised: 14 February 2011
Accepted manuscript online:

PACS:	78.30.-j	(Infrared and Raman spectra)
	33.20.Ea	(Infrared spectra)
	61.66.Fn	(Inorganic compounds)
	61.12.-q

Fund: Project supported by the Grant-in-Aid for Scientific Research on Priority Area from the Ministry of Education, Culture, Sports, Science and Technology, Japan (Grant No. Tokutei 22014008).

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Liu Xiao-Dong(刘晓东), Meng Dong-Dong(孟冬冬), Hagihala Masato(萩原雅人), and Zheng Xu-Guang(郑旭光) Microstructured hydroxyl environments and Raman spectroscopy in selected basic transition-metal halides 2011 Chin. Phys. B 20 087801

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Microstructured hydroxyl environments and Raman spectroscopy in selected basic transition-metal halides

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