Department of Chemistry, University of Guelph , Guelph, Ontario, Canada N1G 2W1.
J Phys Chem B. 2014 Jan 9;118(1):204-14. doi: 10.1021/jp406580q. Epub 2013 Dec 24.
Temperature-dependent Raman studies of aqueous copper(I) chloride complexes have been carried out up to 80 °C, along with supporting ab initio calculations for the species CuCl(n)(H2O)m, n = 0-4 and hydration numbers m = 0-6. Normalized reduced isotropic Raman spectra were obtained from perpendicular and parallel polarization measurements, with perchlorate anion, ClO4(-), as an internal standard. Although the Raman spectra were not intense, spectra could be corrected by solvent baseline subtraction, to yield quantitative reduced molar scattering coefficients for the symmetric vibrational bands at 297 ± 3 and 247 ± 3 cm(-1). The intensity variations of these bands with concentration and temperature provided strong evidence that these arise from the species CuCl2 and CuCl3, respectively. The results from ab initio calculations using density functional theory predict similar relative peak positions and intensities for the totally symmetric Cu-Cl stretching bands of the species CuCl2(H2O)6 and CuCl3(H2O)6, in which the water is coordinated to the chloride ions. A less intense Raman band at 350 ± 10 cm(-1) is attributed to the symmetric Cu-Cl stretching mode of hydrated species CuCl(H2O) with six waters of hydration. Temperature- and concentration-independent quantitative Raman molar scattering coefficients (S) are reported for the CuCl2 and CuCl3species.
已对水合氯化铜（I）配合物进行了温度依赖的喇曼研究，最高温度达到 80°C，同时还进行了物种 CuCl(n)(H2O)m，n = 0-4 和水合数 m = 0-6 的从头算计算。通过垂直和平行偏振测量获得了归一化的简化各向同性喇曼光谱，以高氯酸根阴离子 ClO4(-) 作为内标。尽管喇曼光谱强度不高，但可以通过溶剂基线扣除进行校正，以获得对称振动带在 297 ± 3 和 247 ± 3 cm(-1) 的定量简化摩尔散射系数。这些带的强度随浓度和温度的变化为它们分别来自 CuCl2 和 CuCl3 物种提供了有力的证据。使用密度泛函理论的从头算计算结果预测了物种 CuCl2(H2O)6 和 CuCl3(H2O)6 中完全对称的 Cu-Cl 伸缩带的相对峰位和强度相似，其中水与氯离子配位。一个较弱的喇曼带在 350 ± 10 cm(-1) 归因于具有六个水合配体的水合物种 CuCl(H2O) 的对称 Cu-Cl 伸缩模式。报道了 CuCl2 和 CuCl3 物种的温度和浓度无关的定量喇曼摩尔散射系数 (S)。
