TY - JOUR
T1 - Raman spectroscopy and quantum chemical calculation on YCl3-KCl molten salt system
AU - Xu, Can
AU - Hu, Xianwei
AU - Yu, Jiangyu
AU - Li, Pengwei
AU - Liu, Aimin
AU - Luo, Shaohua
AU - Shi, Zhongning
AU - Wang, Zhaowen
PY - 2023/11
Y1 - 2023/11
N2 - The knowledge on the ionic structure of YCl3-KCl molten system is of guiding significance for the practical production of yttrium metals and yttrium alloys via molten salt electrolysis using this system as electrolyte. In this paper, the theoretical Raman spectra of the ionic groups which may exist in YCl3-KCl molten system are simulated by quantum chemical calculation using Gaussian 09 and GaussView 5.0 programs based on density functional theory (DFT). Then the ionic structures of 20 mol%–60 mol% YCl3-KCl molten salt systems are studied by comparing the Raman shift values of the bands in the theoretical Raman spectra of different ionic groups with the experimental spectra of this system. YCl63−, Y2Cl7−, Y2Cl82− and Y2Cl93− are thought to exist in the molten system. With the increase of temperature, the relative content of YCl63− ionic groups increases while those of Y2Cl7−, Y2Cl82− and Y2Cl93− ionic groups decrease. Moreover, the "lifetime" of all ionic groups decreases within the temperature range of 692–730 °C. Meanwhile, the relative contents of Y2Cl7−, Y2Cl82− and Y2Cl93− increase with the increase of YCl3 content, while that of YCl63− decreases. The wave function analysis of the four ionic groups (YCl63−, Y2Cl7−, Y2Cl82−, and Y2Cl93−) is carried out by Multiwfn program. The net charge in each group, the direction of electron migration during the formation of each group, the sites where electrophilic and nucleophilic reactions are most likely to occur in each ionic group, and the order of bond breaking during chemical reactions for the four groups are obtained. Graphical abstract: [Figure not available: see fulltext.].
AB - The knowledge on the ionic structure of YCl3-KCl molten system is of guiding significance for the practical production of yttrium metals and yttrium alloys via molten salt electrolysis using this system as electrolyte. In this paper, the theoretical Raman spectra of the ionic groups which may exist in YCl3-KCl molten system are simulated by quantum chemical calculation using Gaussian 09 and GaussView 5.0 programs based on density functional theory (DFT). Then the ionic structures of 20 mol%–60 mol% YCl3-KCl molten salt systems are studied by comparing the Raman shift values of the bands in the theoretical Raman spectra of different ionic groups with the experimental spectra of this system. YCl63−, Y2Cl7−, Y2Cl82− and Y2Cl93− are thought to exist in the molten system. With the increase of temperature, the relative content of YCl63− ionic groups increases while those of Y2Cl7−, Y2Cl82− and Y2Cl93− ionic groups decrease. Moreover, the "lifetime" of all ionic groups decreases within the temperature range of 692–730 °C. Meanwhile, the relative contents of Y2Cl7−, Y2Cl82− and Y2Cl93− increase with the increase of YCl3 content, while that of YCl63− decreases. The wave function analysis of the four ionic groups (YCl63−, Y2Cl7−, Y2Cl82−, and Y2Cl93−) is carried out by Multiwfn program. The net charge in each group, the direction of electron migration during the formation of each group, the sites where electrophilic and nucleophilic reactions are most likely to occur in each ionic group, and the order of bond breaking during chemical reactions for the four groups are obtained. Graphical abstract: [Figure not available: see fulltext.].
KW - Ionic structure
KW - Quantum chemical calculation
KW - Raman spectroscopy
KW - Wave function analysis
KW - YCl-KCl molten salt
UR - http://www.scopus.com/inward/record.url?scp=85172985122&partnerID=8YFLogxK
U2 - 10.1007/s12598-023-02458-y
DO - 10.1007/s12598-023-02458-y
M3 - Journal article
SN - 1001-0521
VL - 42
SP - 3886
EP - 3896
JO - Rare Metals
JF - Rare Metals
IS - 11
ER -