(上海大學(xué) 上海市現(xiàn)代冶金與材料制備重點(diǎn)實(shí)驗(yàn)室，上海 200072)
摘 要: 在Na3AlF6-Al2O3系熔鹽中，考慮到可能出現(xiàn)的鍵合結(jié)構(gòu)，構(gòu)建系列鋁氟和鋁氟氧絡(luò)合離子的團(tuán)簇結(jié)構(gòu)模型，分別應(yīng)用量子化學(xué)第一原理(Ab initio)和密度泛函計算方法(DFT)對其進(jìn)行結(jié)構(gòu)優(yōu)化和拉曼頻率計算，對Na3AlF6-Al2O3二元系含和不含LiF和CaF2添加劑的兩種樣品進(jìn)行原位升溫拉曼光譜實(shí)驗(yàn)。結(jié)果表明：兩種方法計算結(jié)果吻合較好；添加劑LiF和CaF2對Al2O3的溶解有促進(jìn)作用；溶解Al2O3中的氧已轉(zhuǎn)化成為Al2OF62-中的橋氧，并得到理論計算模擬結(jié)果的解釋和確認(rèn)。
關(guān)鍵字: Na3AlF6-Al2O3；團(tuán)簇；第一原理計算；拉曼光譜；高溫熔鹽
（Shanghai Key Laboratory of Modern Metallurgy and Materials Processing, Shanghai University, Shanghai 200072, China）
Abstract:Several Al-F and Al-F-O clusters were designed and constructed on the consideration of possible bondings in Na3AlF6-Al2O3 molten salt system. First principle calculation and density function theory (DFT) were applied to optimize the proposed clusters and simulate their vibrational modes and Raman spectra. The samples of binary Na3AlF6-Al2O3 without and with LiF and CaF2 as additives were chosen to recorde by in-situ high temperature Raman spectrometer. The results reveal that the calculation result agrees well with each other. The additives LiF and CaF2 can be help to resolve Al2O3, and oxygen originated from Al2O3 exists as bridging oxygen of A12OF62- anion, which can be confirmed by both experimental and theoretical simulation results.
Key words: Na3AlF6-Al2O3; clusters; first principle calculation; Raman spectroscopy; high temperature molten salt
