Department of Chemistry, Huaiyin Normal University, Huaian 223300, Jiangsu, People's Republic of China.
Spectrochim Acta A Mol Biomol Spectrosc. 2010 Oct 1;77(2):378-87. doi: 10.1016/j.saa.2010.05.018. Epub 2010 May 24.
The vibrational spectra of aluminum halides, AlX(3) (X=F, Cl, Br and I) and their dimers, Al(2)X(6), have been systematically investigated by ab initio restricted Hartree-Fock (RHF) and density functional B3LYP and B3P86 methods with LanL2DZ, SDD, CEP-31G and DGDZVP basis sets. The optimized geometries, calculated vibrational frequencies were evaluated via comparing with the experimental data. The vibrational frequencies, calculated by these methods with different basis sets, were compared to each other. The effect of the methods and the basis sets used on the calculated vibrational frequencies was discussed. The best fittings values between the calculated and the measured vibrational frequencies were achieved by B3LYP/DGDZVP theoretical level, with this method, the deviations are less than 2% for Al-X stretching vibrational modes in AlX(3) and less than 4% for Al-X stretching vibrational modes in Al(2)X(6). Some vibrational frequencies of Al(III) halides were predicted.
卤化铝，AlX(3)（X=F、Cl、Br 和 I）及其二聚体 Al(2)X(6)的振动光谱已通过从头算限制 Hartree-Fock（RHF）和密度泛函 B3LYP 和 B3P86 方法，LanL2DZ、SDD、CEP-31G 和 DGDZVP 基组进行了系统研究。优化了几何形状，通过与实验数据比较评估了计算得到的振动频率。用不同基组的这些方法计算得到的振动频率相互进行了比较。讨论了所使用的方法和基组对计算得到的振动频率的影响。通过 B3LYP/DGDZVP 理论水平实现了计算得到的振动频率与测量值之间的最佳拟合值，在该方法中，AlX(3)中 Al-X 伸缩振动模式的偏差小于 2%，Al(2)X(6)中 Al-X 伸缩振动模式的偏差小于 4%。还预测了一些 Al(III)卤化物的振动频率。
