The molecular geometries, vibrational properties, and thermodynamic properties of the clusters （Cl2GaN3）n （n= 1--4） have been predicted at the B3LYP/6-311 ＋G＊ level. The optimized clusters （Cl2GaN3）n （n=2--4...The molecular geometries, vibrational properties, and thermodynamic properties of the clusters （Cl2GaN3）n （n= 1--4） have been predicted at the B3LYP/6-311 ＋G＊ level. The optimized clusters （Cl2GaN3）n （n=2--4） all possess cyclic structures containing Ga--N,--Ga linkages. The relationships between geometrical parameters and oli- gomerization degree n are discussed. The gas-phase structures of the trimers prefer to exist in boat-twisting confor- mation. As for the tetramer, the $4 symmetry structure is the most stable. The infrared spectra are obtained and as- signed by vibrational analysis. Thermodynamic properties derived from the infrared spectra on the basis of statistical thermodynamic principles are linearly correlated with the oligomerization degree n as well as the temperature. Meanwhile, thermodynamic analysis of the gas-phase reaction suggests that the oligomerization is exothermic and favorable under high temperature.展开更多
基金Project supported by the Shandong Provincial Natural Science Foundation （No. ZR2010BQ034）.
文摘The molecular geometries, vibrational properties, and thermodynamic properties of the clusters （Cl2GaN3）n （n= 1--4） have been predicted at the B3LYP/6-311 ＋G＊ level. The optimized clusters （Cl2GaN3）n （n=2--4） all possess cyclic structures containing Ga--N,--Ga linkages. The relationships between geometrical parameters and oli- gomerization degree n are discussed. The gas-phase structures of the trimers prefer to exist in boat-twisting confor- mation. As for the tetramer, the $4 symmetry structure is the most stable. The infrared spectra are obtained and as- signed by vibrational analysis. Thermodynamic properties derived from the infrared spectra on the basis of statistical thermodynamic principles are linearly correlated with the oligomerization degree n as well as the temperature. Meanwhile, thermodynamic analysis of the gas-phase reaction suggests that the oligomerization is exothermic and favorable under high temperature.
