两类含铝簇合体结构与性质的密度泛函理论研究-无机化学专业论文.docxVIP

2007 2007 届硕士毕业论文：两类含铝簇合体结构与性质的密度泛函理论研究 IV IV correlation functional (B3LYP) at the 6-31l++G(3df,2pd) basis set level. The stable structures were obtained. Using the optimized geometries, we systematically investingated the frontier molecular orbitals and IR properties for them. Furthermore, the thermodynamic function values of m-TMA and d-TMA in the ground state were calculated with CBS-4M, CBS-Lq, CBS-Q and CBS-QB3 methods. With the CBS-4M method, one triplet-state configuration, taken the C2h configuration of d-TMA as the starting point, was optimized to obtain the configuration, which had C1 symmetry and no imaginary frequency. Through the consideration of heterolytic equilibrium of d-TMA, the thermodynamic function values of Al(CH3)2(C2v)、Al(CH3)2(D3d) and Al(CH3)4(C3) radicals were calculated at 1 atm and in the range of 300 ~ 550 K. Considered all species having the same opportunity to appear, which is based on the statistical thermodynamics principle, the average values of Gibbs free energy of dissociation-association equilibrium of TMA were calculated. Fitting these values with respect to temperatures, we gained the linear equation between the equilibrium constants and temperatures. Moreover, we compared this result with the B3LYP calculated and experimental values. Based upon these findings, a new dissociation- association reaction mechanism of d-TMA in gas phase was proposed. To obtain the satisfying geometries and NMR values for alundum cluster ions, firstly, the geometries of Al(H2O)63+ and Al(OH)4– were optimized from HF and DFT methods with various basis sets. Then, we calculated the NMR values for the stable structures and compared these results with the experimental ones. At last, we gained two methods: B3LYP/6-31+G(d) and B3LYP/6-31+G(d,p), which were fit to calculate the NMR values for alundum cluster ions. In succession, the optimization and frequency calculations for five Al13 Keggin configurations were carried out at