Ab initio calculations on some transition metal heptoxides by using effective core potentials

摘要

The ab initio molecular structures and vibrational frequencies for several transition metal heptoxides X_2O_7~(n-) (n = 0, 2, 4) were calculated using effective core potentials at the HF and DFT (B3LYP) levels. The relative merits of different valence basis set arrangements were tested by comparison with experimental results available, in particular with gas-phase Re_2O_7 molecular structure and vibrational frequencies. The calculations were then extended to other heptoxides of the VB, VIB and VIIB transition metal groups. The results indicate that a staggered geometry (either D_(3d) or C_2) is the energy minimum for most of the heptoxides studied. The only exceptions are Mn_2O_7, which clearly prefers an eclipsed C_(2v(syn)) configuration, and Tc_2O_7, for which C_2 and C_(2v(syn)) geometries have nearly the same energy. Particular attention was given to the magnitude of the X-O-X bond angle, as this structural parameter has been a matter of some controversy. The calculated values range from 125 deg (Mn_2O_7) to 180 deg (Group VB heptoxides) and depend on the position of the transition metal in the Periodic Table. A tendency for linearity of the X-O-X moiety on going both downwards the group and backwards the period was observed and discussed.