A density functional study on the geometries of compounds Fe(HCN)(n)(+)(n=1 similar to 6)

作者：Hu JM; Li Y; Li JQ^*; Zhang YF; Chen WK

来源：Chinese Journal of Structural Chemistry, 2004, 23(12): 1346-1355.

• Fe(HCN)(n)(+)(n=1 similar to 6) compounds
• density functional theory
• natural bond orbital

The possible geometries of Fe(HCN)(n)(+) (n = 1similar to6) compounds were studied by using DFT/UB3LYP/6-31G(2df) method. The structure and ground state of each fragmental ion are C-infinityv, ((4)Sigma(+) or (6)Sigma(+)), D-infinityh (4Sigma(g)(+)), D-3h ((4)A(l)), C-2v or Td or C-3v ((4)A(l)), and D-3h ((4)A(l)) or C-4V ((2)A(l)) sequentially with n = 1similar to5. For the compound Fe(HCN)(6)(+), the possible geometry was not obtained. The sequential incremental interaction energy (-Delta(DeltaE)), dissociation energy (AD(0)), enthalpy (-Delta(DeltaH)) and Gibbs free energy (-Delta(DeltaG)), and frequencies for HCN-Fe(HCN)(n-1)(+) were also calculated, and the results are all in good agreement with the experiments. The bond length of Fe-N is lengthened with the increase of cluster size, and the strength of Fe+-N coordination bond varies nonmontonically as increasing the number of ligands. The Fe+-N bond of Fe(HCN)(2)(+) is the strongest in all compounds.

• 出版日期2004
• 单位福州大学