화학공학소재연구정보센터
Inorganic Chemistry, Vol.34, No.16, 4134-4138, 1995
Ab-Initio Interpretation of the Closed-Shell Intermolecular E-Center-Dot-Center-Dot-Center-Dot-E Attraction in Dipnicogen (H(2)E-Eh(2))(2) and Dichalcogen (He-Eh)(2) Hydride Model Dimers
Quasirelativistic pseudopotential ab initio calculations at the second-order Moller-Plesset (MP2) level are reported on dimeric hydrides (H(2)E-EH(2))(2) (E = As, Sb, Pi) and (HE-EH)(2) (E = Se, Te, Po), which serve as models for the nearly collinear chains found in the solid state for organyl-substituted molecules of this type. The intermolecular interaction is repulsive at the Hartree-Fock level but is attractive at the MP2 level. With sufficiently large basis sets, the E E distances approach experimental ones in crystals containing (R(n)E-ER(n))infinity chains with R = Me, SiMe(3), SnMe(3), etc. The calculated dimerization energies (MP2) lie in the range from 8 to 13 kJ mol(-1), increasing from right to left and from top to bottom in the periodic table.