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
Kw. Klinkhammer et P. Pyykko, 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, Inorganic chemistry, 34(16), 1995, pp. 4134-4138
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 sta
te for organyl-substituted molecules of this type. The intermolecular
interaction is repulsive at the Hartree-Fock level but is attractive a
t the MP2 level. With sufficiently large basis sets, the E E distances
approach experimental ones in crystals containing (R(n)E-ER(n))infini
ty chains with R = Me, SiMe(3), SnMe(3), etc. The calculated dimerizat
ion energies (MP2) lie in the range from 8 to 13 kJ mol(-1), increasin
g from right to left and from top to bottom in the periodic table.