Geometry of simple molecules. 2. Modeling the geometry of AX3E and AX2E2 molecules through the nonbonded interaction...

A new conceptual model of molecular geometry is presented, called the nonbonded interaction (NBI) model. This model is applied to the geometries of the AX3E and AX2E2 (A = N, O, P, S, As, Se, or Te; X = H, F, Cl, Br, I, CH(3), tBu, CF3, SiH3, Sn(tBu)3, or SnPh3) molecule types. For these molecules, the NBI model can be quantified on the basis of a balance between terminal atom-terminal atom (X-X) interactions and lone pair-terminal atom (E-X) interactions. The empirically observed X-A-X angles range from 91.0 degrees (SeH2) to 180 degrees (O(Sn(tBu)3)2), and the NBI model predicts the X-A-X angle with a mean unsigned error of 1.0 degrees using the empirical A-X distance, 1.5 degrees using the LMP2/6-31G** A-X distance, and 1.1 degrees using the MMFF94 A-X distance. This level of precision compares well to the LMP2/6-31G**-predicted X-A-X angles and is significantly better than the MMFF94-predicted X-A-X angles. Terminal groups that are not sufficiently spherical (CF3, SiH3, and SnPh3) can still be addressed qualitatively by the NBI model, as can molecules with a mixture of terminal groups. The NBI model is able to explain, often quantitatively, the geometry of all of the molecules studied, without any additional postulates or extensive parametrization.