Bonding and electronic structure of XeF3-.

The xenon-fluoride bond dissociation energy in XeF3- has been measured by using energy-resolved collision-induced dissociation studies of the ion. The measured value, 0.84 +/- 0.06 eV, is higher than that predicted by electrostatic and three-center, four-electron bonding models. The bonding in XeF3- is qualitatively described by using molecular orbital approaches, using either a diradical approach or orbital interaction models. Two low-energy singlet structures are identified for XeF3-, consisting of Y- and T-shaped geometries, and there is a higher energy D3h triplet state. Electronic structure calculations predict the Y geometry to be the lowest energy structure, which can rearrange by pseudorotation through the T geometry. Orbital correlation diagrams indicate that that ion dissociates by first rearranging to the T structure before losing fluoride.

Effect of substituents on the strength of A-Cl- (A = Si, Ge, and Sn) bonds in hypervalent systems: ACl5-, ACl4F-, and A(CH3)3Cl2-.

The gas-phase strengths of the A-Cl(-) bonds in ACl(5)(-), ACl(4)F(-), and A(CH(3))(3)Cl(2)(-) (A = Si, Ge, and Sn) have been determined by measuring thresholds for collision-induced dissociation in a flowing afterglow-tandem mass spectrometer. Bond dissociation energies increase in the order Si < Ge < Sn. Replacement of the three equatorial chlorides with methyl groups weakens the bonds, while replacing one axial chloride with a fluoride strengthens the bonds. Computational results using the B3LYP model with several basis sets parallel the experimental periodic trends, but provide bond dissociation energies lower than experiment by 7-44 kJ mol(-1). MP2 computational results are in better agreement with experiment. The results are consistent with steric hindrance and electrostatic effects playing significant roles in the bonding energetics.

The ionic isomegethic rule and additivity relationships: estimation of ion volumes. A route to the energetics and entropics of new, traditional, hypothetical, and counterintuitive ionic materials.

By virtue of our recently established relationships, knowledge of the formula unit volume, V(m), of a solid ionic material permits estimation of thermodynamic properties such as standard entropy, lattice potential energy, and, hence, enthalpy and Gibbs energy changes for reactions. Accordingly, development of an approach to obtain currently unavailable ion volumes can expose compounds containing these ions to thermodynamic scrutiny, such as predictions regarding stability and synthesis. The isomegethic rule, introduced in this paper, states that the formula unit volumes, V(m), of isomeric ionic salts are approximately the same; this rule then forms the basis for a powerful and successful means of predicting unknown ion volumes (as well as providing a means of validating existing volume and density data) and, thereby, providing solid state thermodynamic data. The rule is exploited to generate unknown ion and (by additivity) corresponding formula unit volumes.

The thermochemistry of group 15 tetrachloride anions.

Bond strengths for a series of Group 15 tetrachloride anions ACl4 (A = P, As, Sb, and Bi) have been determined by measuring thresholds for collision-induced dissociation of the anions in a flowing afterglow-tandem mass spectrometer. The central atoms in these systems have ten electrons, which violates the octet rule: the bond dissociation energies for ACl4- help to clarify the effect of the central atom on hypervalent bond strengths. The 0 K bond energies in kJ mol(-1) are D(Cl3A-CL-) = 90 +/- 7,115 +/- 7,161 +/- 8, and 154 +/- 15, respectively. Computational results using the B3LYP/LANL2DZpd level of theory are higher than the experimental bond energies. Calculations give a geometry for BiCl4 that is essentially tetrahedral rather than the see-saw observed for the other tetrachlorides. NBO calculations predict that the phosphorus and arsenic systems have 3C-4E bonds, while the antimony and bismuth systems are more ionic.