The infrared spectra of the 32S, 34S, 16O, 18O isotopic species of SO2 trapped in solid krypton matrices at 20°K are reported. Under conditions of medium resolution (∼0.8 cm−1), single bands are observed in each of the spectral regions which correspond to the three vibrational modes. Analysis of all the matrix data on the basis of a valence force field which includes anharmonic corrections and in which the bond angle is treated as a variable parameter yields force constants very close to those derivable from the available gas-phase data. The SO2 bond angle which leads to the best fit of the experimental matrix data is 119°37′, in excellent agreement with the angle determined from microwave data. The use of measured isotopic shifts for the determination of the bond angles in triatomic molecules both from matrix and gas-phase studies is examined in considerable detail. It is shown that the use of observed frequencies in calculations involving two isotopic species can lead in many cases to reliable upper and lower limits of the bond angle. The quality of these limits depends on the magnitude of the anharmonic corrections and the stretch–bend interaction. The infrared spectra of matrix isolated SO2 and NO2 under conditions of higher resolution (0.3 cm−1) reveal some interesting features in the asymmetric stretching mode ν3. These features are discussed in terms of a hindered rotation in the solid krypton matrix.

indeterminate. Similar results occur for other multiplebonded situations and for cases where two lone-pair orbitals are localized on one atom. Fortunately, however, when the INDO version 3l of the zero-differential overlap method is employed, reasonable values for coulomb integrals over M.O.'s are obtained; and, in agreement with ab initio results, localization usually 31 J. A. Pople, D. L. Beveridge, and P. A. Dobosh, J. Chern. Phys. 47, 2026 (1967 leads to bent bonds. Further details will be given in a subsequent publication. 32 ACKNOWLEDGMENTSWe wish to thank John A. Tossell for assistance with the diborane calculations, and George N. Reeke for extensive help in preparing the density maps. We also are grateful to the Office of Naval Research for support of this research. 3' M. D. Newton (unpublished).

The reactions of ethylene, propene, and acetylene with two different zeolite models are computationally characterized using both semiempirical and ab initio methods. The MP2/6-31G* level calculations give activation energies which appear too high in comparison with the estimated experimental values. The DFT values seem more reasonable. The AM1 and PM3 transition state structures appear dubious with respect to both ab initio results and generally accepted intuitive descriptions.

Careful calculations are performed to obtain the radial density-density response function for the He and the Be series. This is also done along the adiabatic connection of the density functional theory ͑as the system evolves from the real, physical system to the Kohn-Sham one͒. In this process the electron density is kept constant, while the strength of the interaction between electrons changes. The response functions are analyzed in terms of their eigenvalues and eigenfunctions. The latter change only little along this process. The absolute value of the eigenvalues is in general reduced by the interaction: A screening effect is present. For the near-degenerate systems, we notice that the opposite effect can appear ͑antiscreening͒.