Predictions of molecular structure and energies have been made for each of the members in the ClF n /ClF n - (n = 1-7) series of molecules using density functional theory (DFT). The three different types of prediction for electron affinities determined in this work are: the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE) of the anion. Also reported are the first Cl-F dissociation energies for both the neutral and the anion (D CIFn ). Self-consistent Kohn-Sham orbitals were obtained using four different functional forms and a double-ζ plus polarization (DZP) basis set. When diffuse s- and p-type functions were added to the basis set, the anions were stabilized significantly with respect to the neutrals, and the electron affinity values were increased significantly. Overall, the best agreement with experimental structures was obtained with the DZP++ BHLYP method based upon Becke's half-and-half exchange functional and the Lee-Yang-Parr co...

The monochlorine fluorides (ClFn) and their anions (ClFn-) n = 1-7: structures and energetics

In this paper, we discuss the experimental technique for real-time measurement of the lifetimes of the collision complex of bimolecular reactions. An application to the atom–molecule Br+I_2 reaction at two collision energies is made. Building on our earlier Communication [J. Chem. Phys. 95, 7763 (1991)], we report on the observed transients and lifetimes for the collision complex, the nature of the transition state, and the dynamics near threshold. Classical trajectory calculations provide a framework for deriving the global nature of the reactive potential energy surface, and for discussing the real-time, scattering, and asymptotic (product-state distribution) aspects of the dynamics. These experimental and theoretical results are compared with the extensive array of kinetic, crossed beam, and theoretical studies found in the literature for halogen radical–halogen molecule exchange reactions.

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Femtosecond real-time probing of reactions. VIII. The bimolecular reaction Br+I2

The electronic structures, optimized geometries and harmonic vibrational frequencies of F- 3, Cl- 3, F3 and Cl3 have been studied by ab initio calculations, using various basis sets and different correlation methods, including MP2, CISD and CASSCF For the anions, reasonably consistent results were obtained for the closed-shell singlet ground states However, for the open-shell doublet states of the neutral trihalogens and the triplet states of the anions the optimized geometries and hence the computed harmonic vibrational frequencies were found to be rather basis set and method dependent Calculations based on a single configuration are inadequate for the neutral trihalogens, and the electronic structures of the various open-shell states of both the neutral trihalogens and their anions are rather complex The different effects due to basis set size and dynamic and non-dynamic electron correlation on the various electronic structures, optimized geometries and computed harmonic vibrational frequencies obta

Ab initio studies of X- 3 and X3 (X=F, Cl)

Ab initio calculations using the double-zeta Huzinaga—Dunning—Veillard basis have been performed for the chlorine fluorides CIF itk ( k = 1–7). A detailed discussion of the geometrical and electronic structures, force fields, vibrational frequencies and intramolecular rearrangement surfaces is presented. Good agreement with the results of other basis sets and experimental data is found.

E. Vasini

Papers

The geometry of 21 valence electron radicals