Substituted 1,2-diphenylethanes undergo competitive dissociations upon electron ionization (EI) to generate substituted benzyl cation and benzyl radical pairs. Application of the kinetic method to the previous reported EI mass spectra of these covalently bound precursor ions (data are taken from McLafferty et al. J. Am. Chem. Soc. 1970, 92, 6867)) is used to estimate the ionization energies of substituted benzyl free radicals. A correlation is observed between the Hammett σ constant of the substituents and the kinetic method parameter, ln(k(x)/k(H)), where k(x) is the rate of fragmentation to give the substituted product ion and k(H) is the rate to give the benzyl ion itself. Systems involving weakly bound cluster ions, including proton-bound dimers of meta- and para-substituted pyridines and meta- and para-substituted anilines, and electron-bound dimers of meta- and para-substituted nitrobenzenes, also show good correlations between the kinetic method parameter and the Hammett σ constant.
A localized vibrational mode (LVM) with a remarkable fine structure is observed in the infrared transmission spectrum of a ZnTe epilayer grown with molecular beam epitaxy (MBE) on a GaSb substrate. On the basis of the Zn and Te deposited on the GaSb substrate during the MBE growth of ZnTe, and assuming diffusion of Zn and Te into GaSb, the LVM is attributed to Zn, substitutionally replacing either the cation, Ga (Zn Ga ), or the anion, Sb (Zn Sb ). The frequency of the LVM and its fine structure can then be interpreted in terms of the infrared active modes of 64 Zn substituting for Sb as an anti-site impurity and treating the centre as an XY 4 quasimolecule. With X≡ 64 Zn and Y≡ 69 Ga and 71 Ga, occupying the nearest-neighbour sites reflecting all the possible combinations and permutations as well as the natural isotopic abundance of Ga, the fine structure of the LVM can be accounted for quantitatively.
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