Radiation Synthesis of Iodonium Compounds

MacLachlan, Alexander

doi:10.1021/j100783a505

Cited by 2 publications

(9 citation statements)

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“…[13] reveals that for a perfectly conducting surface for which E , = 1, the imaginary part of i y , becomes equal to i I m y + = y o and iImy-= 0, which coincide with the Dicke result (31, 39) describing the radiative decay of the symmetric and antisymmetric modes arising from the cooperative radiative interaction of two identical atoms in the gas phase, respectively (26)(27)(28)(29).…”

Section: Excitation Spectra Of the Symmetric Modessupporting

confidence: 62%

“…For a perfect conductor e ( o ) = or: and l = 1 the Hamiltonian [3] describes the interaction between the atom A and a perfectly conducting plane of distance R apart or the interaction between the atom A and its image B, which is equivalent to that describing the interaction between two identical atoms in the gas phase at a distance 2R apart (26)(27)(28)(29). All the interactions involved in the Hamiltonian [3] are weak perturbations and, therefore, any time-dependent perturbation method when appropriately chosen is suitable to study the required excitation spectra arising from radiative and nonradiative decay mechanisms.…”

Section: The Model Hamiltonianmentioning

confidence: 99%

“…To discuss the excitation spectrum, we consider the case of short distances of separation between the atom and the metal surface, i.e., where the inequality (2REVo/c) < 1 is satisfied and retardation effects are unimportant (17)(18)(19)(26)(27)(28)(29). In this case, the expressions for y , ( o ) can be calculated from eqs.…”

Section: Excitation Spectra Of the Symmetric Modesmentioning

confidence: 99%

“…In this case, the expressions for y , ( o ) can be calculated from eqs. [lo] and [ l l ] ; the results of such a calculation are known in the literature (26)(27)(28)(29)(32)(33)(34). For (2REwo/c) < 1 an expansion in powers of 2REVo/c yields ReyAB(o) = 0.…”

Section: Excitation Spectra Of the Symmetric Modesmentioning

confidence: 99%

“…In the present study, we confine ourselves only to the case of short distances for which (2REwo/c) < 1, and we are mainly concerned with the effects of surface plasmons on the lifetime of the physisorbed atoms and, hence, variations of the decay process with the distance will be completely ignored. Then the imaginary part of y A B ( o ) is determined by (26)(27)(28)(29) and describes the spontaneous emission probability for the transition Iv) -+ lo), where Po, is the matrix element of the transition dipole moment and is assumed to be real. Then from eq.…”

Section: Excitation Spectra Of the Symmetric Modesmentioning

confidence: 99%

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Adsorbate spectra of rare-gas atoms on metal surfaces

Mavroyannis¹

1988

Can. J. Chem.

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This paper is dedicated to Professor J. A. MorrisonCONSTANTINE MAVROYANNIS. Can. J. Chem. 66, 741 (1988).The optical excitation spectra of neutral rare-gas atoms physisorbed on metal surfaces have been considered. Emphasis has been given to the dynamic effects of the surface plasmons on the lifetimes of the adsorbed atoms. At low coverage and when the damping of the surface plasmons is much greater than the effective radiative damping, the spectral functions of the symmetric and antisymmetric modes consist of asymmetric Lorentzian lines, whose asymmetry depends on the strength of the surface plasmons. At this limit the relative intensities of the symmetric and antisymmetric modes take positive and negative values describing the physical processes of absorption (attenuation) and stimulated emission (amplification), respectively. Hence, the occasional disappearance of the spectral lines of the optical absorption is due to a cancellation process, which takes place between the frequency profiles arising from two nearby excited states of the adsorbed atom. The red shifted peak of the symmetric mode of the higher excited state and the blue shifted peak of the antisymmetric mode of the lower excited state of the atom cancel each other out provided that their frequency profiles nearly coincide. This may be a possible explanation of the persistence-extinction phenomenon that has been observed for a number of rare-gas substrate systems in the low coverage limit, where it has been proposed that a charge-transfer instability exists. Numerical results indicate that the peaks of excited Xe on A1 and excited Kr on Au vanish in the low coverage limit.CONSTANTINE MAVROYANNIS. Can. J. Chem. 66, 741 (1988).On a CtudiC les spectres d'excitation optique d'atomes de gaz rares neutres adsorb& physiquement sur des surfaces mCtalliques. On considkre principalement les effets dynarniques des plasmons de surface sur les temps de vie des atornes adsorb&. Lorsque la couverture est faible et que le ralentissement des plasmons de surface est beaucoup plus grand que le ralentissement radiatif effectif, les fonctions spectrales des modes symktriques et antisymktriques consistent en des raies asymCtriques de Lorentz dont l'asyrnktrie dkpend de la force des plasmons de surface. A cette lirnite, les intensites relatives des modes syrn&triques et antisymktriques prennent des valeurs positive et negative en dtcrivant respectivement les processus physiques d'adsorption (attenuation) et d'emission stirnulees (amplification). I1 s'en suit que la disparition occasionnelle des lignes du spectre d'absorption optique est due B une processus d'annulation qui prend place entre les profils de friquence qui proviennent de deux Ctats excites adjacents de l'atorne adsorbt. La raie deplacte vers le rouge du mode symetrique de 1'Ctat excite le plus eleve de l'atome et la raie dCplacte vers le bleu du mode antisymetrique de 1'Ctat excite le plus bas de l'atorne s'annulent lorsque leurs profils de frkquence coincident. Ceci est une explication possible du phenomkne ...

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Section: Excitation Spectra Of the Symmetric Modessupporting

confidence: 62%

Section: The Model Hamiltonianmentioning

confidence: 99%

Section: Excitation Spectra Of the Symmetric Modesmentioning

confidence: 99%

Section: Excitation Spectra Of the Symmetric Modesmentioning

confidence: 99%

Section: Excitation Spectra Of the Symmetric Modesmentioning

confidence: 99%

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Adsorbate spectra of rare-gas atoms on metal surfaces

Mavroyannis¹

1988

Can. J. Chem.

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Szilard-Chalmers Reactions in Aromatic Iodocompounds

Wheeler

Lecumberry

1970

Radiochimica Acta

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119effective scavengers at concentrations sufficiently low not to interfere appreciably with hot processes. We conclude that IBr and IC1 scavenge hot hydrogen systems with an efficiency comparable to that of I 2 and Br 2 . They are preferable to Br 2 because of their lower reactivity with non-radicals, and to I 2 because of their higher vapor pressure. In scavenging alkyl radicals they have the additional advantage of yielding alkyl chlorides and bromides rather than the higher boiling iodides. SummaryThe radioactive products formed in the activation of iodobenzene, iodosobenzene, iodoxybenzene and diphenyliodonium iodide have been analyzed. The radiochemical yield of zero valent iodine was 13-25%, and iodine was not an effective scavenger for hot iodine atoms. The anionic yield was only appreciable for iodoso-and iodoxy-benzene, and was largely iodide and iodate. The main labeled product in all cases was iodobenzene. Some labeled iodosobenzene was formed from iodoxybenzene. These products resulted from recombination reactions.

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Radiation Synthesis of Iodonium Compounds

Cited by 2 publications

References 0 publications

Adsorbate spectra of rare-gas atoms on metal surfaces

Adsorbate spectra of rare-gas atoms on metal surfaces

Szilard-Chalmers Reactions in Aromatic Iodocompounds

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