Electron spin resonance line-shape analysis for determination of unresolved metal hyperfine splittings in ion pairs. Application to the benzene anion radical

Jones, M. T.; Komarynsky, M.; Rataiczak, Raymond D.

doi:10.1021/j100687a011

Cited by 14 publications

(3 citation statements)

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“…At higher temperatures they appear to merge with the DME data. As noted in ref 1 and 2, the ESR line shapes of potassium benzenide solutions are inhomogeneously broadened due to the presence of unresolved metal hfs. The line shape analysis used to measure the metal hfs also yields the component line width (i.e., the true line width).1,2 Figure 4 shows the component line widths in the two solvents 2:1 (THF/ DME) and DME.…”

Section: Resultsmentioning

confidence: 71%

“…The following relationship between the g value of the reference and the unknown sample was used: gunk = gref " (gIef)2 ß/(hp0) (1) gunk and gref are the g values of the unknown and the reference samples, respectively; AH is the magnetic field difference between the reference and unknown samples; ß, the Bohr magneton; h, is Planck's constant, and v0 the spectrometer frequency. The spectrometer frequency was obtained by directly counting the frequency of the microwave radiation with a Hewlett-Packard 5245L frequency counter and a matched 5260A frequency divider.…”

Section: Methodsmentioning

confidence: 99%

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An electron spin resonance study of the benzene anion radical. A model of its ion pair with alkali metal ions

Jones¹,

Kuechler²

1977

J. Phys. Chem.

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A detailed study of the ESR of potassium, rubidium, and cesium benzenide solutions is described. The g values, metal hyperfine splitting (hfs), and line widths have been measured as a function of solvent, temperature, and metal ion. The g values have been found to depend upon the alkali metal, the temperature, and the solvent. In the case of potassium benzenide, the metal hfs depends upon the temperature and may to a very small extent depend upon the solvent. Estimates of the rubidium and cesium metal hfs are presented. The ESR line width in the case of potassium benzenide is shown to be dependent upon the solvent and the temperature. These various phenomena are strongly suggestive of the existence of an alkali metal ion-benzene anion radical pair. A model for the ion pair is proposed in which the metal ion is placed on the sixfold axis of the benzene anion radical. However, for the temperature dependent effects upon the g values and metal hfs to be observed it is necessary for the metal ion to oscillate parallel to the plane of the benzene ring but with an average position centered on the benzene sixfold axis. MO calculations are presented to show that the expected experimental observations calculated on the basis of the model presented are consistent with the actual experimental observations. IntroductionThe purpose of the study which is described here is to characterize the molecular and electronic structure of the benzene anion radical-alkali metal cation pair. Previous

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Section: Resultsmentioning

confidence: 71%

Section: Methodsmentioning

confidence: 99%

An electron spin resonance study of the benzene anion radical. A model of its ion pair with alkali metal ions

Jones¹,

Kuechler²

1977

J. Phys. Chem.

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“…MPADS™ <=> PADS2™ + M+ (5) The difference between the g value of the dissociated species and that observed at any given set of experimental conditions is given by the following expression: and Ag' = gpADS2" " áfMPADS_ (8) Substitution of the thermodynamic dissociation constant, Kd, defined by eq 5 in eq 6 yields l/Ag = [(Kd/Ag'M+)] + l/Ag'…”

Section: Cspads"mentioning

confidence: 99%

Electron spin resonance studies of ion pair formation in solutions of Fremy's salt

Jones¹,

Ahmed²,

Kastrup³

et al. 1979

J. Phys. Chem.

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It is shown that Fremy's salt ((KS03)2N0) is ion paired under a variety of experimental conditions. When dissolved in dioxane-water solutions in the presence of CsC104, two superimposed spectra are observed. One spectrum is that normally observed. The other has an additional splitting by a single cesium ion. An estimate of the dissociation constant has been made. Solutions of (KS03)2N0 when in the presence of such salts as RbCl and CsCl show g value shifts which are interpreted in terms of the formation of ion pairs with the added alkali metal ions. Analysis of the shifts yields estimates of the dissociation constants of 1.7(±0.4) and 1.4(±0.4) for the RbCl and CsCl salts, respectively, for a single dissociation/association process. Finally, the ESR line shapes for dilute solutions of (KS03)2N0 as a function of added alkali metal ions have been studied. It is shown that in previous work some of the reported distortion was the result of magnetic field modulation at too large a frequency. However, when lower frequencies are used there still remains a small distortion which can be interpreted in terms of a small unresolved metal hfs in the range of 5-20 mG depending upon the salt.

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16.1.1.1 Benzenes

Jones¹

Organic Anion Radicals

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Electron spin resonance line-shape analysis for determination of unresolved metal hyperfine splittings in ion pairs. Application to the benzene anion radical

Cited by 14 publications

References 0 publications

An electron spin resonance study of the benzene anion radical. A model of its ion pair with alkali metal ions

An electron spin resonance study of the benzene anion radical. A model of its ion pair with alkali metal ions

Electron spin resonance studies of ion pair formation in solutions of Fremy's salt

16.1.1.1 Benzenes

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