Ultraviolet photoelectron spectroscopy of the phenide, benzyl and phenoxide anions, with ab initio calculations

Gunion, Robert F.; Gilles, Mary K.; Polak, Mark L.; Lineberger, W. C.

doi:10.1016/0168-1176(92)80115-h

Cited by 221 publications

(344 citation statements)

References 33 publications

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“…This energy is very similar to that in phenoxyl (1.06(5) eV), 39 although the excited neutral state was not explored in detail in that study. Note that for the ortho and para isomers, a conservative error bar of 9 meV is used.…”

Section: A Electron Affinities and Term Energies Of Methylphenoxyl Rmentioning

confidence: 48%

“…If the product anion is the result of deprotonating the alcohol group, the electron affinity of the neutral should be similar to that of the phenoxyl radical (EA = 2.2538 ± 0.0008 eV 38 ). If the product anion is instead the result of CH 3 deprotonation, it is reasonable to expect an EA of the corresponding neutral to be near that of the benzyl radical (EA = 0.912 ± 0.006 eV 39 ). In either case, the electron is likely to localize on the deprotonated group; this should result in both a lengthening of the bond between the deprotonated group and the aromatic ring, as well as an elongation of the ring away from the negative charge when compared to the equilibrium geometry of the corresponding neutral radical.…”

Section: Resultsmentioning

confidence: 99%

“…Combining the highly accurate (error of ± 0.14 kcal/mol) O-H bond dissociation energy for each methylphenol isomer from King et al, 26 as modified by Karsili et al, 37 with the EAs measured in this study allows for the construction of a thermodynamic cycle that provides accurate gas phase acidities. 34 The results will also be compared with the previous work on the phenoxide 38,39 and benzyl 39 anions, which were also studied using anion photoelectron spectroscopy. One might ask if the methylphenoxyls will display a combination of attributes previously shown by those two anions, or will the chemistry and spectroscopy have qualitatively different behavior?…”

Section: Introductionmentioning

confidence: 99%

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Anion photoelectron spectroscopy of deprotonated ortho-, meta-, and para-methylphenol

Nelson

Gichuhi

Miller

et al. 2017

The Journal of Chemical Physics

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The anion photoelectron spectra of ortho-, meta-, and para-methylphenoxide, as well as methyl deprotonated meta-methylphenol, were measured. Using the Slow Electron Velocity Map Imaging (SEVI) technique, the Electron Affinities (EAs) of the o-, m-, and p-methylphenoxyl radicals were measured: 2.1991 ± 0.0014, 2.2177 ± 0.0014, and 2.1199 ± 0.0014 eV, respectively. The EA of mmethylenephenol was also obtained, 1.024 ± 0.008 eV. In all four cases, the dominant vibrational progressions observed are due to several ring distortion vibrational normal modes that were activated upon photodetachment, leading to vibrational progressions spaced by ~500 cm -1 . Using the

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Section: A Electron Affinities and Term Energies Of Methylphenoxyl Rmentioning

confidence: 48%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Anion photoelectron spectroscopy of deprotonated ortho-, meta-, and para-methylphenol

Nelson

Gichuhi

Miller

et al. 2017

The Journal of Chemical Physics

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“…The experimental electron affinities are 2.253 eV for the phenoxyl radical and 1.096 eV for the phenyl radical. 15 Our estimated value of 42.5 kcal/mol (1.84 eV) is closer to that of the phenoxyl radical Proton Affinity and Bond Dissociation Energy. The anion proton affinities for the three oxocyclohexadienylidene isomers are useful for interpreting the results of gas-phase experiments, because it is difficult to measure these quantities.…”

Section: Resultsmentioning

confidence: 67%

“…The experimental electron affinities of phenyl and phenoxyl radicals, which are prototypes for the molecules of interest in the present study, have been reported. 15 However, there are no reports for the electron affinities of oxocyclohexadienylidene systems. The electron affinity for aromatic radicals is interesting, because the addition of an extra electron can change the character of the aromatic ring.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Oxocyclohexadienylidene Isomers: Electronic Structures and Molecular Properties

et al. 2000

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The molecular properties and electronic structures for three isomers of oxocyclohexadienylidene were investigated using multiconfiguration SCF (MCSCF) wave functions. The ground electronic states of the ortho and para isomers are the open shell triplet, whereas the meta isomer has a singlet ground state with significant open shell character. The structural features of the ground states of all three isomers are close to the quinoid type structure. Several molecular properties such as the electron spin density, electron affinity (EA), acidity and bond dissociation energy for the three isomers and/or their corresponding radicals are also considered and are compared with experimental values. In particular, the MCSCF(8,8)/6-31+G* electron spin densities for both ortho and para isomers are very close to the experimental values of the phenoxyl radical. Disciplines Chemistry CommentsReprinted (adapted) with permission from

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Experimental determination of the? and? C?H bond dissociation energies in naphthalene

Reed

Kass

2000

J. Mass Spectrom.

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The acidities of the two different sites in naphthalene (1α and 1β) and the electron affinities of the α‐ and β‐naphthyl radicals were measured using a Fourier transform mass spectrometer. Both carbon–hydrogen bond dissociation energies for naphthalene also were obtained, in this case via the application of a thermodynamic cycle. The final results are $\Delta {\it H}^{\circ}_{\rm acid}({\bf 1}\alpha) = 394.2 \pm 1.2 \hbox{ kcal mol}^{-1}$, $\Delta {\it H}^{\circ}_{\rm acid}({\bf 1}\beta) = 395.5 \pm 1.3 \hbox{ kcal mol}^{-1}$, EA(α) = 31.6 ± 0.5kcal mol−1, EA(β) = 31.6 ± 0.5kcal mol−1, BDE(1α) = 112.2 ± 1.3kcal mol−1 and BDE(1α) = 111.9 ± 1.4kcal mol−1, and they are compared to benzene and phenyl radical as well as ab initio and density functional theory (B3LYP) calculations. Copyright © 2000 John Wiley & Sons, Ltd.

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Ultraviolet photoelectron spectroscopy of the phenide, benzyl and phenoxide anions, with ab initio calculations

Cited by 221 publications

References 33 publications

Anion photoelectron spectroscopy of deprotonated ortho-, meta-, and para-methylphenol

Anion photoelectron spectroscopy of deprotonated ortho-, meta-, and para-methylphenol

Theoretical Study of Oxocyclohexadienylidene Isomers: Electronic Structures and Molecular Properties

Experimental determination of the? and? C?H bond dissociation energies in naphthalene

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