Determination of electron affinities of radicals and bond dissociation energies by electron-attachment studies at thermal energies--electron affinity of acetate radical

Wentworth, W. E.; Chen, Edward; Steelhammer, J. C.

doi:10.1021/j100853a080

Cited by 18 publications

(9 citation statements)

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“…Again, this may well explain the wide variation in h and k values given in the literature. (5) The relative magnitudes of h and k for 0, F, and Cl are in reasonable agreement with similar parameters derived from other experimental measurements.…”

Section: Discussionsupporting

confidence: 89%

Electron affinities of substituted aromatic compounds

Wentworth¹,

Kao²,

Becker³

1975

J. Phys. Chem.

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The effect of the substituents F, Cl, CHg, OCH3, and C=N on the molecular electron affinities (EA) of benzaldehyde and acetophenone were measured experimentally. The substituents F, Cl, and CF3 increase the EA in the order CF3 > Cl > F whereas CH3 lowers the EA. Hückel parameters for the substituents C=0, CH3, F, and Cl were calculated using a general least-squares adjustment to the EA measurements.The inductive and resonance parameters for a substituent were highly correlated as revealed by the value of the correlation coefficients of 0.998 for F and 0.987 for Cl. It is suggested that this high correlation is the reason for many of the wide variations in Hückel parameters reported by different investigators, regardless of the experimental quantity being considered. This type of analysis can also be applied to other semiempirical calculations involving empirical parameters.

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Section: Discussionsupporting

confidence: 89%

Electron affinities of substituted aromatic compounds

Wentworth¹,

Kao²,

Becker³

1975

J. Phys. Chem.

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“…19 Electron affinity is a fundamental thermodynamic property of a molecule. 21 There have been quite a few experimental estimates of the EA of CH 3 COO employing a variety of techniques including ion equilibrium (3.38 eV), 22 electronimpact ion appearance energy (3.30 ( 0.20 eV; 3.28 eV), 23,24 electron attachment methods (3.179 ( 0.052 eV), 25 and anion photodetachment (3.40 ( 0.30; 3.47 ( 0.01 eV). 17,18 Among all these techniques, anion PES directly measures electron binding energies of anions, and in principle is the most accurate method to determine the EA of the corresponding neutral radicals from the 0-0 transition of the anion PES spectrum.…”

Section: Introductionmentioning

confidence: 99%

“…Electron affinity is a fundamental thermodynamic property of a molecule . There have been quite a few experimental estimates of the EA of CH 3 COO employing a variety of techniques including ion equilibrium (3.38 eV), electron-impact ion appearance energy (3.30 ± 0.20 eV; 3.28 eV), , electron attachment methods (3.179 ± 0.052 eV), and anion photodetachment (3.40 ± 0.30; 3.47 ± 0.01 eV). , Among all these techniques, anion PES directly measures electron binding energies of anions, and in principle is the most accurate method to determine the EA of the corresponding neutral radicals from the 0−0 transition of the anion PES spectrum. However, in many cases the 0−0 transitions were not resolved due to the existence of hot bands and limited spectral resolution or simply cannot be detected due to too large anion−neutral geometry changes such that the Franck−Condon factor of the 0−0 transition is negligiable .…”

Section: Introductionmentioning

confidence: 99%

Determination of the Electron Affinity of the Acetyloxyl Radical (CH₃COO) by Low-Temperature Anion Photoelectron Spectroscopy and ab Initio Calculations

Wang

Woo²,

Wang³

et al. 2006

J. Phys. Chem. A

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The electronic structure and electron affinity of the acetyloxyl radical (CH3COO) were investigated by low-temperature anion photoelectron spectroscopy and ab initio calculations. Photoelectron spectra of the acetate anion (CH3COO-) were obtained at two photon energies (355 and 266 nm) and under three different temperatures (300, 70, and 20 K) with use of a new low-temperature ion-trap photoelectron spectroscopy apparatus. In contrast to a featureless spectrum at 300 K, a well-resolved vibrational progression corresponding to the OCO bending mode was observed at low temperatures in the 355 nm spectrum, yielding an accurate electron affinity for the acetyloxyl radical as 3.250 +/- 0.010 eV. This experimental result is supported by ab initio calculations, which also indicate three low-lying electronic states observed in the 266 nm spectrum. The calculations suggest a 19 degrees decrease of the OCO angle upon detaching an electron from acetate, consistent with the vibrational progression observed experimentally.

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“…[11][12][13] The EA of CH 3 COO• is an important thermodynamic property and has been studied with a variety of techniques. [14][15][16][17][18] However, the large geometry change between the acetate anion and CH 3 COO• results in a very weak Franck-Condon factor for the 0 0 0 transition, 7 making it difficult to observe the neutral vibrational ground state. In most cases, only an upper limit of the EA was estimated.…”

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confidence: 99%

Communication: Observation of dipole-bound state and high-resolution photoelectron imaging of cold acetate anions

Huang

Zhu

Wang

2015

The Journal of Chemical Physics

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We report the observation of a dipole-bound state and a high-resolution photoelectron imaging study of cryogenically cooled acetate anions (CH3COO−). Both high-resolution non-resonant and resonant photoelectron spectra via the dipole-bound state of CH3COO− are obtained. The binding energy of the dipole-bound state relative to the detachment threshold is determined to be 53 ± 8 cm−1. The electron affinity of the CH3COO neutral radical is measured accurately as 26 236 ± 8 cm−1 (3.2528 ± 0.0010 eV) using high-resolution photoelectron imaging. This accurate electron affinity is validated by observation of autodetachment from two vibrational levels of the dipole-bound state of CH3COO−. Excitation spectra to the dipole-bound states yield rotational profiles, allowing the rotational temperature of the trapped CH3COO− anions to be evaluated.

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Determination of electron affinities of radicals and bond dissociation energies by electron-attachment studies at thermal energies--electron affinity of acetate radical

Cited by 18 publications

References 1 publication

Electron affinities of substituted aromatic compounds

Electron affinities of substituted aromatic compounds

Determination of the Electron Affinity of the Acetyloxyl Radical (CH₃COO) by Low-Temperature Anion Photoelectron Spectroscopy and ab Initio Calculations

Communication: Observation of dipole-bound state and high-resolution photoelectron imaging of cold acetate anions

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Determination of electron affinities of radicals and bond dissociation energies by electron-attachment studies at thermal energies--electron affinity of acetate radical

Cited by 18 publications

References 1 publication

Electron affinities of substituted aromatic compounds

Electron affinities of substituted aromatic compounds

Determination of the Electron Affinity of the Acetyloxyl Radical (CH3COO) by Low-Temperature Anion Photoelectron Spectroscopy and ab Initio Calculations

Communication: Observation of dipole-bound state and high-resolution photoelectron imaging of cold acetate anions

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Determination of the Electron Affinity of the Acetyloxyl Radical (CH₃COO) by Low-Temperature Anion Photoelectron Spectroscopy and ab Initio Calculations