Carboxyl Free Radicals: Formyloxyl (HCOO.bul.) and Acetyloxyl (CH3COO.bul.) Revisited

Rauk, Arvi; Yu, Dake; Armstrong, David A.

doi:10.1021/ja00097a031

Cited by 52 publications

(63 citation statements)

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“…The obtained results are comparable with theoretical data reported in the literature and with experimental results. 17,18,25 Then we used these relaxed coordinates of the molecule and copper surface as starting positions in the molecule-surface calculations and relaxed the combined system to the minimum-energy configuration for several adsorption geometries. The obtained results are discussed in the following.…”

Section: Resultsmentioning

confidence: 99%

Density-functional theory study on the arrangement of adsorbed formate molecules on Cu(110)

2007

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The interaction of formate molecules with the Cu͑110͒ surface is investigated using density-functional theory calculations. We find that in the most stable structures for low and high coverage, the formate molecules are sitting perpendicular to the Cu͑110͒ surface, and they are adsorbed in a bridge position, i.e., the O u C u O group forms a bridge between two Cu atoms. Other tested configurations are less stable by at least 0.45 eV per formate molecule. In the case of an oxygen-precovered Cu͑110͒ surface with high formate coverage ͓two molecules in a ͑2 ϫ 2͒ unit cell͔ we find a very similar adsorption geometry. We find an attractive interaction between adsorbed formate molecules on the copper surface. Our results are consistent with experimental results by scanning tunneling microscopy and photoelectron diffraction.

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Section: Resultsmentioning

confidence: 99%

Density-functional theory study on the arrangement of adsorbed formate molecules on Cu(110)

2007

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“…Thus, the origin of the first excited electronic state of CH 3 COO• is expected to be the e peak and it is 1371 cm −1 higher than that of the neutral ground state, in good agreement with the calculated 0.1-0.2 eV excitation energy. 7 The s-wave PAD of the 0 0 0 peak indicates that the highest occupied molecular orbital of CH 3 COO − should be a p-type orbital, which is quite different from what was observed for HCOO − : the PAD of the 0 0 0 peak of HCOO• has p-wave character. 21 Moreover, the observed p-wave PAD of the excited state of CH 3 COO − is also different from that reported for the first excited electronic state of HCOO•.…”

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confidence: 82%

“…However, this seemingly simple radical has posed considerable challenge to both experimental and theoretical studies because of the existence of several low-lying electronic states and symmetry breaking issues. [6][7][8][9] Anion photoelectron spectroscopy (PES) is a powerful technique for the study of the electronic structures of shortlived neutral radicals. However, the spectral resolution of PES is usually limited to several meV, preventing the observation of low frequency vibrations.…”

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confidence: 99%

“…21 While information about photoelectron angular distribution (PAD) of CH 3 COO• is lacking, ab inito calculations indicated that the symmetry of the ground state of CH 3 COO• is different from that for HCOO•, that is, the ground state of CH 3 COO• is 2 A ′′ (B 2 ), with a 2 A ′ (A ′ ) lowlying excited state ∼0.1-0.2 eV higher in energy. 7 Molecules with sufficient dipole moments can bind an electron [22][23][24][25] and form dipole-bound anions. [26][27][28][29] Resonances observed in photodetachment experiments provided the first evidence for excited dipole-bound states (DBSs) near detachment thresholds of anions.…”

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confidence: 99%

“…Our observed PAD of the PE images of CH 3 COO − is consistent with the theoretical predication that the ground state of CH 3 COO• is 2 A ′′ (B 2 ) with the 2 A ′ (A ′ ) low-lying excited state. 7 Fig. 2 displays the photodetachment spectrum of CH 3 COO − in the photon energy range 373.65-375.25 nm by monitoring the total electron yield to search for DBSs in the vicinity of the 14 1 0 and 8 1 0 levels of CH 3 COO•.…”

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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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Density functional investigations of carboxyl free radicals: Formyloxyl, acetyloxyl, and benzoyloxyl radicals

Kieninger

Ventura

Suhai

1998

Int. J. Quant. Chem.

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ABSTRACT:The structure of the lowest electronic states of HCOO ؒ in C and C trans-HOCOؒ isomer about 55 kJrmol more stable. These facts agree closely with the most recent CASPT2rANO calculations on this system. Therefore, it is concluded that some DFT models can be used safely for the study of larger radicals of the same type Ž . despite several drawbacks discussed at length in this study . B3PW91, using several basis sets, is subsequently applied to the study of the possible reaction mechanisms of acetyloxyl radical, which exhibits a much more complicated path than formyloxyl, due to the presence of the methyl group. The optimum structures of isomers with coplanar or perpendicular CH and CO bonds were obtained for CH COO ؒ and two saddle points investigated along the same lines.

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Carboxyl Free Radicals: Formyloxyl (HCOO.bul.) and Acetyloxyl (CH3COO.bul.) Revisited

Cited by 52 publications

References 0 publications

Density-functional theory study on the arrangement of adsorbed formate molecules on Cu(110)

Density-functional theory study on the arrangement of adsorbed formate molecules on Cu(110)

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

Density functional investigations of carboxyl free radicals: Formyloxyl, acetyloxyl, and benzoyloxyl radicals

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