The Submillimeter-Wave Spectrum and Quantum Chemical Calculations of Glyoxylic Acid

Bakri, B.; Demaison, J.; Margulès, L.; Møllendal, Harald

doi:10.1006/jmsp.2001.8366

Cited by 28 publications

(19 citation statements)

References 49 publications

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“…Under this condition, the $cCt \to tCt$ interconversion barrier was found to be 42.4 kJ/mol (maximum at ω H1O2C3C4 = 90° and ω O2C3C4O5 = −50.5°). The geometrical parameters of the cTc conformation are in line with the experimental ones coming from electron diffraction spectra19 but the calculated OH and CO bond lengths are 0.081 and 0.014 Å, respectively, shorter whilst the COH angle is 3.4° larger, which indicates that the hydrogen bond effects suffer somewhat underestimation. In any case, our results are practically coincident with those obtained at B3LYP/6311+G* level8 and other similar bases11 whereas bond lengths are closer to the experimental ones than those predicted by the MP2/6‐31G**(5d) basis set 6…”

Section: Resultssupporting

confidence: 77%

“…Also a recent theoretical study of Hirao5 suggests that electrostatic interaction can be responsible for the formic acid conformational preference. Numerous experimental and theoretical papers concerning the chemical physical properties of oxalic,6–16 glyoxylic17–24 and pyruvic25–38 acids are present in the literature but only one of them10 deals with quantitative hydrogen bond energy evaluation. Moreover, investigations in solution are scarce and generally devoted to hydrated clusters of formic, oxalic and pyruvic acids.…”

Section: Introductionmentioning

confidence: 99%

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DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution

Buemi

2009

J of Physical Organic Chem

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DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution Giuseppe Buemi a * The molecular geometries of the possible conformations of formic, oxalic, glyoxylic and pyruvic acids have been fully optimized at DFT B3LYP/6-311RRG(d,p) levels of calculation in vacuum as well as in water and acetone solution. Solutions were treated according to the SCRF PCM approach but some formic acid-water and formic acid-acetone clusters as well as adducts of oxalic acid with two or four water molecules were also taken into account for testing the importance of specific solute-solvent effects. All the most stable isomers of the title compounds are characterized by weak intramolecular hydrogen bonds, whose strengths (E HB ) cannot be correctly estimated as stability difference between the open and chelate forms since the energy of the former isomer is, in turn, stabilized by a weak hydrogen bridge due to the formic acid moiety. Following the Rotation Barrier Method (RBM), proposed some years ago, E HB in the examined molecules (gas phase) falls in the range of 18-22 kJ/mol for oxalic acid (9.6 kJ/mol for the c-C-t isomer), 16.8 kJ/mol for glyoxylic acid and 19.8 kJ/mol for pyruvic acid. Most of them disappear at all, or nearly at all, both in acetone and aqueous solution, in consequence of the solvent effect. The frequencies of the OH and C --O stretching modes, calculated according to the anharmonic oscillator model, are in very good agreement with the experimental literature data, where available.Specific solvent effects can be obtained by considering the adduct with at least one solvent molecule. Figure 2 shows the lowest energy hydrogen bonded complexes formed by trans-and

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Section: Resultssupporting

confidence: 77%

Section: Introductionmentioning

confidence: 99%

DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution

Buemi

2009

J of Physical Organic Chem

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“…The vibration is thus well isolated, as further confirmed by the similarity with the OH stretch frequency in HDSO 4 (3611.3 cm À1 ) [74]. The structure of trans 1 glyoxylic acid, HCOCOOH, the simplest -oxoacid, has been determined at the CCSD(T)/VQZ level of theory [75]. This planar conformer is the most stable one and has the two C¼O groups in anti-periplanar position (trans) to one another.…”

Section: Larger Speciesmentioning

confidence: 80%

The equilibrium OH bond length

Demaison

Herman

Liévin

2007

International Reviews in Physical Chemistry

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“…74,75 The rotational conformers of GA have been observed, including two accessible in the temperature range of this study. [76][77][78][79][80][81][82][83][84] The lowest energy conformer, the Trans-cis ͑Tc͒, contains an intramolecular hydrogen bond. The Transtrans ͑Tt͒ conformer where the acidic hydrogen is rotated away from the aldehyde group, which precludes intramolecular hydrogen bonding, is 1.2 kcal/mol higher in energy.…”

Section: Introductionmentioning

confidence: 99%

Dynamics and spectroscopy of vibrational overtone excited glyoxylic acid and 2,2-dihydroxyacetic acid in the gas-phase

Takahashi

Plath

Axson

et al. 2010

The Journal of Chemical Physics

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The early time dynamics of vibrationally excited glyoxylic acid and of its monohydrate 2,2-dihydroxyacetic acid are investigated by theoretical and spectroscopic methods. A combination of "on-the-fly" dynamical simulations and cavity ring-down spectroscopy on the excited O-H stretching vibrational levels of these molecules observed that conformers that possess the correct structure and orientation react upon excitation of Deltaupsilon(OH)=4,5, while the structurally different but near isoenergetic conformers do not undergo unimolecular decay by the same direct and fast process. Experiment and theory give a femtosecond time scale for hydrogen atom chattering in the vibrationally excited glyoxylic acid. This process is the precursor for the concerted decarboxylation of the ketoacid. We extrapolate the results obtained here to suggest a rapid subpicosecond overall reaction. In these light-initiated reactions, relatively cold hydroxycarbenes, stable against further unimolecular decay, are expected products since most of the excitation energy is consumed by the endothermicity of the reaction. Glyoxylic acid and its monohydrate are atmospherically relevant ketoacids. The vibrational overtone initiated reactions of glyoxylic acid leading to di- and monohydroxycarbenes on subpicosecond time scales are potentially of importance in atmospheric chemistry since the reaction is sufficiently rapid to avoid collisional dissipation.

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The Submillimeter-Wave Spectrum and Quantum Chemical Calculations of Glyoxylic Acid

Cited by 28 publications

References 49 publications

DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution

DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution

The equilibrium OH bond length

Dynamics and spectroscopy of vibrational overtone excited glyoxylic acid and 2,2-dihydroxyacetic acid in the gas-phase

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