Formic Anhydride in the Gas Phase, Studied by Electron Diffraction and Microwave and Infrared Spectroscopy, Supplemented with Ab-Initio Calculations of Geometries and Force Fields

Wu, Guofeng; Shlykov, Sergey A.; Alseny, F. S. Van; Geise, H. J.; Sluyts, E.J.; Veken, B.J. van der

doi:10.1021/j100021a022

Cited by 20 publications

(28 citation statements)

References 11 publications

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“…Nevertheless, we prefer the combination model 1/set iii with the lowest R value and k ( u ) closest to unity. Moreover, it gives results most consistent with previous results of FA and AA; , for example, the best geometrical constraints come from 4-21G calculated geometries after correction to r α ° level. The indices of resolution in FAA are somewhat lower than in FA and AA.…”

Section: Electron Diffractionsupporting

confidence: 86%

“…In fact they clearly demonstrate that as far as C−O, OC−O, and C−O−C are concerned, the difference of FAA vs FA is more important than the difference in conformation (sp vs ap), whereas as far as CO, the opposite holds. Second, as we noted before, ,, it may be seen (Table ) that stretch−stretch constants between bonds sharing a common nucleus are positive and diminish in the order CO > C−O > C−C > C−H. Stretch−stretch constants between bonds without a common nucleus are alternating negative and positive, depending whether there is an odd or an even number of bonds between them.…”

Section: Vibrational Spectroscopymentioning

confidence: 58%

“…Hence, the number of refinable vibrational and geometrical parameters must be reduced. We used the same semirigid approach for FAA as we did before for FA, because both molecules were shown (see above) to have the same rigidity. Vibrational amplitudes, u , and vibrational amplitudes perpendicular to the internuclear distances, K °, computed from the force field, , are given in Table .…”

Section: Electron Diffractionmentioning

confidence: 99%

“…The major advantage of the combined approach is that it produces a model in agreement with all available gas-phase structural data. We aim to produce for FAA such a self-consistent model (see ref for procedures and refs , , and 8−11 for examples).

2 Experimental leveled intensities, I ( s ), with final backgrounds, B ( s ), for FAA.

3 Experimental (○) and theoretical () s M( s ) curve for FAA.…”

Section: Introductionmentioning

confidence: 99%

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Formic Acetic Anhydride in the Gas Phase, Studied by Electron Diffraction and Infrared Spectroscopy, Supplemented with ab-Initio Calculations of Geometries and Force Fields

Wu¹,

Shlykov²,

Alsenoy³

et al. 1996

J. Phys. Chem.

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The structure of formic acetic anhydride was studied by the joint analysis of gas-phase electron diffraction and infrared data, supported with extensive ab-initio calculations on the 4-21G and 6-31G** levels. All data agree with the gas phase at room temperature existing in the planar (sp,ap) conformer. Best electron diffraction geometry was obtained using geometrical constraints derived from 4-21G calculations after correction to r α° level. Also, the scaled 4-21G force field performed better than its 6-31G** counterpart. The new model of formic acetic anhydride is self-consistent, reproduces the IR frequencies with a root-mean-square deviation of 8.8 cm-1, and results in an improved frequency assignment as well as in a good qualitative agreement between observed and calculated IR band intensities. Formic acetic anhydride is conformationally and spectroscopically very different from acetic anhydride, but strongly resembles formic anhydride, although differences remain. The similarities with formic anhydride are ascribed to an attractive nonbonded H (formyl)···O= interaction, while the dissimilarities are ascribed to a larger electronic interaction between two formyl moieties rather than between a formyl and an acetyl moiety.

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Section: Electron Diffractionsupporting

confidence: 86%

Section: Vibrational Spectroscopymentioning

confidence: 58%

Section: Electron Diffractionmentioning

confidence: 99%

2 Experimental leveled intensities, I ( s ), with final backgrounds, B ( s ), for FAA.

3 Experimental (○) and theoretical () s M( s ) curve for FAA.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Formic Acetic Anhydride in the Gas Phase, Studied by Electron Diffraction and Infrared Spectroscopy, Supplemented with ab-Initio Calculations of Geometries and Force Fields

Wu¹,

Shlykov²,

Alsenoy³

et al. 1996

J. Phys. Chem.

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show abstract

“…The parent compound, formic anhydride, HC(O)-O-C(O)H, has been studied extensively by gas electron diffraction (GED) [1,2], microwave spectroscopy [3], and quantum chemical calculations [4]. All investigations result in a planar [sp, ap] conformation which is stabilized by an intramolecular O Á Á Á H bond.…”

Section: Introductionmentioning

confidence: 99%