IR Spectrum of the Other Rotamer of Formic Acid, <i>cis</i>-HCOOH

Pettersson, Mika; Lundell, Jan; Khriachtchev, Leonid; Räsänen, Markku

doi:10.1021/ja972362l

Cited by 221 publications

(256 citation statements)

References 17 publications

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“…[10][11][12] Nevertheless, it should be emphasized that the elementary mechanism of IR-induced rotamerization is far from being completely understood. For instance, direct coupling of the excited overtone levels with the torsional manifold is a very high-order process, thus quite improbable.…”

Section: Figurementioning

confidence: 99%

“…3 It has repeatedly been reported for other carboxylic acid monomers that selective excitation of the OH stretching vibrations are of great utility to study conformational isomerization processes in this type of compound. [10][11][12] Furthermore, contrary to UV irradiation, IR irradiation does not usually lead to decomposition of the matrix-isolated molecules. Because the IR irradiation carried out in the previous study on oxalic acid was not selective, we decided to submit this compound to a new investigation, where selective narrowband and tunable IR irradiation was used, to better characterize the observed isomerization processes and, in particular, to search for other conformational species.…”

Section: Introductionmentioning

confidence: 99%

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Infrared-Induced Rotamerization of Oxalic Acid Monomer in Argon Matrix

Maçôas¹,

Fausto²,

Pettersson³

et al. 2000

J. Phys. Chem. A

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Infrared-induced conformational isomerization of oxalic acid monomer isolated in an argon matrix at 7.5 K was studied by infrared spectroscopy. For the first time, three conformational states of this molecule were identified experimentally and their vibrational spectra are assigned. In good agreement with density functional theory predictions, all the observed conformers exhibit a trans OdC-CdO axis, differing in the relative conformation of their O-C-O-H axes. In the most stable conformer (belonging to the C 2h symmetry point group), two intramolecular OH‚‚‚Od hydrogen bonds are present. The second (C s ) most stable conformer shows a single OH‚‚‚Od bond, and the third one (C 2h ) does not exhibit any intramolecular hydrogen bond. Using narrowband tunable irradiation in the near-infrared region it was possible to promote very efficiently conformer interconversions, which was followed spectroscopically.

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Section: Figurementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Infrared-Induced Rotamerization of Oxalic Acid Monomer in Argon Matrix

Maçôas¹,

Fausto²,

Pettersson³

et al. 2000

J. Phys. Chem. A

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“…The higher-energy cis form can be efficiently prepared in rare-gas matrices by selective vibrational excitation of trans-FA. 11,12 The higher-energy conformer decays back to the ground-state form via tunneling of the −OH hydrogen atom. 12,13 The lifetime of the higher-energy cis conformer strongly depends on the surrounding, changing from 6.25 h in a nitrogen matrix 14 to 75 min in a xenon matrix 13 and to 5 s in a neon matrix.…”

Section: ■ Introductionmentioning

confidence: 99%

Dimers of the Higher-Energy Conformer of Formic Acid: Experimental Observation

et al. 2012

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We report on the first experimental observation of formic acid dimers composed of two molecules of the higher-energy cis conformer. The cis−cis formic acid dimers are prepared in an argon matrix by selective vibrational excitation of the ground state trans conformer (deuterated form HCOOD) combined with thermal annealing of the matrix at about 30 K. Five cis−cis formic acid dimers are predicted by ab initio calculations (interaction energies from −16.9 to −27.2 kJ mol −1 ), and these structures are used for the assignment of the experimental spectra. Selective vibrational excitation of the obtained cis−cis dimers leads to the formation of several trans−cis dimers, which supports the proposed assignments.

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“…[1][2][3][4][5][6][7] These studies have been mainly motivated by our interest in the conformational dynamics of the carboxylic group as a way to understand the process of intramolecular vibrational energy relaxation, which plays an important role in molecular reactivity. Interestingly, the photolysis of formic acid was shown to be conformationally dependent, being acknowledged as one of the first clear cases of optical control of chemical reactivity.…”

Section: Introductionmentioning

confidence: 99%

Internal Rotation in Propionic Acid: Near-Infrared-Induced Isomerization in Solid Argon

et al. 2005

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The conformational system of propionic acid (CH 3 CH 2 COOH) is studied in solid argon. It is predicted by the ab initio calculations that this molecule has four stable conformers. These four structures are denoted T t , T g ( , C t , and C g ( , and they differ by the arrangement around the C-O and C R -C bonds. The ground-state T t conformer is the only form present at 8 K after deposition of an argon matrix containing propionic acid. For the CH 3 CH 2 COOH and CH 3 CH 2 COOD isotopologues, narrow-band excitation of the first hydroxyl stretching overtone of the conformational ground state promotes the C R -C and C-O internal rotations producing the T g ( and C t conformers, respectively. A subsequent vibrational excitation of the produced T g ( form induces its conversion to the C g ( conformer by rotation around the C-O bond. In the dark, all of the produced conformers decay to the conformational ground state at different rates. The decay kinetics and its temperature dependence allow the identification of the conformers by IR absorption spectroscopy, which is supported by ab initio calculations of their vibrational spectra. For the CH 3 CH 2 COOD isotopologue, the excitation of molecules isolated in different matrix sites results in site-dependent photoisomerization rates for the C R -C and C-O internal rotations, which also confirm the identification of the photoproducts.

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IR Spectrum of the Other Rotamer of Formic Acid, cis-HCOOH

Cited by 221 publications

References 17 publications

Infrared-Induced Rotamerization of Oxalic Acid Monomer in Argon Matrix

Infrared-Induced Rotamerization of Oxalic Acid Monomer in Argon Matrix

Dimers of the Higher-Energy Conformer of Formic Acid: Experimental Observation

Internal Rotation in Propionic Acid: Near-Infrared-Induced Isomerization in Solid Argon

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