Origin of the CO Stretch Mode Splitting in the Formic Acid Dimer

and, Weili Qian; Krimm, Samuel

doi:10.1021/jp9610123

Cited by 27 publications

(43 citation statements)

References 35 publications

(106 reference statements)

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“…For the dimers of formic and acetic acid, the cyclic structures are the only isomers detected in gas phase work. [29][30][31][32][33] Evidence that helium nanodroplets trap the dimers in the acyclic (headto-tail) structure has recently come from an infrared spectroscopic study of formic acid dimers. 34 There is also prior evidence from formic acid monomers in argon matrices that the acyclic structure is a precursor to the cyclic structure as the matrix is annealed.…”

Section: Anions With Attached Helium Atomsmentioning

confidence: 99%

Electron attachment and electron ionization of acetic acid clusters embedded in helium nanodroplets

Silva

Jaksch

Martins

et al. 2009

Phys. Chem. Chem. Phys.

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The effect of incident electrons on acetic acid clusters is explored for the first time. The acetic acid clusters are formed inside liquid helium nanodroplets and both cationic and anionic products ejected into the gas phase are detected by mass spectrometry. The cation chemistry (induced by electron ionization at 100 eV) is dominated by production of protonated acetic acid (Ac) clusters, Ac n H + , although some fragmentation is also observed. In the case of anion production (at 2.8 eV electron energy) there is a clear distinction between the monomer and the clusters. For the monomer the dominant product is the dehydrogenated species, [Ac-H] À , whereas for the clusters both the parent anion, Ac n À , and the dehydrogenated species, [Ac n -H] À , have similar abundances. A particularly intriguing contrast between the monomer and cluster anions is that helium atoms are seen attached to the latter whereas no evidence of helium atom attachment is found for the monomer. This surprising observation is attributed to the formation of acyclic (head-to-tail) acetic acid clusters in helium nanodroplets, which have more favourable electronic properties for binding helium atoms. The acyclic clusters represent a local minimum on the potential energy surface and in the case of the dimer this is distinct from the cyclic isomer (the global minimum) identified in gas phase experiments.

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Section: Anions With Attached Helium Atomsmentioning

confidence: 99%

Electron attachment and electron ionization of acetic acid clusters embedded in helium nanodroplets

Silva

Jaksch

Martins

et al. 2009

Phys. Chem. Chem. Phys.

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“…Several Fourier-transform-infrared studies have been carried out on formic acid dimer in the gas phase, [25][26][27][28] which indicated the existence of a cyclic, double-hydrogenbonded structure. Ab initio studies [29][30][31][32][33][34] have been carried out that clearly show that this structure corresponds to the global minimum on the potential surface. 23 Recently, a highresolution spectroscopic study of a carboxylic acid dimer in the gas phase was reported by two of us.…”

Section: Introductionmentioning

confidence: 95%

Polar isomer of formic acid dimers formed in helium nanodroplets

Madeja

Havenith

Nauta

et al. 2004

The Journal of Chemical Physics

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The infrared spectrum of formic acid dimers in helium nanodroplets has been observed corresponding to excitation of the "free" OH and CH stretches. The experimental results are consistent with a polar acyclic structure for the dimer. The formation of this structure in helium, as opposed to the much more stable cyclic isomer with two O-H...O hydrogen bonds, is attributed to the unique growth conditions that exist in helium droplets, at a temperature of 0.37 K. Theoretical calculations are also reported to aid in the interpretation of the experimental results. At long range the intermolecular interaction between the two monomers is dominated by the dipole-dipole interaction, which favors the formation of a polar dimer. By following the minimum-energy path, the calculations predict the formation of an acyclic dimer having one O-H...O and one C-H...O contact. This structure corresponds to a local minimum on the potential energy surface and differs significantly from the structure observed in the gas phase.

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“…The complex has been extensively studied, both experimentally [36][37][38][39][40][41][42][43][44] and theoretically. [45][46][47][48][49][50][51][52] According to electron diffraction studies, the structure of FAD is planar with C 2h symmetry, 37,39 as shown in Fig. 4.…”

Section: Formic Acid Dimer "Hcooh…mentioning

confidence: 99%

High-resolution CO-laser sideband spectrometer for molecular-beam optothermal spectroscopy in the 5–6.6 μm wavelength region

Merker

Engels

Madeja

et al. 1999

Review of Scientific Instruments

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Articles you may be interested inA two-color tunable infrared/vacuum ultraviolet spectrometer for high-resolution spectroscopy of molecules in molecular beams Rev. Sci. Instrum. 83, 014102 (2012); 10.1063/1.3673639 An axial molecular-beam diode laser spectrometer Rev. Sci. Instrum. 75, 46 (2004); 10.1063/1.1634364 A sub-Doppler resolution double resonance molecular beam infrared spectrometer operating at chemically relevant energies (2 eV) Rev. Sci. Instrum. 71, 4032 (2000)

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Origin of the CO Stretch Mode Splitting in the Formic Acid Dimer

Cited by 27 publications

References 35 publications

Electron attachment and electron ionization of acetic acid clusters embedded in helium nanodroplets

Electron attachment and electron ionization of acetic acid clusters embedded in helium nanodroplets

Polar isomer of formic acid dimers formed in helium nanodroplets

High-resolution CO-laser sideband spectrometer for molecular-beam optothermal spectroscopy in the 5–6.6 μm wavelength region

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