Mono, di, tri and tetraethylene glycol: Spectroscopic characterization using density functional method and experiment

Naganathappa, Mahadevappa; Chaudhari, Ajay

doi:10.1016/j.vibspec.2017.12.006

Cited by 2 publications

(3 citation statements)

References 47 publications

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“…Many papers have been published that quote the original microwave experiment of Bastiansen [39], for instance [53][54][55][56][57][58][59][60][61][62][63][64][65]. However, we were unable to find any precise determination of the experimental geometry in gas phase.…”

Section: Insert Figurementioning

confidence: 73%

“…Many papers − have been published that quote the original microwave experiment of Bastiansen . However, we were unable to find any precise determination of the experimental geometry in the gas phase (a “plausible” r 0 structure was derived from a microwave study by Caminati and Corbelli).…”

Section: Resultsmentioning

confidence: 90%

“…For the stable structures, when they are available, the first entry corresponds to the experimental values, followed by other accurate calculations and, at last, our own calculations at DFT and, eventually, MP2 levels, according to the following specifications: (a) 2ClEtOH, microwave spectroscopy, electron diffraction, ωB97X-D/cc-pVTZ calculations in this paper, and ωB97X-D/aug-cc-pVQZ and MP2/aug-cc-pVTZ calculations; (b) 1ClEtOH, ωB97X-D/cc-pVTZ calculations in this paper, ωB97X-D/aug-cc-pVQZ and MP2/aug-cc-pVTZ calculations; (c) vinyl alcohol syn-conformer microwave spectrum, CCSD(T)/ANO2, CCSD(T)/cc-pVQZ, and our own ωB97X-D/cc-pVTZ calculations; (d) vinyl alcohol anticonformer microwave spectrum, CCSD(T)/ANO2, CCSD(T)/cc-pVQZ, and our own ωB97X-D/cc-pVTZ calculations; (e) vinyl alcohol syn-conformer complexed with the HCl molecule arising from the dehalogenation of 1ClEtOH; the signed italicized numbers show the difference of geometries in the complex with respect to those in the isolated molecules, ωB97X-D/cc-pVTZ, this work; (f) same as (e) but for the anticonformer; (g) experimental and theoretical data for oxirane from ref and our own ωB97X-D/cc-pVTZ calculations; (h) structure of the oxirane HCl complex and ωB97X-D/cc-pVTZ, this work (signed italicized values are geometry differences with respect to the isolated monomers). This complex was studied experimentally by Legon et al, who predicted a structure similar to the one found here but with a significantly larger O–H bond length; (i) acetaldehyde, experimental, CCSD(T)/cc-pVQZ, and our own ωB97X-D/cc-pVTZ calculations; (j) acetaldehyde-HCl complex, ωB97X-D/cc-pVTZ, this work; (k) ethylene glycol, semiexperimental data, CCSD(T)/aug′-cc-pVQZ calculations, and our own ωB97X-D/cc-pVTZ calculations; (l) ethylene glycol HCl complex, ωB97X-D/cc-pVTZ, this work. (m–s) transition states and ωB97X-D/cc-pVTZ calculations.…”

Section: Resultsmentioning

confidence: 99%

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Computational Evidence Suggests That 1-Chloroethanol May Be an Intermediate in the Thermal Decomposition of 2-Chloroethanol into Acetaldehyde and HCl

et al. 2019

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The dehalogenation of 2-chloroethanol (2ClEtOH) in gas phase with and without participation of catalytic water molecules has been investigated using methods rooted into the density functional theory. The well-known HCl elimination leading to vinyl alcohol (VA) was compared to the alternative elimination route towards oxirane and shown to be kinetically and thermodynamically more favorable. However, the isomerization of VA to acetaldehyde in the gas phase, in the absence of water, was shown to be kinetically and thermodynamically less favorable than the recombination of VA and HCl to form the isomeric 1-chloroethanol (1ClEtOH) species. This species is more stable than 2ClEtOH by about 6 kcal mol -1 -1 ). Thus, it is concluded that while 1ClEtOH may be a plausible intermediate in the gas phase dehalogenation of 2ClEtOH, it is unlikely that it plays a major role in water complexes (or, by inference, aqueous solution). It is also shown that neither in the gas phase nor in the cluster with one water molecule, the oxirane path is competitive with the VA alcohol path.

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Section: Insert Figurementioning

confidence: 73%

Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 99%

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Computational Evidence Suggests That 1-Chloroethanol May Be an Intermediate in the Thermal Decomposition of 2-Chloroethanol into Acetaldehyde and HCl

et al. 2019

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An experimental and computational view of the photoionization of diol–water clusters

Wannenmacher,

Lu,

Amarasinghe

et al. 2024

The Journal of Chemical Physics

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In the interstellar medium, diols and other prebiotic molecules adsorb onto icy mantles surrounding dust grains. Water in the ice may affect the reactivity and photoionization of these diols. Ethylene glycol (EG), 1,2-propylene glycol, and 1,3-propylene glycol clusters with water clusters were used as a proxy to study these interactions. The diol–water clusters were generated in a continuous supersonic molecular beam, photoionized by synchrotron-based vacuum ultraviolet light from the Advanced Light Source, and subsequently detected by reflectron time-of-flight mass spectrometry. The appearance energies for the detected clusters were determined from the mass spectra, collected at increasing photon energy. Clusters of both diol fragments and unfragmented diols with water were detected. The lowest energy geometry optimized conformers for the observed EG–water clusters and EG fragment–water clusters have been visualized using density functional theory (DFT), providing insight into hydrogen bonding networks and how these affect fragmentation and appearance energy. As the number of water molecules clustered around EG fragments (m/z 31 and 32) increased, the appearance energy for the cluster decreased, indicating a stabilization by water. This trend was supported by DFT calculations. Fragment clusters from 1,2-propylene glycol exhibited a similar trend, but with a smaller energy decrease, and no trend was observed from 1,3-propylene glycol. We discuss and suggest that the reactivity and photoionization of diols in the presence of water depend on the size of the diol, the location of the hydroxyl group, and the number of waters clustered around the diol.

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Mono, di, tri and tetraethylene glycol: Spectroscopic characterization using density functional method and experiment

Cited by 2 publications

References 47 publications

Computational Evidence Suggests That 1-Chloroethanol May Be an Intermediate in the Thermal Decomposition of 2-Chloroethanol into Acetaldehyde and HCl

Computational Evidence Suggests That 1-Chloroethanol May Be an Intermediate in the Thermal Decomposition of 2-Chloroethanol into Acetaldehyde and HCl

An experimental and computational view of the photoionization of diol–water clusters

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