The ν21 ring puckering mode of 3-oxetanone: A far infrared spectroscopic investigation using synchrotron radiation

Chen, Ziqiu; Wijngaarden, Jennifer van

doi:10.1016/j.jms.2012.08.006

Cited by 11 publications

(8 citation statements)

References 28 publications

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“…The achieved FIR deviations of significantly below 0.0001 cm –1 for the three data subsets with the strongest lines compare favorably with those achieved with the same source and spectrometer. The recent fits for 3-oxetanone, , for example, were at the level of just below 0.0001 cm –1 or higher. The fits for thiophosgene, had a deviation of 0.000 085 cm –1 for the parent 35 Cl 2 S, but a higher value, 0.000 110 cm –1 for 35 Cl 37 ClS.…”

Section: Resultsmentioning

confidence: 97%

Far-Infrared Spectrum of S(CN)₂ Measured with Synchrotron Radiation: Global Analysis of the Available High-Resolution Spectroscopic Data

Kisiel

Winnewisser

et al. 2013

J. Phys. Chem. A

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The high resolution Fourier transform spectrum of the chemically challenging sulfur dicyanide, S(CN)2, molecule was recorded at the far-infrared beamline of the synchrotron at the Canadian Light Source. The spectrum covered 50-350 cm(-1), and transitions in three fundamentals, ν4, ν7, and ν8, as well as in the hot-band sequence (n + 1)ν4 - nν4, n = 1-4, have been assigned and measured. Global analysis of over 21,300 pure rotation and rotation vibration transitions allowed determination of precise energies for 12 of the lowest vibrationally excited states of S(CN)2, including the five lowest fundamentals. These results constitute an extensive set of benchmarks for ab initio anharmonic force field calculations and the observed and calculated vibration-rotation constants and anharmonic frequencies are compared. The semiexperimental equilibrium, r(e)(SE), geometry of S(CN)2 has also been evaluated. In the course of the measurements, new information concerning the physical chemistry of S(CN)2 has been obtained.

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Section: Resultsmentioning

confidence: 97%

Far-Infrared Spectrum of S(CN)₂ Measured with Synchrotron Radiation: Global Analysis of the Available High-Resolution Spectroscopic Data

Kisiel

Winnewisser

et al. 2013

J. Phys. Chem. A

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“…Small, oxygen-containing ring structures are commonly used in synthetic and pharmaceutical chemistry − and may also occur as intermediates during the oxidation of hydrocarbon radicals. − Cyclic structures exhibiting a high degree of ring strain are often prone to thermal decomposition, even at relatively low temperatures, due to their instability. − The cyclic ketone 3-oxetanone (Figure ) is an archetype of such small, ring-strained compounds. Most studies of 3-oxetanone have focused on how ring strain and the electronic interactions of atoms in the ring relate to its planar equilibrium geometry. ,− The occurrence of 3-oxetanone is suspected in the decomposition of the acetonylperoxy radical, an intermediate formed during the atmospheric processing of acetone . Atmospheric degradation of acetone produces the acetonyl radical, CH 3 C(O)CH 2 , which reacts with O 2 to form the acetonylperoxy radical.…”

Section: Introductionmentioning

confidence: 99%

Pyrolysis Reactions of 3-Oxetanone

et al. 2015

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The pyrolysis products of gas-phase 3-oxetanone were identified via matrix-isolation Fourier transform infrared spectroscopy and photoionization mass spectrometry. Pyrolysis was conducted in a hyperthermal nozzle at temperatures from 100 to 1200 °C with the dissociation onset observed at ∼600 °C. The ring strain in the cyclic structure of 3-oxetanone causes the molecule to decompose at relatively low temperatures. Previously, only one dissociation channel, producing formaldehyde and ketene, was considered as significant in photolysis. This study presents the first experimental measurements of the thermal decomposition of 3-oxetanone demonstrating an additional dissociation channel that forms ethylene oxide and carbon monoxide. Major products include formaldehyde, ketene, carbon monoxide, ethylene oxide, ethylene, and methyl radical. The first four products stem from initial decomposition of 3-oxetanone, while the additional products, ethylene and methyl radical, are believed to be due to further reactions involving ethylene oxide.

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“…Synchrotron-based high-resolution infrared investigations characterizing the ground state vibrational bands of 3-oxetanone molecule have been reported recently. 14,15 Several studies have been reported in the literature on the decomposition reactions of small heterocyclic molecules and their substituted variants. For the thermal decomposition of 3oxetanone, two different dissociation patterns 16,17 can be considered as shown in Figure 1.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Semiempirical and ab initio , calculations indicated a planar geometry with C 2 v symmetry for this molecule (see Figure ), which is consistent with infrared , and microwave spectroscopic predictions. Synchrotron-based high-resolution infrared investigations characterizing the ground state vibrational bands of 3-oxetanone molecule have been reported recently. , …”

Section: Introductionmentioning

confidence: 99%

Dissociation Chemistry of 3-Oxetanone in the Gas Phase

2017

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3-Oxetanone is a strained cyclic molecule which plays an important role in synthetic chemistry. A few studies exist in the literature about the equilibrium properties of this molecule and the dissociation patterns of substituted 3-oxetanones. For the unsubstituted 3-oxetanone, formation of ketene (CHCO) and formaldehyde (HCHO) was considered to be the major dissociation pathway. In a recent work, pyrolysis products of 3-oxetanone molecule in the gas phase were investigated by Fourier transform infrared spectroscopy and photoionization mass spectrometry. In this study, an additional dissociation channel forming ethylene oxide (c-CHO) and carbon monoxide CO was reported. In the present work, gas phase dissociation chemistry of 3-oxetanone was investigated by electronic structure theory, ab initio classical chemical dynamics simulations, and Rice-Ramsperger-Kassel-Marcus (RRKM) rate constant calculations. The barrier height for the ethylene oxide channel was found to be much higher than the ketene pathway. The dynamics simulations were performed at three different total energies, viz., 150, 200, and 300 kcal/mol, and multiple reaction pathways and varying branching ratios observed. A new dissociation channel involving a ring-opened isomer of ethylene oxide was identified in the simulations. This pathway has a lower energy barrier and was dominant in our dynamics simulations.

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The ν21 ring puckering mode of 3-oxetanone: A far infrared spectroscopic investigation using synchrotron radiation

Cited by 11 publications

References 28 publications

Far-Infrared Spectrum of S(CN)₂ Measured with Synchrotron Radiation: Global Analysis of the Available High-Resolution Spectroscopic Data

Far-Infrared Spectrum of S(CN)₂ Measured with Synchrotron Radiation: Global Analysis of the Available High-Resolution Spectroscopic Data

Pyrolysis Reactions of 3-Oxetanone

Dissociation Chemistry of 3-Oxetanone in the Gas Phase

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The ν21 ring puckering mode of 3-oxetanone: A far infrared spectroscopic investigation using synchrotron radiation

Cited by 11 publications

References 28 publications

Far-Infrared Spectrum of S(CN)2 Measured with Synchrotron Radiation: Global Analysis of the Available High-Resolution Spectroscopic Data

Far-Infrared Spectrum of S(CN)2 Measured with Synchrotron Radiation: Global Analysis of the Available High-Resolution Spectroscopic Data

Pyrolysis Reactions of 3-Oxetanone

Dissociation Chemistry of 3-Oxetanone in the Gas Phase

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Product

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Far-Infrared Spectrum of S(CN)₂ Measured with Synchrotron Radiation: Global Analysis of the Available High-Resolution Spectroscopic Data

Far-Infrared Spectrum of S(CN)₂ Measured with Synchrotron Radiation: Global Analysis of the Available High-Resolution Spectroscopic Data