The evolution of the structural, vibrational and electronic properties of the cyclic ethers – on ring size. An ab initio study

Ford, T.A.

doi:10.1016/j.molstruc.2014.03.064

Cited by 6 publications

(4 citation statements)

References 68 publications

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“…46 However, the structures are nearly isoenergetic, with a difference of ≤0.2 kJ mol −1 . 47 Moreover, whereas much work has focused on aspects of the rotational spectroscopy, not much has been done on the thermochemical implications, specifically on the nature of the ring-puckering vibrations that, in essence, drive pseudorotation.…”

Section: ■ Computational Methodologymentioning

confidence: 99%

“…Experiment has shown that the C s structure of THF with a CCCC dihedral angle of 0° is the global minimum; it is only at quite high levels of theory, such as MP2/aug-cc-pVTZ, that this is reflected by calculations, which suggest that the C 2 structure is the more stable . However, the structures are nearly isoenergetic, with a difference of ≤0.2 kJ mol –1 . Moreover, whereas much work has focused on aspects of the rotational spectroscopy, not much has been done on the thermochemical implications, specifically on the nature of the ring-puckering vibrations that, in essence, drive pseudorotation.…”

Section: Computational Methodologymentioning

confidence: 99%

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H-Atom Abstraction Reactions by Ground-State Ozone from Saturated Oxygenates

Würmel

Simmie

2017

J. Phys. Chem. A

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Theoretical insights into H-abstraction by ozone from saturated species have been virtually nonexistent, in sharp contrast to the situation for reactions with unsaturated species. Our computed rate constants for reactions with tetrahydrofuran and its methyl derivatives, obtained at various levels of theory, show that abstraction occurs primarily at the carbons situated beside the heterocyclic oxygen, with least likely reaction from the methyl groups. All of the methods tested are in broad relative agreement with this conclusion and with recent experiments although they do differ widely in terms of their absolute values. Abstraction leads variously to the formation of hydrotrioxides, ROOOH, or more directly to R-OH + O(Δ). To understand some of the observed behaviors, dimethyl and diethyl acyclic ethers, methyl and ethyl hydroperoxides, and the alcohols methanol and ethanol were also included in this study. For the simplest system, CHOH + O → HC═O + HO, an all-electron scalar relativistic CCSD(T)/CBS approach yields a barrier height that differs by >5 kJ mol when an additional multireference treatment up to CCSDT(Q) is considered.

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Section: ■ Computational Methodologymentioning

confidence: 99%

Section: Computational Methodologymentioning

confidence: 99%

H-Atom Abstraction Reactions by Ground-State Ozone from Saturated Oxygenates

Würmel

Simmie

2017

J. Phys. Chem. A

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“…The full conformational space of five–membered ring includes pure 10 Envelope ( E ) and 10 Twist ( T ) conformations (and their intermediates) [ 35 , 36 , 37 , 38 ]. However, in our case, they can be reduced to six unique conformations due to the symmetry of the furan ring—see Supplementary Materials for the conformational circle.…”

Section: Resultsmentioning

confidence: 99%

Impact of Deuteration and Temperature on Furan Ring Dynamics

2021

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Despite significant progress in conformational analysis of cyclic molecules, the number of computational studies is still limited while most of that available in the literature data have been obtained long time ago with outdated methods. In present research, we have studied temperature driven conformational changes of the furan ring at three different temperatures. Additionally, the effect of deuteration on the ring dynamics is discussed; in addition, the aromaticity indices following the Bird and HOMA schemes are computed along all trajectories. Our ab initio molecular dynamic simulations revealed that deuteration has changed the furan ring dynamics and the obvious consequences; in addition, the shape and size of molecule are expected to be different.

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“…The conformation of tetrahydrofuran (THF) molecules in vapor has been the subject of considerable computational and experimental studies [8][9][10][11], the most recent of which stated that the difference between the most stable twisted C 2 conformer and the bent C s conformer is 17 ± 15 cm −1 [4]. Because of low symmetry, all modes are allowed in both the Raman and the infrared spectrum.…”

Section: Introductionmentioning

confidence: 99%

Low Temperature Raman Spectroscopy of Tetrahydrofuran: Phonon Spectra Compared to Matrix Isolation Spectra in Air

Mohaček-Grošev

2024

Crystals

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The conformation of tetrahydrofuran (THF) molecules in vapor has been the subject of considerable computational and experimental studies, the most recent by Park and Kwon stated that the difference between the most stable, twisted C2 conformer and the bent Cs conformer is 17 ± 15 cm−1. Because of low symmetry, all modes from both conformers are allowed in the Raman and infrared spectra. In 1982, Aleksanyan and Antipov observed the emergence of two Raman bands at 249 and 303 cm−1 at 20 K, while only one band at 293 cm−1 was present in solid THF at 142. They assigned the 249 cm−1 band to the restricted pseudorotational motion of THF in the solid state, because on heating, the band diminishes and is too weak to be observed near melting point (at 142 K). Cadioli et al. reported a study of the vibrational spectrum of tetrahydrofuran, giving a complete assignment of all bands including those present in the low-temperature Raman spectrum at 85 K and infrared bands observed at 90 K. They assigned the band at 242 cm−1 in the Raman spectrum at 85 K as an overtone of the lowest normal mode (pseudorotational mode), while the 299 cm−1 band in the same spectrum was assigned as a radial mode. In the following, low-temperature Raman spectra of solid THF together with the Raman matrix isolated spectrum of THF in air will be presented and compared to published data. Our results indicate that the band observed at 245 cm−1 at 10 K is too strong to be assigned as an overtone, since its intensity is of the same magnitude as the 299 cm−1 band.

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The evolution of the structural, vibrational and electronic properties of the cyclic ethers – on ring size. An ab initio study

Cited by 6 publications

References 68 publications

H-Atom Abstraction Reactions by Ground-State Ozone from Saturated Oxygenates

H-Atom Abstraction Reactions by Ground-State Ozone from Saturated Oxygenates

Impact of Deuteration and Temperature on Furan Ring Dynamics

Low Temperature Raman Spectroscopy of Tetrahydrofuran: Phonon Spectra Compared to Matrix Isolation Spectra in Air

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