High-resolution infrared studies of the ν10, ν11, ν14, and ν18 levels of [1.1.1]propellane

Kirkpatrick, Robynne; Masiello, Tony; Martin, Matthew A.; Nibler, Joseph W.; Maki, Arthur G.; Weber, Alfons; Blake, Thomas A.

doi:10.1016/j.jms.2012.09.001

Cited by 4 publications

(5 citation statements)

References 25 publications

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“…The relation is − B z = B 0 + ∑ v α normalv ( harm ) d normalv / 2 [see ref , p 106, for justification of this relation] and the α sum from the Gaussian calculations is −0.000079 cm –1 . The uncertainty in this correction is unknown, but for similar compounds we have found − that the theoretical α values generally agree with experiment to within about 10%. Accordingly, we consider 20% to be a conservative estimate, yielding the value of 0.13778 (2) cm –1 given for B z in Table .…”

Section: Spectroscopic Analysismentioning

confidence: 54%

“…In addition, the Anharm/Vibrot options of Gaussian were used to obtain cubic and quartic potential constants for radialene that, with the quadratic terms, gave bond lengths, angles, and the rotational constants B e and C e for the equilibrium structure, as well as the vibration–rotation α corrections necessary to get the ground state B 0 and C 0 values. Although more time-intensive (for radialene, 32 h on a fast PC with four processors), we have found that such anharmonic calculations typically yield remarkably accurate values for most structural and rovibrational parameters of similar molecules. − …”

Section: Methodsmentioning

confidence: 85%

“…To our knowledge, no experimental spectroscopic or structural studies have been reported on radialene for the past three decades, although several authors have made use of ab initio theory to describe the bonding, aromaticity, electron affinity, and the harmonic vibrational frequencies of the molecule. , Nevertheless, there remain interesting questions about the structure of, and bonding in, radialene. In spectroscopic terms it is a symmetric top, and like several other small symmetric strained-ring molecules with interesting bonding arrangements studied by our group − (Figure ), radialene is expected to give high-resolution vibration–rotation spectra amenable to detailed analysis. Accordingly, we undertook a spectroscopic investigation of radialene using modern high-resolution methods.…”

Section: Introductionmentioning

confidence: 80%

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High-Resolution Infrared and Electron-Diffraction Studies of Trimethylenecyclopropane ([3]-Radialene)

et al. 2013

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Combined high-resolution spectroscopic, electron-diffraction, and quantum theoretical methods are particularly advantageous for small molecules of high symmetry and can yield accurate structures that reveal subtle effects of electron delocalization on molecular bonds. The smallest of the radialene compounds, trimethylenecyclopropane, [3]-radialene, has been synthesized and examined by these methods. The first high-resolution infrared spectra have been obtained for this molecule of D3h symmetry, leading to an accurate B0 rotational constant value of 0.1378629(8) cm(-1), within 0.5% of the value obtained from electronic structure calculations (density functional theory (DFT) B3LYP/cc-pVTZ). This result is employed in an analysis of electron-diffraction data to obtain the rz bond lengths (in Å): C-H = 1.072(17), C-C = 1.437(4), and C═C = 1.330(4). The results indicate that the effects of rehybridization and π-electron delocalization affects each result in a shortening of about 0.05 Å for the C-C bond in radialene compared to ethane. The analysis does not lead to an accurate value of the HCH angle; however, from comparisons of theoretical and experimental angles for similar compounds, the theoretical prediction of 117.5° is believed to be reliable to within 2°.

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Section: Spectroscopic Analysismentioning

confidence: 54%

Section: Methodsmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 80%

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High-Resolution Infrared and Electron-Diffraction Studies of Trimethylenecyclopropane ([3]-Radialene)

et al. 2013

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“…Mills [9] and used by others in the analysis of the spectrum of allene [10,11] and by us in previous work on D 3h symmetric top molecules such as propellane [12,13]. This convention was chosen by Cartwright and Mills to achieve agreement between experimental and theoretical signs for q + for symmetric tops of C 3v symmetry and, as applied to molecules of D 2d symmetry,…”

Section: Rovibrational Level Expressionsmentioning

confidence: 99%

“…[0.0] 0.053 H JK ×10 13 [0.0] −5.45 H KJ ×10 13 [0.0] 8.99 H K ×10 13 [0.0] −3.90 Δ 2 ×10 9 1.172 (16) 1.22…”

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confidence: 99%

Analysis of several high-resolution infrared bands of spiropentane, C5H8

Maki¹,

Price

Harzan

et al. 2015

Journal of Molecular Spectroscopy

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The high-resolution infrared absorption spectrum of spiropentane (C 5 H 8) has been measured from 200 to 4000 cm −1 , and a detailed analysis is presented for eight bands in the region from 700 to 2200 cm −1. Two fundamental perpendicular bands were analyzed, ν 22 and ν 24 near 1050 and 780 cm −1 , respectively, along with two fundamental parallel bands, ν 14 and ν 16 near 1540 and 990 cm −1 , respectively. Two other fundamentals, ν 17 and ν 23 , are seen as intense overlapping bands near 880 cm −1 and are Coriolis-coupled, producing a complex mixture in which only Pbranch transitions could be tentatively assigned for ν 17. In addition, three binary combination bands were fit at about 1570, 2082, and 2098 cm −1 which are assigned as either 2ν 24 or ν 5 +ν 16 in the first case, ν 4 +ν 22 in the second case, and 2ν 22 in the latter case. The two l-type resonance constants, q + and q − , were determined for each of the two perpendicular fundamentals ν 22 and ν 24. Those two constants were also responsible for splittings observed in the K = 3 levels of ν 24. For the ground state the order of the split K = 2 B 1 /B 2 levels has been reversed from that reported previously, based on the measurements and assignments for the ν 24 band. Rovibrational parameters deduced from the analyses are compared with those obtained from density functional Gaussian calculations at the anharmonic level.

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Molecules with Five Carbon Atoms

Vogt

2019

Structure Data of Free Polyatomic Molecules

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High-resolution infrared studies of the ν10, ν11, ν14, and ν18 levels of [1.1.1]propellane

Cited by 4 publications

References 25 publications

High-Resolution Infrared and Electron-Diffraction Studies of Trimethylenecyclopropane ([3]-Radialene)

High-Resolution Infrared and Electron-Diffraction Studies of Trimethylenecyclopropane ([3]-Radialene)

Analysis of several high-resolution infrared bands of spiropentane, C5H8

Molecules with Five Carbon Atoms

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