Analysis of rotational structure in the high-resolution infrared spectrum and assignment of vibrational fundamentals of butadiene-2,3-13C2

Craig, Norman C.; Moore, Michael C.; Patchen, Amie K.; Sams, Robert L.

doi:10.1016/j.jms.2005.11.002

Cited by 8 publications

(5 citation statements)

References 15 publications

(28 reference statements)

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“…Adjustments for FR are not included in Table ; * indicates one component of an FR doublet. Calculated anharmonic frequencies are from CCSD(T)(FC)/aug-cc-pVTZ level of theory with core valence corrections. d The C–C stretch and CH 2 rock are strongly coupled. e The CH-wag and CH 2 twist are strongly coupled. f Ref . g Ref . h Ref . …”

Section: Theoretical Calculationsmentioning

confidence: 99%

Gas-Phase Raman Spectra of s-trans- and s-gauche-1,3-Butadiene and Their Deuterated Isotopologues

2011

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The gas-phase Raman spectra of 1,3-butadiene and its 2,3-d(2),1,1,4,4-d(4) and d(6) isotopologues have been recorded using intense (6 W) green laser excitation and sensitive CCD detection. Hundreds of bands have been observed and assigned for each isotopologue. These spectra provide the best data to date for the s-trans conformer and also provide the first direct observation of the gas-phase Raman bands of the s-gauche conformer. Spectra recorded at elevated temperatures up to 250 °C for the d(0) and d(6) species help confirm the assignment of bands for the gauche rotamer. DFT computations were utilized to complement the studies. For the most part, the observed gas-phase gauche bands are in good agreement with previous matrix isolation studies. A best set of frequencies are reported for the fundamentals of the gauche rotamer of the d(0) and d(6) species.

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Section: Theoretical Calculationsmentioning

confidence: 99%

Gas-Phase Raman Spectra of s-trans- and s-gauche-1,3-Butadiene and Their Deuterated Isotopologues

2011

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“…Rotational constants are available for BDE and a number of its isotopomers. These include ground-state rotational constants for BDE, 16 18 and BDE-2,3-13 C 2 19 obtained from the analysis of rotational structure in high-resolution infrared spectra. Ground-state rotational constants of BDE-1,1-d 2 , which has a tiny dipole moment, are available from the microwave investigation.…”

Section: Introductionmentioning

confidence: 99%

Equilibrium Structures for Butadiene and Ethylene: Compelling Evidence for Π-Electron Delocalization in Butadiene

2006

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Equilibrium structures have been determined for s-trans-1,3-butadiene and ethylene after adjusting the rotational constants obtained from rotational spectroscopy by vibration-rotation constants calculated from the results of quantum chemical calculations. For butadiene, the formal C=C bond length is 1.338 A, and the formal C-C bond length is 1.454 A. For ethylene, the C=C bond length is 1.3305 A. These values appear to be good to 0.001 A. It is shown for the first time that pi-electron delocalization has the structural consequences of increasing the length of the formal double bond by 0.007 A and decreasing the length of the formal single bond by 0.016 A. Comparisons are made with structures computed with several quantum chemical models. The MP2/cc-pVTZ results agree best with the new re structure.

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“…1/10 constants of eight isotopologues: the normal [9], 1,1-d 2 [10], 2,3-d 2 [9], 1,4-trans,trans-d 2 [11], 1,4-cis,cis-d 2 [11], 1,4-cis,trans-d 2 [11], 1- 13 C 1 [12], and 2,3-13 C 2 [13] species. With the notable exception of butadiene-1,1-d 2 which is slightly polar and was thus investigated using microwave spectroscopy by Caminati et al [10], the rotational constants of all other isotopologues were derived from highresolution ro-vibrational measurements.…”

Section: Accepted Articlementioning

confidence: 99%

“…Determination of the ground state constants thus relied on the assignments of rotational transitions in its dense vibrational bands, a challenging feat overcome in 2004 with the high-resolution analysis of three infrared bands, namely ν 17 (3100 cm −1 ), 8 ν 11 (908 cm −1 ), 9 and ν 20 (1596 cm −1 ). 9 From extensive isotopic investigations, Craig and co-workers 1 soon afterward derived a full semiexperimental structure from the ground state rotational constants of eight isotopologues: the normal, 9 1,1-d 2 , 10 2,3-d 2 , 9 1,4-trans,trans-d 2 , 11 1,4-cis,cis-d 2 , 11 1,4-cis,trans-d 2 , 11 1-13 C 1 , 12 and 2,3-13 C 2 13 species. With the notable exception of butadiene-1,1-d 2 , which is slightly polar and was thus investigated using microwave spectroscopy by Caminati et al, 10 the rotational constants of all other isotopologues were derived from high-resolution ro-vibrational measurements.…”

Section: ■ Introductionmentioning

confidence: 99%

Synchrotron-Based High Resolution Far-Infrared Spectroscopy of trans-Butadiene

et al. 2020

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The high resolution far-infrared spectrum of trans-butadiene has been re-investigated by Fouriertransform spectroscopy at two synchrotron radiation facilities, SOLEIL and the Canadian Light Source, at temperatures ranging from 50 to 340 K. Beyond the well-studied bands, two new fundamental bands lying below 1100 cm −1 , ν 10 and ν 24 , have been assigned using a combination of cross-correlation (ASAP software) and Loomis-Wood type (LWWa software) diagrams. While the ν 24 analysis was rather straightforward, ν 10 exhibits obvious signs of a strong perturbation, presumably owing to interaction with the dark ν 9 + ν 12 state. Effective rotational constants have been derived for both the v 10 = 1 and v 24 = 1 states. Since only one weak, infrared active fundamental band (ν 23 ) of trans-butadiene remains to be observed at high resolution in the far-infrared, searches for the elusive gauche conformer can now be undertaken with considerably greater confidence in the dense ro-vibrational spectrum of the trans form.

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Analysis of rotational structure in the high-resolution infrared spectrum and assignment of vibrational fundamentals of butadiene-2,3-13C2

Cited by 8 publications

References 15 publications

Gas-Phase Raman Spectra of s-trans- and s-gauche-1,3-Butadiene and Their Deuterated Isotopologues

Gas-Phase Raman Spectra of s-trans- and s-gauche-1,3-Butadiene and Their Deuterated Isotopologues

Equilibrium Structures for Butadiene and Ethylene: Compelling Evidence for Π-Electron Delocalization in Butadiene

Synchrotron-Based High Resolution Far-Infrared Spectroscopy of trans-Butadiene

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