The far-infrared spectrum of acrolein, CH2CHCHO: The ν18 fundamental and (ν17+ν18)−ν18 hot bands

McKellar, A. R. W.; Tokaryk, D. W.; Appadoo, D.R.T.

doi:10.1016/j.jms.2007.06.001

Cited by 23 publications

(4 citation statements)

References 22 publications

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“…The good agreement between computation and experiment for all vibrations reported in ref further confirms their tentative assignment to the cis -acrolein. In passing, we note that for trans -acrolein, several fundamental and nonfundamental transitions were assigned in high-resolution (HR) measurements, , which confirmed the values reported in Table . Concerning overtones and combination bands, experimental data for trans -acrolein (on which HR measurements were focused on) agree well with our computations: 313 and 324 cm –1 for 2 v 18 , 484 and 488 cm –1 for v 18 + v 13 , 650 and 654 cm –1 for 2 v 13 , respectively.…”

Section: Resultssupporting

confidence: 86%

“…Recently, Jaman and Bhattacharya investigated the rotational spectra of the lowest torsional levels. After nearly complete determinations of the fundamental transitions in the infrared (IR) spectra of both conformers performed more than 30 years ago, , further analyses of the far-infrared spectrum of trans -acrolein including overtones and combination bands were reported in the last years , together with a structural determination based on NMR spectroscopy . Furthermore, the difference between the acrolein conformers in the gas phase (660 ± 40 cm –1 ) was derived from the temperature dependence of the intensities of electronic-vibrational spectrum bands. , …”

Section: Introductionmentioning

confidence: 99%

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Molecular Structure and Spectroscopic Signatures of Acrolein: Theory Meets Experiment

et al. 2014

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A comprehensive study of the molecular structure and IR spectrum of cis and trans acrolein has been performed by an integrated computational approach coupling methods rooted in the coupled-cluster ansatz and the density functional theory. From the one side, DFT anharmonic force fields allow us to determine very reliable semiexperimental structures for both isomers, which are in remarkable agreement with the geometries issuing from CCSD(T) computations accounting for the extrapolation to the complete basis set and core correlation. The same kind of coupled-cluster computations provide dipole moment, relative energies, and interconversion barrier in remarkable agreement with experiments. Finally, harmonic CCSD(T) results coupled to DFT evaluation of mechanical and electrical anharmonicity allow us, in the framework of second-order perturbative vibrational theory, to confirm most of the experimental assignments of IR spectra, and to suggest some additional interpretations for congested regions including fundamental bands together with overtones and combination bands.

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Section: Resultssupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Molecular Structure and Spectroscopic Signatures of Acrolein: Theory Meets Experiment

et al. 2014

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“…38 Given the number of states involved in DPM and DPM-d 12 , analysis of such perturbations becomes intractable without first state-by-state assignments using double resonance methods. The A symmetry of these zero-order levels makes both Fermi and perpendicular Coriolis coupling mechanisms possible.…”

Section: B the S 2 States Of Dpm And Dpm-d 12mentioning

confidence: 99%

Rotationally resolved studies of S and the exciton coupled S1/S2 origin regions of diphenylmethane and the d12 isotopologue

Stearns

Pillsbury

Douglass

et al. 2008

The Journal of Chemical Physics

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Rotationally resolved microwave and ultraviolet spectra of jet-cooled diphenylmethane (DPM) and DPM-d(12) have been obtained in S(0), S(1), and S(2) electronic states using Fourier-transform microwave and UV laser/molecular beam spectrometers. The S(0) and S(1) states of both isotopologues have been well fit to asymmetric rotor Hamiltonians that include only Watson distortion parameters. The transition dipole moment (TDM) orientations of DPM and DPM-d(12) are perpendicular to the C(2) symmetry axes with 66(2)%:34(2)% a:c hybrid-type character, establishing the lower exciton S(1) origin as a completely delocalized, antisymmetric combination of the zero-order locally excited states of the toluene-like chromophores. In contrast, the rotational structures of the S(2) origin bands at S(1)+123 cm(-1) and S(1)+116 cm(-1), respectively, display b-type Q-branch transitions and lack the central a-type Q-branch features that characterize the S(1) origins, indicating TDM orientations parallel to the C(2)(b) symmetry axes as anticipated for the upper exciton levels. However, rotational fits were not possible in line with expectations from previous work [N. R. Pillsbury, J. A. Stearns, C. W. Muller, T. S. Zwier, and D. F. Plusquellic, J. Chem. Phys. 129, 114301 (2008)] where the S(2) origins were found to be largely perturbed through vibronic interactions with the S(1) symmetric, antisymmetric torsional, and butterfly levels in close proximity. Predictions from a dipole-dipole coupling model and ab initio theories are shown to be in fair agreement with the observed TDM orientations and exciton splitting. The need to include out-of-ring-plane dipole coupling terms indicates that in-plane models are not sufficient to fully account for the excitonic interactions in this bichromophore.

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“…Torsional levels constants. Analysis of the far-infrared spectrum of trans acrolein in the ν 18 fundamental and (ν 17 + ν 18 ) − ν 18 hot bands were reported by McKellar et al [15]. Very recently, 10 μm high-resolution rotational spectral analysis of the ν 11 , ν 16 , ν 14 and ν 16 + ν 18 − ν 18 bands of trans-acrolein were reported by Xu et al [16].…”

Section: Transitionsmentioning

confidence: 90%

Millimeter-Wave Rotational Spectra of trans-Acrolein (Propenal) (CH₂CHCOH): A DC Discharge Product of Allyl Alcohol (CH₂CHCH₂OH) Vapor and DFT Calculation

Jaman

Bhattacharya

2012

Journal of Atomic, Molecular, and Optical Physics

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Millimeter-wave rotational spectrum oftrans-acrolein (propenal) (CH2CHCOH) produced by applying a DC glow discharge through a low-pressure (~10–20 mTorr) flow of allyl alcohol (CH2CHCH2OH) vapor has been observed in the ground and several excited torsional states in the frequency region: 60.0–99.0 GHz. A least-square analysis of the measured and previously reported rotational transition frequencies has produced a set of rotational and centrifugal distortion constants for the ground as well as excited torsional states. Detailed DFT calculations were also carried out with various functional and basis sets to evaluate the spectroscopic constants, dipole moment, and various structural parameters of thetransconformer of propenal for the ground state and compared with their corresponding experimental values. A linear variation of the inertia defect values with torsional quantum number (v=0,1,2,3) demonstrates that the equilibrium configuration oftrans-propenal is planar.

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The far-infrared spectrum of acrolein, CH2CHCHO: The ν18 fundamental and (ν17+ν18)−ν18 hot bands

Cited by 23 publications

References 22 publications

Molecular Structure and Spectroscopic Signatures of Acrolein: Theory Meets Experiment

Molecular Structure and Spectroscopic Signatures of Acrolein: Theory Meets Experiment

Rotationally resolved studies of S and the exciton coupled S1/S2 origin regions of diphenylmethane and the d12 isotopologue

Millimeter-Wave Rotational Spectra of trans-Acrolein (Propenal) (CH₂CHCOH): A DC Discharge Product of Allyl Alcohol (CH₂CHCH₂OH) Vapor and DFT Calculation

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The far-infrared spectrum of acrolein, CH2CHCHO: The ν18 fundamental and (ν17+ν18)−ν18 hot bands

Cited by 23 publications

References 22 publications

Molecular Structure and Spectroscopic Signatures of Acrolein: Theory Meets Experiment

Molecular Structure and Spectroscopic Signatures of Acrolein: Theory Meets Experiment

Rotationally resolved studies of S and the exciton coupled S1/S2 origin regions of diphenylmethane and the d12 isotopologue

Millimeter-Wave Rotational Spectra of trans-Acrolein (Propenal) (CH2CHCOH): A DC Discharge Product of Allyl Alcohol (CH2CHCH2OH) Vapor and DFT Calculation

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Millimeter-Wave Rotational Spectra of trans-Acrolein (Propenal) (CH₂CHCOH): A DC Discharge Product of Allyl Alcohol (CH₂CHCH₂OH) Vapor and DFT Calculation