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

Jaman, A.I.; Bhattacharya, Rahul

doi:10.1155/2012/363247

Cited by 3 publications

(6 citation statements)

References 26 publications

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“… a Best estimate from eq . b B 0 from ref (parent species: ref ) and vibrational corrections at the B2PLYP/aug-cc-pVTZ level. Given uncertainties are 3 times the standard deviation of the fit. c Substitution structure, ref . d Equilibrium values computed at the best-estimated structure using the CCSD(T)/aug-cc-pVQZ level of theory. e Equilibrium values of footnote d corrected for vibrational and temperature effects at the B2PLYP/aug-cc-pVTZ level. f Reference . …”

Section: Resultsmentioning

confidence: 99%

“… b B 0 from ref (parent species: ref ) and vibrational corrections at the B2PLYP/aug-cc-pVTZ level. Given uncertainties are 3 times the standard deviation of the fit. …”

Section: Resultsmentioning

confidence: 99%

“…[28][29][30]33,86 ), i.e., an accuracy of 0.001−0.002 Å for bond distances and about 0.05−0.1 degrees for angles. To the best of our knowledge, despite the number of theoretical investigations on acrolein and its trans−cis isomerization, 16 Focusing on the semiexperimental equilibrium structure, which was obtained as explained in the methodology section, we note that for both trans-and cis-acrolein very good residuals were obtained: in terms of observed − calculated differences for equilibrium rotational constants, the root-mean-square (rms) deviation is ∼0.0001 MHz for trans and ∼0.0002 MHz for cis. We furthermore point out the importance of the electronic corrections to rotational constants, in particular for the trans form.…”

Section: ■ Methodologymentioning

confidence: 99%

“…Winnewisser et al extended the analysis of the ground state of the trans form to the millimeter wave region up to 180 GHz, thus yielding an improved and extended set of ground-state rotational and centrifugal distortion constants. 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 .…”

Section: Introductionmentioning

confidence: 99%

“…Several quantum-chemical computations ,,− have paralleled the experimental work, but none of them employed the state-of-the art methods, which are nowadays able to provide for small- to medium-sized molecules structures and spectroscopic parameters rivaling the most sophisticated experimental techniques (see, for example, refs − ). It is the purpose of the present study to fill this gap by means of an integrated approach based on the coupled-cluster (CC) ansatz, together with the extrapolation to complete basis set (CBS) limit and inclusion of core–valence (CV) correlation effects for energies and structures.…”

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: Resultsmentioning

confidence: 99%

“… b B 0 from ref (parent species: ref ) and vibrational corrections at the B2PLYP/aug-cc-pVTZ level. Given uncertainties are 3 times the standard deviation of the fit. …”

Section: Resultsmentioning

confidence: 99%

Section: ■ Methodologymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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Extending the Applicability of the Semi-experimental Approach by Means of “Template Molecule” and “Linear Regression” Models on Top of DFT Computations

et al. 2021

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The accurate determination of equilibrium structures for isolated molecules plays a central role in the evaluation and interpretation of stereoelectronic, thermodynamic, and spectroscopic properties. For small semi-rigid systems, state-of-the-art quantum-chemical computations can rival the most sophisticated experimental results. For larger molecules, cheaper yet accurate approaches need to be defined. The double-hybrid rev-DSD-PBEP86 functional already delivers remarkable results that can be further improved by means of a “Lego brick” model. This is based on the idea that a molecular system can be seen as formed by different fragments (the “Lego bricks”), whose accurate semi-experimental (SE) equilibrium geometries are available. The template molecule (TM) approach can be used to account for the modifications occurring when going from the isolated fragment to the molecular system under investigation, with the linear regression (LR) model employed to correct the linkage between the different fragments. The resulting TM-SE_LR approach has been tested with respect to available SE equilibrium structures and rotational constants. Indeed, the latter parameters straightforwardly depend on the equilibrium geometry of the system under consideration. The main outcome of our study is the reliability, robustness, and accuracy of this novel approach. The molecular systems considered for benchmarking the TM-SE_LR scheme are those formally issued from addition/elimination reactions of nucleophilic unsaturated radicals (e.g., CN, C2H, and phenyl) to alkenes, imines, and aldehydes, whose rotational spectra have been investigated, but accurate structural determinations are not yet available.

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Millimeter wave free-jet spectrum of acrolein and several isotopologues

et al. 2020

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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

Cited by 3 publications

References 26 publications

Molecular Structure and Spectroscopic Signatures of Acrolein: Theory Meets Experiment

Molecular Structure and Spectroscopic Signatures of Acrolein: Theory Meets Experiment

Extending the Applicability of the Semi-experimental Approach by Means of “Template Molecule” and “Linear Regression” Models on Top of DFT Computations

Millimeter wave free-jet spectrum of acrolein and several isotopologues

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