Internal rotation in Jahn–Teller coupled systems: The ethene and allene cations

Schulenburg, A. M.; Merkt, F.

doi:10.1016/j.chemphys.2010.08.017

Cited by 7 publications

(9 citation statements)

References 42 publications

(66 reference statements)

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“…In addition, the rotational constants, J− T coupling constants, and the lowest two torsional levels were also determined. 15,16 Few theoretical calculations of the potential energy surfaces (PESs) of C 3 H 4 + have been reported. Theoretical calculations have predicted that the allene cation is more stable than the propyne cation by 15.4 kcal mol −1 + with the CCSD(T)/cc-pVTZ//B3LYP/6-311G** level of a theory.…”

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confidence: 99%

“…For instance, Marquez et al 18 simulated the photoelectron spectrum of the propyne cation (X 2 E) with spin−orbit interaction using an intensity borrowing approach and compared their results with the experimental results obtained by Xing et al 13 In addition, Schulenburg and Merkt used Fourier series instead of Taylor series to treat the J−T effect and the hindered internal rotations of the PES for the allene cation, which were compared with their previous PFI− PE data. 16 Although the IR spectra of allene cations in solid matrices are reported, 12 the IR features of propyne cations and their photochemistry remain unclear. Herein, we measured the IR spectra of the isomers of C 3 H 4 + in solid Ar and observed the UV light-induced isomerization of allene cations into propyne cations.…”

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confidence: 99%

“…Subsequently, Schulenburg and Merkt used a similar technique to record the photoelectron spectra of H 2 CCCH 2 ; the rovibronic progression of H 2 CCCH 2 + was observed mainly by the torsional mode. In addition, the rotational constants, J–T coupling constants, and the lowest two torsional levels were also determined. , …”

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confidence: 99%

“…Later, other calculations focused on the simulations of photoelectron spectra with spin–orbit interactions were reported. For instance, Marquez et al simulated the photoelectron spectrum of the propyne cation ( X 2 E) with spin–orbit interaction using an intensity borrowing approach and compared their results with the experimental results obtained by Xing et al In addition, Schulenburg and Merkt used Fourier series instead of Taylor series to treat the J–T effect and the hindered internal rotations of the PES for the allene cation, which were compared with their previous PFI–PE data …”

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confidence: 99%

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Photoisomerization and Infrared Spectra of Allene and Propyne Cations in Solid Argon

Liu

Chen

Chin

et al. 2015

J. Phys. Chem. Lett.

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Allene and propyne as well as their cationic forms play important roles in combustion and interstellar chemistry and serve as a model system for molecular spectroscopic studies. Both cations show Jahn−Teller (J−T) distortions in their ground states. These J−T distortions make the theoretical and experimental studies of their electronic structures difficult. We produced allene cations upon electron bombardment during matrix deposition of Ar containing a small proportion of allene. The intensities of the absorption features of the allene cation decreased after irradiation with UV light, whereas new bands attributed to propyne cations increased. The observed line wavenumbers, relative intensities, and deuterium-substituted isotopic ratios of the isomers of C 3 H 4 + agree satisfactorily with those predicted by density functional theory at the B3PW91/ aug-cc-pVTZ level of theory. This method produced the hydrocarbon cations of interest with few other fragments that enabled the clear identification of the IR spectra of allene and propyne cations.

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confidence: 99%

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confidence: 99%

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confidence: 99%

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Photoisomerization and Infrared Spectra of Allene and Propyne Cations in Solid Argon

Liu

Chen

Chin

et al. 2015

J. Phys. Chem. Lett.

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“…Studies of molecular dynamics have been of interest in both computational and experimental research areas . Recently, dynamic phenomena such as rotations and tautomerism have been the subject of theoretical researches. In this line, potential energy surfaces (PESs) for dynamic motion have been studied by both computational and experimental methods .…”

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Tautomerism, dynamic properties and level crossing in 2‐(pyridin‐2‐yl) furan‐3‐ol by density functional theory and natural bond orbital analysis

Tavakol

2011

J of Physical Organic Chem

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Tautomerism, dynamic properties and level crossing in 2-(pyridin-2-yl) furan-3-ol by density functional theory and natural bond orbital analysis Hossein Tavakol a * 2-(Pyridin-2-yl)furan-3-ol (PYFO, T1) and (2E)-2-(pyridin-2(1H)-ylidene)furan-3(2H)-one (PYFO, T2) were considered to study their tautomerism interconversions, relative rotations of rings, OH bond rotations, and possibility of crossing between those energy surfaces using density functional theory methods at the Becke, three-parameter, Lee-Yang-Parr/6-311++G** level of theory. The optimized structures of both tautomers and the transition state of tautomerism are completely planar. A study of tautomerism in PYFO shows that T1 tautomer is about 24.38 kJ/mol more stable than T2. The rate constants of tautomerism interconversion for converting T1 to T2 is 1.98 Â 10 8 M -1 s -1 and for converting T2 to T1 is 3.70 Â 10 12 M -1 s -1 at room temperature that show the possibility of this tautomerism with high rate at ambient temperature. Rotation of OH bond in T1 shows two minimum (at 0 (global minimum) and 180 (local minimum)) and a transition state at 110 (and 265 ) with 47.10 kJ/mol barrier energy. Relative rotation of rings shows global minimum at 0 for both tautomers and local minimum at 154 and 206 for T1 and 180 for T2. The barrier energy for ring rotation of T1 was observed at 90 and 270 with 63.69 kJ/mol height and for T2 was observed at 120 with 170.86 kJ/mol height. Interestingly, the energy levels of ring rotations for T1 and T2 are the same and crossing between them was observed. Therefore, although these two potentials do not have the same symmetries, because of the crossing between their energy level, crossing is not avoided. a Another barrier energy for ring rotation in T1, between 154 and 180 degrees: ΔG # = 1.06 and k = 4.05 Â 10 12 . TAUTOMERISM, DYNAMIC PROPERTIES AND LEVEL CROSSING IN 2-(PYRIDIN-2-YL) FURAN-3-OL

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Atomic and Molecular Tunneling Processes in Chemistry

Qüack

Seyfang

2021

Molecular Spectroscopy and Quantum Dynamics

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Internal rotation in Jahn–Teller coupled systems: The ethene and allene cations

Cited by 7 publications

References 42 publications

Photoisomerization and Infrared Spectra of Allene and Propyne Cations in Solid Argon

Photoisomerization and Infrared Spectra of Allene and Propyne Cations in Solid Argon

Tautomerism, dynamic properties and level crossing in 2‐(pyridin‐2‐yl) furan‐3‐ol by density functional theory and natural bond orbital analysis

Atomic and Molecular Tunneling Processes in Chemistry

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