Photodissociation and infrared spectra of ethylene cations in solid argon

Chen, Sian-Cong; Liu, Meng-Chen; Huang, Tzu-Ping; Chin, Chih‐Hao; Wu, Yu-Jong

doi:10.1016/j.cplett.2015.04.050

Cited by 9 publications

(6 citation statements)

References 31 publications

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“…19 Additional weak bands were also observed and are associated with the products generated by electron bombardment of the matrix sample. These products were readily characterized as C 2 H 2 (HCCH, 737.3/741.0 and 3284.9/3309.0 cm −1 ), 20 C 3 H 3 (H 2 CCCH, 686.8 cm −1 ), 12,19 and C 3 H 2 (HCCCH, 547.8 and 3263.0/3266.7 cm −1 ). 12,19 In addition, five lines observed at 874.4, 791.4, 1307.3, 2929.0, and 3020.8 cm −1 , indicated by A + in Figures 1A and 2A, might be attributed to the H 2 CCCH 2 + cation that were reported in solid Ne 12 (Table 1).…”

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confidence: 99%

“…Lines pointing upward indicate the production of species, whereas those pointing downward indicate the destruction of species. When the matrix sample was maintained in darkness for a prolonged period, the trapped electrons diffused slowly to recombine with the cations forming neutral species. , Figure A shows that bands of A + decreased and bands of A increased, indicating that A + and A are counterparts. Therefore, this result confirms that the A + bands are correctly assigned as absorption features of allene cations.…”

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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%

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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“…Furthermore, the observed photolytic behavior of the * bands is similar to that of H 2 C 3 H 2 + and Ar 2 H + cations suggesting it might be a charged species. The decrease in the cationic species upon irradiation with 385-nm light has been demonstrated in many previous studies 23 , 24 , 26 and this may be because the UV light caused the slowly diffusing trapped electrons to recombine with the cations. The increase in the H 3 C 3 H + cations upon irradiation with 385-nm light in this study is due to the isomerization of H 2 C 3 H 2 + 24 .…”

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confidence: 55%

“…We employed a “clean” method of matrix isolation for investigating the IR spectra of cations of interest using electron bombardment of an Ar matrix containing a small proportion of neutral counterparts during matrix deposition. We demonstrated the advantages of this method with ethylene and allene cations 23 , 24 . Our method can be used to obtain IR spectra with a high resolution, the true IR intensities, and a wider spectral coverage of cations of interest.…”

Section: Introductionmentioning

confidence: 95%

Direct IR Absorption Spectra of Propargyl Cation Isolated in Solid Argon

Chin

Lin

Huang

et al. 2018

Sci Rep

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The direct infrared (IR) absorption spectra of propargyl cations were recorded. These cations were generated via the electron bombardment of a propyne/Ar matrix sample during matrix deposition. Secondary photolysis with selected ultraviolet (UV) light was used for grouping the observed bands of various products. The band assignment of the propargyl cation in solid Ar was performed according by referring to the previous infrared photodissociation (IRPD) and velocity-map imaging photoelectron (VMI-PE) data, and via theoretical predictions of the anharmonic vibrational wavenumbers, band intensities, and deuterium-substituted isotopic ratios. Almost all the IR active bands with an observable intensity were recorded and the ν11 mode was reported for the first time.

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“…•+ in the range of 13 to 33°, depending on the approximation level employed [6,7]; the most trusted experimental estimate is ca. 29° [8].…”

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Noncovalent interactions in crowded olefinic radical cations

Fokin

Bahonsky

Koso

et al. 2020

J. org. pharm. chem.

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Noncovalent interactions in crowded olefinic radical cations Aim. To study the effect of electronic (α-and β-hyperconjugations) and steric (noncovalent interactions) factors on the structures of olefinic radical cations. Results and discussion. The effect of intramolecular dispersion interactions on the structures of crowded alkenes in the neutral and ionized forms has been studied at the density functional theory (DFT) level with and without dispersion corrections included, as well as at the MP2 theory level with medium size basis sets. The results obtained are compared to the available experimental data. An excellent agreement has been found between the experimental and MP2/DFT-computed geometries of sesquihomoadamantene, adamantylidene adamantane, bis-2,2,5,5-tetramethylcyclopentylidene, bis-D 3-homocub-4-ylidene, and bis-C S-homocub-8-ylidene in the neutral and ionized forms. The experimental ionization potentials are better reproduced with the DFT-methods. Experimental part. The structure and composition of compounds were proved by the methods of 1 H and 13 C NMR-spectroscopy, and GC-MS-analysis. Elemental analysis was performed for the compounds obtained. Conclusions. The twisting of the olefinic moieties in the sesquihomoadamantene and adamantylidene adamantane radical cations is determined by the balance between the σ-π-hyperconjugation and residual oneelectron π-bonding and is close to that of the prototypical ethylene radical cation (29°). The twisting reaches 55° for the bis-2,2,5,5-tetramethylcyclopentylidene radical cation due to substantial steric repulsions between methyl groups. At the same time, the ionized states of bis-D 3-homocub-4-ylidene and bis-C S-homocub-8-ylidene retain their planarity due to β-CC-hyperconjugation and intramolecular dispersion attractions.

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Photodissociation and infrared spectra of ethylene cations in solid argon

Cited by 9 publications

References 31 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

Direct IR Absorption Spectra of Propargyl Cation Isolated in Solid Argon

Noncovalent interactions in crowded olefinic radical cations

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