Electronic absorption spectra of the cyclohexadienyl radical in .gamma.-irradiated solids at 77.deg.K

Shida, Tadamasa; Hanazaki, Ichiro

doi:10.1021/j100696a042

Cited by 16 publications

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“…19 The c-C 6 H 7 radical is an important intermediate in the initial step in the hydrogenation of aromatic compounds in both the gaseous phase and the condensed phase. The UV-visible spectra of c-C 6 H 7 have been studied in the condensed phase [25][26][27][28][29][30] and in the gaseous phase. [31][32][33] The dispersed laser-induced fluorescence spectra of c-C 6 H 7 radical, produced via H-abstraction of 1, 4cyclohexadiene by Cl atom, yield wavenumbers for six vibrational modes of the ground electronic state.…”

Section: Introductionmentioning

confidence: 99%

A new method for investigating infrared spectra of protonated benzene (C6H7+) and cyclohexadienyl radical (c-C6H7) using para-hydrogen

Bahou

Lee

2012

The Journal of Chemical Physics

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We use protonated benzene (C(6)H(7)(+)) and cyclohexadienyl radical (c-C(6)H(7)) to demonstrate a new method that has some advantages over other methods currently used. C(6)H(7)(+) and c-C(6)H(7) were produced on electron bombardment of a mixture of benzene (C(6)H(6)) and para-hydrogen during deposition onto a target at 3.2 K. Infrared (IR) absorption lines of C(6)H(7)(+) decreased in intensity when the matrix was irradiated at 365 nm or maintained in the dark for an extended period, whereas those of c-C(6)H(7) increased in intensity. Observed vibrational wavenumbers, relative IR intensities, and deuterium isotopic shifts agree with those predicted theoretically. This method, providing a wide spectral coverage with narrow lines and accurate relative IR intensities, can be applied to larger protonated polyaromatic hydrocarbons and their neutral species which are difficult to study with other methods.

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Section: Introductionmentioning

confidence: 99%

A new method for investigating infrared spectra of protonated benzene (C6H7+) and cyclohexadienyl radical (c-C6H7) using para-hydrogen

Bahou

Lee

2012

The Journal of Chemical Physics

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“…Consequently, it is assigned to the radical anion of the dye, C152a •– . The radical cation DMA •+ also absorbs in this region, but its absorption coefficient is probably too small relative to that of C152a •– to make this species visible. , These data could be well reproduced by global analysis assuming a series of three successive steps, A → B → C →. , The resulting evolution-associated difference spectra and time constants are shown in Figure S8.…”

Section: Resultsmentioning

confidence: 80%

Photoinduced Electron Transfer between Dipolar Reactants: Solvent and Excitation Wavelength Effects

Verma,

Budkina,

Vauthey

2024

J. Phys. Chem. B

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Electron transfer (ET) quenching in nonpolar media is not as well understood as in polar environments. Here, we investigate the effect of dipole−dipole interactions between the reactants using ultrafast broadband electronic spectroscopy combined with molecular dynamics simulations. We find that the quenching of the S 1 state of two polar dyes, coumarin 152a and Nile red, by the polar N,N-dimethylaniline (DMA) in cyclohexane is faster by a factor up to 3 when exciting on the red edge rather than at the maximum of their S 1 ← S 0 absorption band. This originates from the inhomogeneous broadening of the band due to a distribution of the number of quencher molecules around the dyes. As a consequence, red-edge excitation photoselects dyes in a DMA-rich environment. Such broadening is not present in acetonitrile, and no excitation wavelength dependence of the ET dynamics is observed. The quenching of both dyes is markedly faster in nonpolar than polar solvents, independently of the excitation wavelength. According to molecular dynamics simulations, this is due to the preferential solvation of the dyes by DMA in cyclohexane. The opposite preferential solvation is predicted in acetonitrile. Consequently, close contact between the reactants in acetonitrile requires partial desolvation. By contrast, the recombination of the quenching product is slower in nonpolar than in polar solvents and exhibits much smaller dependence, if any, on the excitation wavelength.

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“…Much less is known about H atom addition to substituted benzenes; radiolysis of the solute in methanol glasses2 3456•9 and H atom addition in matrix experiments with toluene, xylene, and ethyl-benzene10-12 have led to substituted cyclohexadienyl radical absorption spectra. In the case of styrene and phenylacetylene in methanol glasses, irradiation effected H addition to the substituent to give -methylbenzyl or 1-phenylethyl (2) and a-styryl (3) radicals, respectively, which were characterized by absorption…”

Section: Discussionmentioning

confidence: 99%

Charge exchange in gas-surface collisions: the three electronic state system

Olson¹,

Garrison²

1987

J. Phys. Chem.

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Electronic absorption spectra of the cyclohexadienyl radical in .gamma.-irradiated solids at 77.deg.K

Cited by 16 publications

References 0 publications

A new method for investigating infrared spectra of protonated benzene (C6H7+) and cyclohexadienyl radical (c-C6H7) using para-hydrogen

A new method for investigating infrared spectra of protonated benzene (C6H7+) and cyclohexadienyl radical (c-C6H7) using para-hydrogen

Photoinduced Electron Transfer between Dipolar Reactants: Solvent and Excitation Wavelength Effects

Charge exchange in gas-surface collisions: the three electronic state system

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