Resonance Raman Spectroscopy of the 1-Methylallyl Radical

Tarrant, Darcy H.; Getty, James D.; Liu, and Xianming; Kelly, Peter B.

doi:10.1021/jp9526253

Cited by 10 publications

(16 citation statements)

References 31 publications

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“…stretch, 3033 cm −1 ), and ν 1 (C1H 2 antisym. stretch, 3105 cm −1 ) 62 Although the other conformer cis-1-methylallyl (4b) has a similar allyl structure, its predicted IR spectrum (Fig. 6(c)) differs significantly from that of trans-1-methylallyl (4a), especially in the region 600-1000 cm −1 , and matches poorly the observed spectrum in both wavenumbers and relative intensities.…”

Section: Assignment Of Lines In Group B To Trans-1-methylallylmentioning

confidence: 54%

Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cℓ2 in solid para-hydrogen

Bahou

Tanaka

et al. 2012

The Journal of Chemical Physics

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The reactions of chlorine and hydrogen atoms with trans-1,3-butadiene in solid para-hydrogen (p-H(2)) were investigated with infrared (IR) absorption spectra. When a p-H(2) matrix containing Cl(2) and trans-1,3-butadiene was irradiated with ultraviolet light at 365 nm, intense lines at 650.3, 809.0, 962.2, 1240.6 cm(-1), and several weaker ones due to the trans-1-chloromethylallyl radical, ●(CH(2)CHCH)CH(2)Cl, appeared. Observed wavenumbers and relative intensities agree with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3PW91/6-311++g(2d, 2p) method. That the Cl atom adds primarily to the terminal carbon atom of trans-1,3-butadiene is in agreement with the path of minimum energy predicted theoretically, but in contrast to the reaction of Cl + propene in solid p-H(2) [J. Amicangelo and Y.-P. Lee, J. Phys. Chem. Lett. 1, 2956 (2010)] in which the addition of Cl to the central C atom is favored, likely through steric effects in a p-H(2) matrix. A second set of lines, intense at 781.6, 957.9, 1433.6, 2968.8, 3023.5, 3107.3 cm(-1), were observed when the UV-irradiated Cl(2)/trans-1,3-butadiene/p-H(2) matrix was further irradiated with IR light from a SiC source. These lines are assigned to the trans-1-methylallyl radical, ●(CH(2)CHCH)CH(3), produced from reaction of 1,3-butadiene with a H atom resulted from the reaction of Cl atoms with solid p-H(2) exposed to IR radiation.

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Section: Assignment Of Lines In Group B To Trans-1-methylallylmentioning

confidence: 54%

Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cℓ2 in solid para-hydrogen

Bahou

Tanaka

et al. 2012

The Journal of Chemical Physics

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“…Within the past few years, RRS has been successfully applied to the study of several small gas phase hydrocarbon radicals. Raman spectra of the methyl, − allyl, − 1-methylallyl, and 2-methylallyl radicals have yielded information regarding the excited state dynamics, ground state vibrational structure, and excited state frequencies of these elusive species. Pulsed lasers were used to generate and probe the radicals.…”

Section: Ch3 B Bandmentioning

confidence: 99%

Resonance Raman Spectroscopy of Dissociative Polyatomic Molecules

et al. 1996

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Resonance Raman spectroscopy as a probe of the early stages in the dissociation dynamics of polyatomic molecules has become a valuable complement to photofragmentation studies. While these spontaneous Raman experiments are obtained in the frequency domain, they often reflect evolution of the molecule during the first few femtoseconds of bond breaking. Coupled with progress in classical and quantum calculations of large-amplitude motion, unique insights have become available for a number of small polyatomic molecules. The development of this field to date is reviewed.

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“…The 1-methylallyl radical, hereafter shortened to methylallyl, has also been studied experimentally ,,,,− and theoretically. ,,,,, Most notably, its IR spectrum was recorded following its isolation in a solid para -H 2 matrix. The radical was produced following UV irradiation of a co-deposited mixture of Cl 2 and 1,3-butadiene .…”

Section: Introductionmentioning

confidence: 99%

Helium Nanodroplet Isolation of the Cyclobutyl, 1-Methylallyl, and Allylcarbinyl Radicals: Infrared Spectroscopy and Ab Initio Computations

2017

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Gas-phase cyclobutyl radical (CH) is produced via pyrolysis of cyclobutylmethyl nitrite (CH(CH)ONO). Other CH radicals, such as 1-methylallyl and allylcarbinyl, are similarly produced from nitrite precursors. Nascent radicals are promptly solvated in liquid He droplets, allowing for the acquisition of infrared spectra in the CH stretching region. For the cyclobutyl and 1-methylallyl radicals, anharmonic frequencies are predicted by VPT2+K simulations based upon a hybrid CCSD(T) force field with quadratic (cubic and quartic) force constants computed using the ANO1 (ANO0) basis set. A density functional theoretical method is used to compute the force field for the allylcarbinyl radical. For all CH radicals, resonance polyads in the 2800-3000 cm region appear as a result of anharmonic coupling between the CH stretching fundamentals and CH bend overtones and combinations. Upon pyrolysis of the cyclobutylmethyl nitrite precursor to produce the cyclobutyl radical, an approximately 2-fold increase in the source temperature leads to the appearance of spectral signatures that can be assigned to 1-methylallyl and 1,3-butadiene. On the basis of a previously reported CH potential energy surface, this result is interpreted as evidence for the unimolecular decomposition of the cyclobutyl radical via ring opening, prior to it being captured by helium droplets. On the CH potential surface, 1,3-butadiene is formed from cyclobutyl ring opening and H atom loss, and the 1-methylallyl radical is the most energetically stable intermediate along the decomposition pathway. The allylcarbinyl radical is a higher-energy CH intermediate along the ring-opening path, and the spectral signatures of this radical are not observed under the same conditions that produce 1-methylallyl and 1,3-butadiene from the unimolecular decomposition of cyclobutyl.

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Resonance Raman Spectroscopy of the 1-Methylallyl Radical

Cited by 10 publications

References 31 publications

Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cℓ2 in solid para-hydrogen

Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cℓ2 in solid para-hydrogen

Resonance Raman Spectroscopy of Dissociative Polyatomic Molecules

Helium Nanodroplet Isolation of the Cyclobutyl, 1-Methylallyl, and Allylcarbinyl Radicals: Infrared Spectroscopy and Ab Initio Computations

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