The Stabilization of Methyl Radical

Mador, Irving L.

doi:10.1063/1.1740479

Cited by 16 publications

(8 citation statements)

References 6 publications

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“…Photographs taken simultaneously with the photolysis flash, using the vapour, always show the resonant 2833 line of lead to be a prominent feature in conjunction with the band system. Mador 16 has also shown that at temperatures as low as 40°K thin films of irradiated methyl iodide and lead tetramethyl disintegrated violently and attributed this to rapid radical reactions taking place even at this temperature. Tt therefore seems more likely that a product of photolysis is involved.…”

Section: Discussionmentioning

confidence: 99%

Flash photolysis of lead tetramethyl

Clouston¹,

Cook²

1958

Trans. Faraday Soc.

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The photolytic decomposition of lead tetramethyl has been studied in the vapour phase using a high-intensity flash of light and absorption spectroscopy. It has been found that more than 90 % of the theoretical amount of lead originally present in the sample had been deposited after a sample of lead tetramethyl had been subjected to a light flash of energy 2500 J. During the photolysis an absorption system in the region of 3000 A has been observed with a lifetime not exceeding 400 psec. Unequivocal evidence has not been obtained to make a positive assignment of the new spectrum but shifts in the band system, when a deuterated sample of lead tetramethyl is photolyzed under identical conditions, leave no doubt that a mode involving hydrogen atoms in the upper state has been excited. The experimental conditions are such that a transition due to the free methyl radical or a lead polymethyl radical seems most likely to be responsible for the band system.

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Section: Discussionmentioning

confidence: 99%

Flash photolysis of lead tetramethyl

Clouston¹,

Cook²

1958

Trans. Faraday Soc.

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“…I t is believed that both Iz and CH, were in the cold solid. X radiation of [Pb(CH3)4] a t 4.2" K. 35 failed to produce any infrared bands not assignable to stable molecules.…”

Section: Low-temperature Radical Formationmentioning

confidence: 93%

“…Photolysis of methyl iodide (CHsI) a t 4.2" K. 35 produced films that violently disintegrated upon warming and redeposited as a yellow-brown film. I t is believed that both Iz and CH, were in the cold solid.…”

Section: Low-temperature Radical Formationmentioning

confidence: 99%

“…Mador and Williams6 photolyzed hydrazoic acid with 2537 A. radiation during and after deposition a t 4" K. and a t 77" K. They found the same products and the same visible and infrared absorption bands that were detected after vapor-phase decomposition. Photolysis of methyl iodide (CHsI) a t 4.2" K. 35 produced films that violently disintegrated upon warming and redeposited as a yellow-brown film. I t is believed that both Iz and CH, were in the cold solid.…”

Section: Low-temperature Radical Formationmentioning

confidence: 99%

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Stabilization of Free Radicals at Low Temperatures

Broida¹

1957

Annals of the New York Academy of Sciences

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“…In the latter matrices, the cage effect prevents the photofragments from being separated. [11][12][13][14] The advantageous feature of the mitigation of the cage effect in the p-H 2 matrix is attributed to the fact that solid p-H 2 forming a hexagonal close packed crystal is a quantum solid having the following properties: ͑1͒ a large lattice constant, ͑2͒ a large amplitude of the zero-point lattice vibration, and ͑3͒ a large thermal conductivity. 3 Due to the properties of ͑1͒ and ͑2͒, solid p-H 2 can be regarded as a spacious and soft lattice for foreign molecules, and due to ͑3͒, the excess energy imparted to nascent photofragments is quickly removed and the fragments are rapidly frozen to be protected from geminate recombination.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced reactions of methyl radical in solid parahydrogen

Fushitani

Sogoshi

Wakabayashi

et al. 1998

The Journal of Chemical Physics

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Photolysis of methyl iodide in solid parahydrogen (p-H2) at about 5 K is studied with ultraviolet light at 253.7 and 184.9 nm. It is found that the light at 253.7 nm produces only methyl radical, whereas the light at 184.9 nm yields both methyl radical and methane. The mechanism of the formation of the photoproducts is elucidated by analyzing the temporal behavior of the observed vibrational absorption. It is concluded that methyl radical in the ground state does not react with p-H2 molecules appreciably but that the radical in the electronic excited state of B̃(2A1′), accessible by reabsorption of 184.9 nm photons by the radical, decomposes to a singlet methylene CH2 ã(1A1) and a hydrogen atom (2S) and that the singlet methylene reacts with a p-H2 molecule to give methane.

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The Stabilization of Methyl Radical

Cited by 16 publications

References 6 publications

Flash photolysis of lead tetramethyl

Flash photolysis of lead tetramethyl

Stabilization of Free Radicals at Low Temperatures

Photoinduced reactions of methyl radical in solid parahydrogen

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