Optical measurements on solvated electrons in pulse-irradiated liquid propane

Gillis, Hugh A.; Klassen, Norman V.; Teather, George G.; Lokan, K.H.

doi:10.1016/0009-2614(71)80339-1

Cited by 34 publications

(11 citation statements)

References 7 publications

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“…1. The maximum around 2100 nln is attributed to the solvated electron (e,-) by comparison with our previous work (2,15) and the maximum around 625 nm is attributed to RH' by comparison with the spectra of Louwrier and Hamill (4). A comparison of the three spectra of Fig.…”

Section: Spectra Of Solcated Electrotz and Positive Ionsupporting

confidence: 79%

“…Electrons solvated or trapped in hydrocarbons have strong absorption bands with maxima in the near infrared and they have been the subject of many optical investigations in both glasses and liquids (1)(2)(3). In hydrocarbons, especially at low temperatures, an electron is usually thermalized at a distance from a positive ion in the same spur such that the coulombic energy between the pair is greater than the kinetic energy.…”

Section: Introductionmentioning

confidence: 99%

“…The ion-pair is described as geminate and will undergo geminate recombination unless one or both members of the pair is scavenged by solute. Geminate recombination was demonstrated in liquid propane at 88 K (2) and in liquid 3-methylhexane at 126 K (3) by the observation that half-lives for electron decay are independent of initial concentration.…”

Section: Introductionmentioning

confidence: 99%

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Optical study of electrons and positive ions in pulse-irradiated liquid 3-methyloctane at low temperatures

Gillis¹,

Klassen²,

Woods³

1977

Can. J. Chem.

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HUGH A. GILLIS, NOR MA^ V. KLASSEN, and ROBERT J. WOODS. Can. J. Chem. 55,2022Chem. 55, (1977. The spectrum of pulse-irradiated liquid 3-methyloctane at 127 K has maxima around 625 and 2100 nm. The latter is well-known as being due to the solvated electron (e,-). The former is attrib~~ted to a positive ion because it is eliminated by the addition of triethylamine, but remains in solutions of electron scavengers, and is very similar to bands observed earlier by Louwrier and Hamill in glassy solutions at 77 K of higher hydrocarbons in CCI, or COzbubbled 3-methylpentane. At temperatures of 127 K and less the initial decay rate of e,-is greatly decreased by the addition of -6 mol% triethylamine. The result is interpreted as indicating that at low temperatures the mobility of the initial hydrocarbon positive ion is much greater than that of either e,-or the positive ion in triethylamine solutions, and therefore the initial hydrocarbon positive ion must be the parent radical cation which moves by resonance charge transfer. As the temperature of pure 3-nlethyloctane is raised from 103 to 153 K, the initial G E , ,~~ decreases by about 3 0 x while initial G E~~, ,~ almost doubles; because of these and other observations it is tentatively suggested that a second solvated electron is also produced. Chern. 55.2022Chern. 55. (1977. Le spectre du methyl-3 octane liquide irradie par pulsation a 127 K a deux maxima autour de 625 et 2100 nm. On sait que le dernier maximum est dCi aux electrons solvates (e,-). Le premier est attribue a union positif parce qu'il est elimine par l'addition de triethylamine mais demeure dans des solutions de piegeurs d'electron et est trts semblable i des bandes qui ont Cte observees antirieurement par Louwrier et Hamill dans des solutions d'hydrocarbures de poids molCculaires plus eleves dissous dans des verres de CCI, a 77 K ou de methyl-3 pentane dans -1equel on a fait barbotter du CO,. A des temperatures de 127 K ou moins, le taux de dkconlposition initial de e,-diminue rapidement par addition -6 m o l z de triethylamine. On interprete des risultats comme indiquant qu'a basse temperature la mobilite de I'ion positif de I'hydrocarbure initial est beaucoup plus grande que celle de soit e,-ou I'ion positif dans des solutions de triithylamine et qu'ainsi l'ion positif de I'hydrocarbure initial doit @tre le cation radical parent qui se deplace par transfert de charge en resonance. A mesure que I'on augmente la temperature du methyl-3 octane de 103 a 153 K, le G~650 initial dirninue par environ 30% alors que le G E~,~~ initial double pratiquement; a cause de ces observations et d'autres, on suggere d'une f a~o n non definitive qu'il y a aussi production d'une seconde espece d'electron solvate.[Traduit par le journal]

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Section: Spectra Of Solcated Electrotz and Positive Ionsupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Optical study of electrons and positive ions in pulse-irradiated liquid 3-methyloctane at low temperatures

Gillis¹,

Klassen²,

Woods³

1977

Can. J. Chem.

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“…16 Two possible mechanisms of these shifts have been discussed for electrons initially in shallow traps or in traps with a wide distribution of depths. [3][4][5][6][7][8][9][10][11][12][13][14][15] In mechanism I the electric field of the electron promotes reorientation of the surrounding dipoles of the medium to deepen the shallow traps. In mechanism II it is postulated that the electrons are thermally excited out of the shallow traps and redistributed into deeper traps.…”

Section: Discussionmentioning

confidence: 99%

Spectral shifts of trapped electrons in alkane glasses at 76.deg.K

Klassen¹,

Gillis²,

Teather³

1972

J. Phys. Chem.

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The spectra of the trapped electron in 3-methylpentane and 3-methylhexane glasses at 76°K as determined by pulse radiolysis have been found to shift toward the blue on a time scale of mseconds, seconds, and minutes. For 3-methylhexane Xmax is approximately 2000 and 1700 nm at 3 psec and 380 sec, respectively. For 3-methylpentane Xmax is approximately 1900 at 10 psec and shifts to about 1700 nm at 380 sec. The spectra at 380 sec are very similar to those determined by others after 60Co irradiation. Geminate recombination occurs simultaneously with the spectral shifts, but an experiment with added biphenyl indicates that the mechanism involved in the spectral shifts is predominantly molecular reorientation rather than detrapping-retrapping.

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“…Electrons have not been detected by optical absorption in alkanes in which the mobility is greater than 10 cm2/Vs. For example, Gillis, et al [82]report seeing no infrared absorption in pulse irradiated liquid methane at 93 K. This is not surprising since the electron imobility in methane is 500 cm2/Vs[8 11 and trapping does not occur. Geminately recombining electrons have however been detected by IR absorption in 2,2,4-trimethylpentane in a subpicosecond laser pulse experiment.…”

Section: Ym-1mentioning

confidence: 99%

Electrons in Nonpolar Liquids

Holroyd¹

2003

Charged Particle and Photon Interactions With Matter

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Optical measurements on solvated electrons in pulse-irradiated liquid propane

Cited by 34 publications

References 7 publications

Optical study of electrons and positive ions in pulse-irradiated liquid 3-methyloctane at low temperatures

Optical study of electrons and positive ions in pulse-irradiated liquid 3-methyloctane at low temperatures

Spectral shifts of trapped electrons in alkane glasses at 76.deg.K

Electrons in Nonpolar Liquids

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