Vacuum-ultraviolet photolysis of XeF2: XeF(B) fluorescence and quenching

Brashears, H. C.; Setser, D. W.; Desmarteau, D. D.

doi:10.1016/0009-2614(77)80219-4

Cited by 38 publications

(10 citation statements)

References 14 publications

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“…Since the discovery of the first noble-gas compounds in 1962, XeF 2 has attracted great attention and its chemical activity, electronic and geometric properties have been investigated experimentally and theoretically because of its simple structure with D ϱh symmetry and unique electronic properties. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] From the photochemical point of view it is a special molecule since strong XeF* excimer emission has been detected in photolysis in the vacuum UV region.…”

Section: Introductionmentioning

confidence: 99%

Photodissociative excitation processes of XeF2 in the vacuum ultraviolet region 105–180 nm

Kono

Shobatake

1995

The Journal of Chemical Physics

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Photodissociative excitation processes of XeF 2 are studied by absorption and photofragment fluorescence spectroscopies in the vacuum UV region 105-180 nm. The quantum yields are measured along with the dispersed fluorescence spectra for emissions from XeF* ͑B, C, and D͒ excimers formed from XeF 2 excited by linearly polarized, monochromatized synchrotron radiation. Fluorescence anisotropy, R, of XeF* fragment emission was also measured against excitation light wavelength in the region 105-165 nm. The quantum yields for XeF* excimer formation are found to be very high; especially in the valence band region shorter than 130 nm it reaches almost unity. From the fluorescence measurements we have observed new peaks assigned to 5 u →5dR Rydberg transitions. The intense 5 u3/2 →6sR bands which appear around 143 nm exhibit no fluorescence excitation bands; even fluorescence dips are observed at 143.18 and 144.25 nm whereas very weak positive fluorescence bands are observed at 141.04 and 142.11 nm. The R values for the very broad valence bands which underlie intense Rydberg bands are found to be high. The 5 u series of Rydberg bands exhibit low R values. Based on the energetics and the results of quantum yields and fluorescence anisotropy values, the valence and Rydberg bands observed are assigned from the viewpoint of symmetry of the excited state, and the dynamics of the dissociation processes is discussed.

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Section: Introductionmentioning

confidence: 99%

Photodissociative excitation processes of XeF2 in the vacuum ultraviolet region 105–180 nm

Kono

Shobatake

1995

The Journal of Chemical Physics

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“…In our initial experiments, we were able to obtain fluorescence emission from XeF (B) using a mixture of F 2 and Xe diluted in He. Both XeF 2 and UF 6 were also tried as F atom sources. The XeF 2 yielded a very weak fluorescence signal, presumably because of the poor overlap between the XeF 2 absorption spectrum and the flashlamp emission spectrum.…”

Section: Methodsmentioning

confidence: 99%

“…However, the intensity of the emission increased an order of magnitude when UF 6 was substituted for F 2 as the F atom donor. This is due to the fact that UF 6 has a larger absorption cross-section in the near ultraviolet than F 2 . 9 The increased signal allowed a much wider range of gas mixtures to be explored.…”

Section: Methodsmentioning

confidence: 99%

“…As a result, each gas fill can only be used for one shot. To verify that the observed signal was not due to laser light scattered from these particles, a gas mixture containing only He and UF 6 was photolyzed under the same condi- Gas samples are introduced to the cell through a high purity stainless steel manifold which was passivated with F 2 before use.…”

Section: Methodsmentioning

confidence: 99%

“…Assuming that the rate constant reported by Rokni, Jacob, Mangano, and Brochu of 3 x 10 -31 cm 6 sec -' for the reaction XeF* + Xe + M -products 7 leads exclusively to XeF* formation, the time constant for 10 torr Xe …”

Section: B 460-nm Emissionmentioning

confidence: 99%

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