Electronic quenching of XeCl(<i>B</i>,<i>C</i>) and Xe2Cl*

Yu, Y. C.; Wategaonkar, Sanjay; Setser, D. W.

doi:10.1063/1.462249

Cited by 17 publications

(5 citation statements)

References 33 publications

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“…The rate constants for reactions 12-14 under these experimental conditions have previously been measured. 15 Owing to the relatively high xenon pressures used in these experiments, collisional coupling of the XeCl* (B,C) states was assumed to be maintained, 31 and therefore, the effective radiative lifetime of this coupled state is ca. 25 ns 30 (corresponding to a rate constant of k 18 ) 4.0 × 10 7 s -1 ).…”

Section: Resultsmentioning

confidence: 99%

Absolute Fluorescence Yields from Electron-Irradiated Gases. 3. XeCl* and XeI*

1997

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The absolute total fluorescence yield for the XeCl* (B,C) 2Σ1/2 + → 2Σ1/2 + transition has been determined from pulse electron-irradiated Xe/CFCl3 gas mixtures. Since no experimental resolution of the two formation pathways was achieved, individual, unquenched limiting yields for the excited state, Xe* + CFCl3 → XeCl* + .CHCl2, G o* = 2.4 ± 0.6, and ionic recombination, Xe2 + + Cl- + Xe → XeCl* + 2Xe, G o + = 3.2 ± 0.5, reactions have been calculated by modeling the dependence of the total fluorescent yield on xenon and halide gas pressure. Analogous experiments were also conducted for the formation of the XeI* exciplex from the irradiation of Xe/CF3I gas mixtures. Individual values for the two component formation processes were again calculated from total gas yields, giving G o* = 0.31 ± 0.08 and G o + = 4.5 ± 0.6. These yields are compared to the predictions of current theoretical models, and the effects of alternate recombination pathways are discussed.

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Section: Resultsmentioning

confidence: 99%

Absolute Fluorescence Yields from Electron-Irradiated Gases. 3. XeCl* and XeI*

1997

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“…The 7p[3/2] 2 state was investigated, rather than 7p[5/2] 2 , because of the larger two-photon cross section for the former, even though the rate constants had been measured for 7p[5/2] 2 . The long-lived XeCl(C) and XeF(C) concentrations are collisionally transferred into the B states or quenched, and only the D−X and B−X spectra were recorded. The spectra from HCl, Cl 2 , CCl 4 , CF 2 Cl 2 , and NF 3 are shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

Quenching Rate Constants and Product Assignments for Reactions of Xe(7p[3/2]₂, 7p[5/2]₂, and 6p‘[3/2]₂) Atoms with Rare Gases, CO, H₂, N₂O, CH₄, and Halogen-Containing Molecules

Алексеев

Setser

1996

J. Phys. Chem.

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Two-photon excitation of Xe atoms in a static gas cell was used to prepare the Xe(7p[3/2] 2 , 7p[5/2] 2 , and 6p′[3/2] 2 ) states in mixtures of Xe with rare gases, H O at 300 K. The total quenching rate constants were measured, and product fluorescence spectra were used to assign reaction pathways. The total quenching constants for these Xe* Rydberg states by molecular reagents are very large, corresponding to cross sections of 200-1500 Å 2 . Qualitative models are introduced to discuss the quenching processes, which are mainly reactive quenching and excitation transfer. For reagents with very large electron affinities, ion-pair formation may be important. A correlation of the quenching cross section with the dipole moment of the reagent was observed. These three Xe* states have nearly the same energy (∼11 eV), but the Xe(7p) states nominally have the Xe + ( 2 P 3/2 ) ion-core, whereas the Xe(6p′) states have the Xe + ( 2 P 1/2 ) core. The XeCl(D) and XeF(D) states also have the Xe + ( 2 P 1/2 ) core, and the fraction of XeCl(D) and XeF(D), relative to XeCl(B,C) or XeF(B,C), formed by the reactions of Xe-(6p′[3/2] 2 ) atoms with halogen-containing reagents can be used to measure the degree of conservation of the Xe + ( 2 P 1/2 ) core. The Xe(7p) and Xe(6p′) reactions actually gave nearly the same B and D distributions, with XeCl(B) and XeF(B) being favored, and the Xe + ( 2 P 1/2 ) ion-core state is not conserved during the reactions of Xe(6p′) atoms. Two-photon excitation of the Xe(7p,6p′) states leads to intense amplified spontaneous emission (ASE) unless special feature are incorporated into the experimental design. This ASE emission can cause complications because other Xe* states are generated during the laser pulse. The measurements reported here are free from ASE, but some consequences of ASE for experiments with Xe(6p′ and 7p) excitation are summarized. The relative two-photon cross sections of the Xe(6p, 6p′, 7p) states also are discussed.

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“…Lifetimes measured using optical methods of Rg 2 X(4 2 G) preparation are in good agreement. For the Xe 2 Cl molecule experimental values are 245 +10 ns (McCown and Eden 1983) and 242 ± 10 ns (Yu et al 1992).…”

Section: 32mentioning

confidence: 98%

Ab initio study of rare gas halides

Алексеев¹

2014

J. Phys. B: At. Mol. Opt. Phys.

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The electronic structures of the Ne 2 F, Ar 2 F, Kr 2 F, Xe 2 F, Ar 2 Cl, Kr 2 Cl, Xe 2 Cl, Kr 2 Br, Xe 2 Br, and Xe 2 I molecules have been studied on the CASSCF/CASPT2 level, with inclusion of the spin-orbit interaction. For the lowest strongly bound Rg 2 X(4 2 G) state we report R Rg-Rg and R Rg-X equilibrium bond lengths, dissociation energy, radiative lifetime and frequencies of three vibrational modes. Except for the antisymmetric stretch mode, a similar set of results was obtained for another five bound states above Rg 2 X(4 2 G). To compare equilibrium bond lengths and some other molecular properties, calculations were also performed for Rg 2 + and RgX diatomics on the same level of theory and using the same basis sets. The ab initio results obtained in this work are of interest for experimental and theoretical studies of Rg 2 X(4 2 G) formation mechanisms.

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Electronic quenching of XeCl(B,C) and Xe2Cl*

Cited by 17 publications

References 33 publications

Absolute Fluorescence Yields from Electron-Irradiated Gases. 3. XeCl* and XeI*

Absolute Fluorescence Yields from Electron-Irradiated Gases. 3. XeCl* and XeI*

Quenching Rate Constants and Product Assignments for Reactions of Xe(7p[3/2]₂, 7p[5/2]₂, and 6p‘[3/2]₂) Atoms with Rare Gases, CO, H₂, N₂O, CH₄, and Halogen-Containing Molecules

Ab initio study of rare gas halides

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Electronic quenching of XeCl(B,C) and Xe2Cl*

Cited by 17 publications

References 33 publications

Absolute Fluorescence Yields from Electron-Irradiated Gases. 3. XeCl* and XeI*

Absolute Fluorescence Yields from Electron-Irradiated Gases. 3. XeCl* and XeI*

Quenching Rate Constants and Product Assignments for Reactions of Xe(7p[3/2]2, 7p[5/2]2, and 6p‘[3/2]2) Atoms with Rare Gases, CO, H2, N2O, CH4, and Halogen-Containing Molecules

Ab initio study of rare gas halides

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Quenching Rate Constants and Product Assignments for Reactions of Xe(7p[3/2]₂, 7p[5/2]₂, and 6p‘[3/2]₂) Atoms with Rare Gases, CO, H₂, N₂O, CH₄, and Halogen-Containing Molecules