Experimental detection of chemical radiative collisions

doi:10.1016/0009-2614(78)80416-3

Chemical Physics Letters

Volume 53, Issue 1, 1 January 1978, Pages 170-173

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Abstract

Absorption has been measured in a mixture of Xe + F₂ which is apparently induced by collisions. The spectral dependence (1580—1900 Å) of the absorption coefficient differs in detail from that of XeF₂. The rather large magnitude of this absorption coefficient is in the range previously estimated for the reaction Xe + F₂ +_ħω → XeF* + F.

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Tunable synchrotron radiation has been used to excite selectively gas phase mixtures of rare gas atoms and molecular halogens in the vacuum UV region. The fluorescence excitation spectra of the B—X and D—X transitions of XeCl* and the B—X transition of KrCl* and XeBr* have been recorded. The excitation spectra show that electronic excitation of either rare gas atoms or molecular halogens in rare gas-halogen mixtures leads to formation of rare gas halide excimers. The atomic and molecular precursors for excimer formation were identified and their formation mechanisms are discussed.
Absorption spectrum of the complex Xe+F<inf>2</inf>
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The absorption spectrum of the complex Xe+F₂ in the spectral ranges: (1) 165.0—155.4 nm, (2) 145.3—130.6 nm, (3) 128.8—122.0 nm has been studied. In the first range the structureless spectrum obtained is in good agreement with the result of our earlier papers. The spectrum shows an intensive structure in the second and the third ranges. The nature of the structure obtained has been discussed qualitatively.
Wavelength dependence of the photoassociation of Kr(4p6 1S<inf>0</inf>)-F(2p5 2P) collision pairs
1992, Chemical Physics Letters
The excitation spectrum for the photoassociation (bound←free absorption) of thermalized pairs of Kr(4p⁶¹S₀) and F(2p⁵²P) atoms in Kr/F₂ gas mixtures at 300 K has been recorded in the ultraviolet (208⩽λ⩽250 nm). By photodissociating F₂ in the presence of Kr and subsequently photoexciting Kr—F collision pairs in the ground state thermal continuum with tunable laser radiation, deeply modulated Franck—Condon structure associated with bound←free transitions terminating on the lowest 26 vibrational levels of the B ²Σ ion pair state of the KrF molecule was observed. Since the KrF ground state interaction potential is repulsive, photoassociation occurs in a narrow (ΔR≈0.7 Å) Franck—Condon region and structural information regarding the upper and lower state potentials, as well as the dependence of the electronic transition moment on internuclear separation, can be extracted from the spectrum. The Kr—F system is presented here as an example of the effectiveness of photoassociation as a tool with which one can determine the chemical, structural and optical properties of small excimer molecules that are otherwise difficult to access experimentally.
Mechanism of the two-photon laser assisted reaction of Xe and Cl<inf>2</inf> to form XeCl
1992, Journal of Molecular Structure
Two-photon laser assisted reactions of Xe and Cl₂ at low pressure has been used to prepare xenon chloride in excited states (XeCl^*(B[ $12$ ], C[ $32$ ])). Dispersed luminescence spectra due to the XeCl transition, B[ $12$ −> X[ $12$ ], in the spectral region 290 –310 nm were recorded for different excitation wavelengths. The vibrational energy disposal was assessed through spectral simulation of the emission spectra. The mechanism for XeCl(B) formation is discussed in terms of a simple global model.
Cooperative two-photon-induced chemical bond formation during a Kr+F<inf>2</inf> collision to form KrF*
1990, Chemical Physics Letters
The reactive Kr⁺F₂⁻ potential energy surface is probed by two-photon, laser-induced chemical bond formation during a Kr+F₂ collision. This is compared with the pulsed laser excitation (two-photon) of Kr(2p₉) followed by collision with F₂ leading to the formation of KrF(B, C). In addition to reporting the excitation spectrum for the two-phonon-induced collision process, these techniques were used to determine quenching rate constants of Kr₂F^*. Quenching by Xe gives XeF(B, C) with rate constant (1.5±0.2)×10⁻¹⁰ cm³ s⁻¹; the quenching rate constant for F₂ is (1.5±0.2)×10⁻¹⁰ cm³ s⁻¹, and the radiative lifetime of Kr₂F^* is 240±35 ns. The quenching rate constant for the coupled Kr(2p₈) and Kr(2p₉) levels by F₂ is (13±2)×10⁻¹⁰ cm³ s⁻¹.
Cooperative optical transitions in impurity centers coupled via host atoms
1987, Chemical Physics Letters

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Chemical Physics Letters

Abstract

References (6)

Chem. Phys. Letters

Spectrochim. Acta

Cited by (23)

Fluorescence excitation spectra of XeCl(B,D), KrCl(B), and XeBr(B) excimers

Absorption spectrum of the complex Xe+F<inf>2</inf>

Wavelength dependence of the photoassociation of Kr(4p<sup>6 1</sup>S<inf>0</inf>)-F(2p<sup>5 2</sup>P) collision pairs

Mechanism of the two-photon laser assisted reaction of Xe and Cl<inf>2</inf> to form XeCl

Cooperative two-photon-induced chemical bond formation during a Kr+F<inf>2</inf> collision to form KrF<sup>*</sup>

Cooperative optical transitions in impurity centers coupled via host atoms