Crossed beam study of the I2+F2→IF(B)+IF(X) reaction: Spectrum of the chemiluminescence and rovibrational distribution of IF(B)

Billy, N.; Girard, B.; Gouédard, G.; Vigué, J.; Caprio, Dung Di; Caillaud, B.; Gall, Jean Le; Venturi, M.

doi:10.1063/1.455776

Cited by 3 publications

(4 citation statements)

References 34 publications

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“…If two mechanisms (direct and migratory) are active in the F 2 + 12 chemiluminescent reaction, they should most probably lead to different rovibrational distritution of the products. Our results (24) exhibit such a bimodality: the lowest vibrational levels (v = 0-2) have a cold rotational distribution, while the higher vibrational levels (mostly v = 3-7 as for higher v values the rotational distribution is severely truncated by the B state predissociation) have a very hot rotational distribution. We may tentatively assume that this bimodal rovibrational distribution is due to the existence of two mechanisms (direct and migratory) in this reaction.…”

Section: ) Discussionmentioning

confidence: 78%

“…The monochromator (Jobin-Yvon THR 1500) receives the light through the same three-lens system used already in our previous chemiluminescence experiment (24). The photomultiplier we use now is Burle C31034A, with a GaAs photocathode, cooled to -50'C by a thermoelectric chamber (Products for Research TE210 RF), giving a dark count rate around 1-2 counts per second.…”

Section: ) the Experimentsmentioning

confidence: 99%

“…A detailed description of our beam machine has been given in references (24,39,40). We recall here the main features and describe the modifications:…”

Section: ) the Experimentsmentioning

confidence: 99%

“…KAHLER and Y.T. LEE (7), we have made a detailed study of the F 2 + 12 chemiluminescent reactive collision, under crossed-beam conditions (24). We have used here the same techniques to study the series of reactions with the following iodides: HI, CF 3 I , CH3I , CH 2 1 2 , CHI 3 , CI 4 .…”

Section: ) Introductionmentioning

confidence: 99%

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Crossed-beam studies of some chemiluminescent reactions producing IF

Khalil

Billy

Gouédard

et al. 2000

Phys. Chem. Chem. Phys.

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This paper describes the study of the chemiluminescent branch of the reactive collisions of molecular Ñuorine with a series of iodides, HI, and All these reactions can produce IF in its A and F 2 CF 3 I, CH 3 I, CH 2 I 2 CHI 3 . B excited states, but in crossed molecular beam conditions, only the B state can contribute to the observed chemiluminescence signals. These signals have been studied as a function of the reactant densities and of the collision kinetic energy, providing in particular estimates of the reaction thresholds. The spectrum of the chemiluminescence has been recorded and analyzed in terms of the IF B state rovibrational F 2 ] HI distribution. To explain our observations, we have extended a model, previously developed by C. C. Kahler and Y. T. Lee for the chemiluminescent reaction, by introducing a migratory step. I 2 ] F 2

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Section: ) Discussionmentioning

confidence: 78%

Section: ) the Experimentsmentioning

confidence: 99%

“…A detailed description of our beam machine has been given in references (24,39,40). We recall here the main features and describe the modifications:…”

Section: ) the Experimentsmentioning

confidence: 99%

Section: ) Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Crossed-beam studies of some chemiluminescent reactions producing IF

Khalil

Billy

Gouédard

et al. 2000

Phys. Chem. Chem. Phys.

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Differential cross section as a function of the product internal state: The F+I2→IF(v,J)+I reactive collision

Girard¹,

Billy²,

Gouédard³

et al. 1991

The Journal of Chemical Physics

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We have measured the differential cross section of the F+I2→IF+I reactive collision as a function of the rovibrational state of IF. This measurement was made by an analysis of the Doppler profiles of the laser-induced fluorescence detection signals, as suggested by Kinsey [J. Chem. Phys. 66, 2560 (1977)]. This paper describes in detail the experiment and the way we analyze the data to deduce the differential cross section. The shape of the cross section appears to vary noticeably with the rotational energy of IF and to a lesser extent with its vibrational energy. Several partial explanations are possible, and the choice remains not clear as long as we have no precise information on the potential-energy surfaces of the I2F system.

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IF(A,B) electronic excitation in F+I2F induced by the surface reaction F(ad)+I2(ad)

Wagemann

Chen

Wanner

1991

The Journal of Chemical Physics

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This paper reports on a dynamical study of the reaction of an effusive F atom beam with iodine molecules condensed on a temperature-controlled LiF(001) surface. The observation of IF ground state products by laser-induced fluorescence and of IF(A,B) excited species by visible chemiluminescence can be explained by means of a reaction scheme consisting of two channels. In the first channel IF (X 1Σ+) ground state molecules are formed on the surface and desorb into the gas phase above a threshold temperature of about 200 K, where they are probed by laser-induced fluorescence. The vibrational population ratio [N′(v=0)/N′(v=1)] shows equilibrium of the desorbing molecules with the surface. The population distribution of the IF(v=0) rotational manifold can be well-characterized by a rotational temperature which follows the surface temperature. Surface equilibration of products implies that, unlike in the gas phase reaction F+I2, the products have no memory of their exoergic formation, indicating a Langmuir–Hinshelwood mechanism. In a second reaction channel I2F, as the intermediate in the reaction of fluorine atoms with adsorbed iodine molecules, stabilizes at the surface and desorbs into the gas phase above a surface temperature of 300 K. There it reacts with F atoms according to the chemiluminescence process F+I2F→IF*+IF. This gas phase reaction is identified by the exoergicity limit of the IF (B 3Π) state vibrational population distribution, obtained from analysis of the B→X chemiluminescence. In comparison with Kahler and Lee’s molecular beam synthesis of I2F from I2 and F2 with subsequent secondary encounter with the product F atom, the above reaction scheme represents an alternative induction of the F+I2F reaction. It can explain visible IF chemiluminescence from fluorine–iodine systems under experimental conditions in which F atoms are present and I2 wall adsorption is possible. In this work, evidence is given that I2F is a common precursor in the two reaction channels. The overall branching ratio strongly favors the formation of IF ground state molecules in these experiments.

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Crossed beam study of the I2+F2→IF(B)+IF(X) reaction: Spectrum of the chemiluminescence and rovibrational distribution of IF(B)

Cited by 3 publications

References 34 publications

Crossed-beam studies of some chemiluminescent reactions producing IF

Crossed-beam studies of some chemiluminescent reactions producing IF

Differential cross section as a function of the product internal state: The F+I2→IF(v,J)+I reactive collision

IF(A,B) electronic excitation in F+I2F induced by the surface reaction F(ad)+I2(ad)

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