55130-03-5Relevant academic research and scientific papers
Rate constants and branching fractions for xenon halide formation from Xe(3P2) and Xe(3P1) reactions
Lin, Daimay,Yu, Y. C.,Setser, D. W.
, p. 5830 - 5832 (1984)
The rate constants for XeF(B,C ), XeCl(B,C ), and XeI(B,C ) formation from reactions of Xe(3P1) and Xe(3P2) with NF3, NZF4, NF2, CCl4, and CF3I have been measured relative to XeCl(B,C ) formation from the reacti
State-to-state relaxation processes for XeCl(B,C)
Dreiling, T. D.,Setser, D. W.
, p. 4360 - 4378 (1981)
The XeCl(B-X) and (C-A) emission spectra obtained from reaction of Xe(3P2 or 3P1) with Cl2, CCl4, and COCl2 in the presence of He, Ne, Ar, Kr, and N2 bath gases were used to study the vibrational relaxation and transfer between the B and C states of XeCl.By using the different Cl donors, different ranges of vibrational energy were emphasized.The bound-free emission spectra were simulated for various pressures of bath gas to obtain vibrational distributions.Numerical modeling of the XeCl(B) and XeCl(C) vibrational populations and the B/C intensity ratio as a function of pressure gave rate constants for vibrational relaxation and transfer, as well as the model for the state-to-state processes.For Ar as the bath gas, vibrational relaxation can be characterized by an exponential gap model Pij e-0.1ΔE/kT, with rate constants of (1-6), (6-12), and (20-30)x10-11 cm3 molecule-1 sec-1 for the v ranges of 0-30, 30-70, and 70-130, respectively.The rate constants for electronic state transfer are (3-11), (11-15), and (15-15)x10-11 cm3 molecule-1 sec-1 for the same v ranges.The vibrational energy loss upon electronic state transfer was best described by a Poisson-type function displaced to lower energy from the initial energy.These basic models also describe the relaxation in the other gases with He and Ne being less efficient and Kr and N2 more efficient than Ar.The magnitudes of the rate constants and the models are discussed.
Xe(3P2)+HCL(v=1): Vibrational enhancement of XeCl* formation
Chang, R. S. F.
, p. 2943 - 2948 (1982)
Formation of XeCl* from the Xe+(3P2)+HCl is slightly endothermic.In this work laser excitation of HCl (υ=1) in the presence of Xe(3P2 produuced in a flowing afterglow apparatus allows direct observation of XeCl* fluorescence from the Xe(3P2)+HCl(υ=1) reaction.The formation rate constant is determined to have a lower limit of 2*10-10 cm3 s-1.
Translational Energy Dependence of Reaction Dynamics in Kinematically Constrained Systems. Xe(3P2) + HCl, HBr, HI and CH3I
Hartree, William S.,Simons, John P.
, p. 11 - 16 (1990)
The fully dispersed chemiluminescence spectra excited by reactions of Xe(3P2) with HI, HBr, HCl and CH3I have been recorded under superthermal beam-Maxwellian gas conditions.Direct spectral inversion has enabled determination of the rare-gas halide product vibrational energy distributions at selected collision energies in the range T> ca. (4-90)kJ mol-1.The mean vibrational energy disposals v> are found to increase linearly with the mean collision energy T>.This result, together with earlier measurements of reactive excitation functions (K.M.Johnson, J.P.Simons, P.A.Smith, C.Washington and A.Kvaran, Mol.Phys., 1986, 57, 255) and with the kinematic constraint on the dynamics, allows separate estimates of the mean energy disposals into rotation and translation, as well as the mean reactive cross-section.
Energy disposal in the two-photon laser-assisted reaction in xenon and chlorine gas mixtures
Kohel,Keto
, p. 10551 - 10559 (2000)
The two-photon laser assisted reaction in a low pressure xenon and chlorine gas mixtures is studied to characterize the role of the entrance channel in determining the vibrational state distribution. A high degree of vibrational excitation in the XeCl product is measured. The measurements are in contrast with the vibrationally cold excimer observed following laser excitation in molecular beam experiments. The mean vibrational energy in the XeCl excimer depends upon the laser wavelength. As the laser is tuned toward shorter wavelength, an increasing fraction of the available energy from the reaction is observed.
Vibrational energy and bimolecular reactions: Enhancement of the electron transfer derived product channels for quenching of Xe(3P2) and Kr(3P2) atoms by CFnCl4-n, C2FnCl6-n
Sobczynski, R.,Setser, D. W.,Slagle, A. R.
, p. 1132 - 1144 (1990)
The yields of XeCl(B,C) and KrCl(B,C) from the reactions of Xe(3P2) and Kr(3P2) metastable atoms with chlorofluoromethanes and chlorofluoroethanes are enhanced by the addition of vibrational energy to the molecu
Reactive quenching of two-photon excited xenon atoms by Cl2
Bruce, M. R.,Layne, W. B.,Meyer, Enno,Keto, J. W.
, p. 420 - 427 (1990)
Total binary and tertiary quench rates have been measured for the reaction Xe (5p5np, np', n = 6,7) + Cl2 at thermal temperatures.Xenon atoms are excited by state-selective, two-photon absorption with an ultraviolet laser.The time-dependent fluorescence from the excited atom in the infrared, visible, and from XeCl* (B) product near 308 nm have been measured with subnanosecond time resolution.The decay rates are measured as a function of Cl2 pressure to 20 Torr and Xe pressure to 400 Torr.The measured reaction rates (k2 ca. 10-9 cm3 s-1) are consistent with a harpoon model described in a separate paper.We also measure large termolecular reaction rates for collisions with xenon atoms (k3 ca. 10-28 cm6 s-1).Total product fluorescence has been examined using a gated optical multichannel analyzer.We measure unit branching fractions for high vibrational levels of XeCl* (B) with very little C state fluorescence observed.
Spin-orbit state selective formation of rare gas chlorides from three-body ionic-recombination reactions of Rg+ (2P1/2,3/2) + Cl- + He at thermal energy
Tsuji, Masaharu,Furusawa, Makoto,Kuono, Hiroyuki,Nishimura, Yukio
, p. 4291 - 4300 (1991)
The ArCl(C-A), KrCl(B-X,C-A,D-X), and XeCl(B-X,C-A,D-X) emissions have been observed from ionic-recombination reactions of Rg+ (Rg = Ar, Kr, or Xe) with Cl- in the flowing afterglow.Positive Rg+ ions are formed by He(23S)/Rg Penning ionization, while negative Cl- ions are produced through thermal electron attachment to CCl4.The dependence of RgCl* emissions intensities on the buffer He gas pressure indicates that the excimer emission arise from three-body reactions of Rg+ + Cl- + He.The spin-orbit state selectivity in the KrCl* and XeCl* formation is studied by isolating one of the spin-orbit levels of Rg+, 2P1/2 or 2P3/2.Although the Kr+ (2P1/2) reaction provides the KrCl(B-X,C-A,D-X) emissions with B:C:D distribution of 0.19 +/- 0.02:0.12 +/- 0.01:0.69 +/- 0.04, only XeCl(D-X)emission is observed from the Xe+ (2P1/2) reaction.The Kr+ (2P3/2) and Xe+ (2P3/2) reactions give the RgCl(B-X,C-A) emission with B:C branching ratios of 0.60 +/- 0.06:0.40 +/- 0.04 for KrCl* and 0.62 +/- 0.06:0.38 +/- 0.04 for XeCl*.The high propensities for the D formation from the Rg+ (2P1/2) reactions and for the B and C formation from the Rg+ (2P3/2) reactions suggest that Rg+ (2P1/2) + Cl- and Rg+ (2P3/2) + Cl- characters are conserved well for the formation of RgCl* in the three-body ionic-recombination reactions.The relative formation rate of RgCl(D) from the Rg+ (2P1/2) reaction to that of RgCl(B,C) from the Rg+ (2P3/2) reaction was estimated to be 0.14 +/- 0.02 for KrCl* and 0.033 +/- 0.006 for XeCl*.The slower RgCl(D) formation rates are attributed to fast predissociation of + (2P1/2)Cl-> intermediates into Rg* + Cl and/or Rg + Cl than that of + (2P3/2)Cl->* ones.
Comparison of the Rg+(2P1/2)/Cl-/He and Rg+(2P3/2)/Cl-/He three-body ionic-recombination reactions for the formation of RgCl*, Rg*, and Cl*<
Tsuji, Masaharu,Muraoka, Toshihiko,Kouno, Hiroyuki,Nishimura, Yukio
, p. 1079 - 1086 (1992)
Three-body ionic-recombination reactions of Rg+ + Cl- + He (Rg = Kr or Xe) leading to RgCl* excimers and their predissociation products (Rg* and Cl*) have been studied by observing emission spectra in
XeF* and XeCl* Formation in Low-Pressure Tesla Coil Discharges
Wren, D. J.,Setser, D. W.,Ku, J. K.
, p. 284 - 291 (1982)
The XeCl* and XeF* emission spectra have been studied from mixtures of Xe with HCl, Cl2, CCl4, NF3, BF3, C2F6, and SF6 in a tesla-coil-driven discharge.The XeX* emission spectra were recorded at pressures below 0.75 torr for all reagents except BF3, and C2F6, which did not give XeF* emission.Low-pressure pulsed dc discharge experiments in Xe/Cl2 and Xe/HCl mixtures gave XeCl* emission spectra very similar to those observed from the tesla-driven discharge.Computer simulations of the XeCl(B-X) spectra from discharges of Xe with Cl2, CCl4, and HCl provide an estimate for the XeCl(B) vibrational distributions.Since Xe(3P2) and Xe(3P1) reacting with HCl and SF6 do not give XeX*, the observation of XeX* from these two reagents requires the reactions of Xe Rydberg states or recombination of Xe+ and Cl- or F- ions.Arguments based upon XeCl* and XeF* vibrational and electronic state populations and the time dependence of the emission suggest that Rydberg state reactions are the dominant mechanism contributing to the XeX* excitation from the low-pressure discharge of Xe/HCl and Xe/SF6 mixtures.
