Yutaka Matsumi

Quantum yields for production of O(1D) in the ultraviolet photolysis of ozone: Recommendation based on evaluation of laboratory data

[1] The quantum yield for O( 1 D) production in the photolysis of ozone in the ultraviolet region as a function of wavelength and temperature is a key input for modeling calculations in the atmospheric chemistry. To provide the modeling community with the best possible information, the available data are critically evaluated, and the best possible recommendations for the quantum yields are presented. Since the authors of this paper are the principal investigators of the groups which have provided most of the recent experimental data for the O( 1 D) quantum yields, the basic assumptions made by each group, the input parameters used in obtaining the quantum yields, and possible sources of systematic errors are well examined. The fitting expression of the O( 1 D) yield as a function of photolysis wavelength λ and temperature Tis presented in the ranges of 306 nm < X < 328 nm and 200 K < T < 300 K. The recommendation values of the O( 1 D) quantum yield for 290 nm < X < 306 nm and 328 nm < λ <350 nm are also presented. The formation mechanisms of O( 1 D) in the photolysis of ozone which result in the wavelength and temperature dependence of the O( 1 D) yields are interpreted.

Fine‐structure branching ratios and Doppler profiles of Cl(2Pj) photofragments from photodissociation of the chlorine molecule near and in the ultraviolet region

Photofragment chlorine atoms in the 2Pj states from Cl2 at 266–500 nm are measured by a resonance‐enhanced multiphoton ionization technique. The measured branching ratio of [Cl*(2P1/2)]/[Cl(2P3/2)] increases monotonically with dissociation wavelengths from (9.5±1.8)×10−3 at 308 nm to (4.7±0.5)×10−1 at 475 nm. At 375 nm≤λ≤475 nm, Doppler profiles of the chlorine atoms indicate adiabatic formation of two Cl(2P3/2) from the 1Π(1u) state of Cl2 and Cl(2P3/2)+Cl*(2P1/2) from the B 3Π(0+u) state. On the other hand, at a shorter wavelength (308 nm), Cl*(2P1/2) is generated from the 1Π(1u) state through nonadiabatic transitions during the dissociation. The relative contribution of the 1Π(1u)←X 1Σ(0+g) and B 3Π(0+u)←X 1Σ(0+g) transitions in the photoabsorption is estimated from the obtained branching ratios at 375 nm≤λ≤475 nm.

Formation of O(3Pj) photofragments from the Hartley band photodissociation of ozone at 226 nm

The photodissociation of ozone at 226 nm is studied for O3→O2(X3 Σ−g)+O(2p3Pj) by probing O(3Pj) atomic photofragments with a resonance‐enhanced multiphoton ionization method. Angular and kinetic energy distributions are determined by measuring time‐of‐flight spectra as a function of the angle between the polarization vector of the dissociation laser and the detector axis. The Doppler width of O(3Pj) photofragments is also measured. The translational energy distribution is well represented by assuming the formation of vibrationally excited O2 molecules with an average vibrational quantum number of 12. The anisotropy parameter β for the angular distribution is found to be 0.7±0.1. The predissociation dynamics from the photoprepared O3(1B2) state to the repulsive potential surface is discussed.

Dynamics of the reactions of O(1D) with HCl, DCl, and Cl2

The reactions O(1D)+HCl→OH+Cl (1a) and OCl+H (1b), O(1D)+DCl→OD+Cl (2a) and OCl+D (2b), and O(1D)+Cl2→OCl+Cl (3) are studied at an average collision energy of 7.6, 7.7, and 8.8 kcal/mol for (1), (2), and (3), respectively. H, D, and Cl atoms are detected by the resonance‐enhanced multiphoton ionization technique. The average kinetic energies released to the products are estimated from Doppler profile measurements of the product atoms. The relative yields [OCl+H]/[OH+Cl] and [OCl+D]/[OD+Cl] are directly measured, and a strong isotope effect (H/D) on the relative yields is found. The fine‐structure branding ratios [Cl(2P1/2]/[Cl(2P3/2)] of the reaction products are also measured. The results suggest that nonadiabatic couplings take place at the exit channels of the reactions (1a) and (2a), while the reaction (3) is totally adiabatic.

Emission spectra of SiH(A 2Δ→X 2Π) and SiCl2(Ã 1B1→X̃ 1A1) in the VUV photolyses of silane and chlorinated silanes

Vacuum UV photolyses of silane and chlorinated silanes were investigated by using rare gas resonance lamps. Strong emissions, from the A 2Δ→X 2Π transition of SiH and the 1P0→1D2 transition of Si were observed in the photolysis of SiH4 by Ar and Kr resonance lamps. It was suggested that the threshold energies for the appearance of both emissions were lower than the values obtained by the electron impact of SiH4 reported by Perrin et al. A new broad unstructured emission band in the region 300–400 nm was observed in the photolysis of SiH2Cl2 and SiHCl3 by Ar, Kr, and Xe lamps. The band was attributed to the A 1B1→X 1A1 transition of SiCl2 radicals from the measurement of the appearance energy of the emission by using synchrotron orbital radiation.

Mechanism of the ultraviolet photodissociation of chloroethylenes determined from the Doppler profiles, spatial anisotropy, and power dependence of the photofragments

Doppler profiles of chlorine and hydrogen atomic fragments produced in the photodissociation of mono‐ and dichloroethylenes at 193 nm have been measured in a pump‐and‐probe experiment using 2+1 resonance‐enhanced multiphoton ionization. In a second experiment, the angular distributions of the Cl fragments produced from chloroethylenes at 235 and 238 nm were measured using a perfect‐focusing mass spectrometer. In a third experiment, we measured the power dependence of the relative yields of H, Cl, HCl, and HCl+ produced from vinyl chloride at 193 nm. For Cl detachment, two primary processes have been confirmed. One produces an isotropic angular distribution of photofragments, while the other produces an anisotropic distribution. For H atom detachment, an isotropic angular distribution and a Boltzmann velocity distribution were found. The ratio of yields of the Cl and H fragments was found to be 4±1 for CH2CCl2 and higher than 10 for t‐CHClCHCl and CCl2CClH. The H, Cl, and HCl yields were found to be first ...

Fine structure branching ratios and Doppler spectroscopy of chlorine atoms from the photodissociation of alkyl chlorides and chlorofluoromethanes at 157 and 193 nm

Alkyl chlorides (R=CH3, C2H5, C3H7, and C4H9), chloromethanes (CHnCl4−n), and chlorofluoromethanes (CFnCl4–n) are photodissociated at 157 and 193 nm. The chlorine atom photofragments are detected by a resonance enhanced multiphoton ionization technique. The branching ratios of the Cl photofragments [Cl*(3p2P1/2)]/[Cl(3p2P3/2)] are almost identical (0.23±0.03) for alkyl monochlorides at 157 and 193 nm and for CH2Cl2 and CHCl3 at 157 nm, while the ratios are rather small (0.10±0.02) for CH2Cl2 and CHCl3 at 193 nm. No discernible isotope effects on the branching ratios were observed when D atoms were substituted for H atoms in chloromethanes. For CCl4, CF3Cl, CF2Cl2, CFCl3 at 157 and 193 nm, the ratios are small (<0.05) irrespective of the number of Cl atoms in the parent molecules. The Doppler profiles of the chlorine photofragments have been obtained and it is found that (a) CF3Cl undergoes a perpendicular optical transition at 157 nm and (b) for halomethanes containing more than two Cl atoms, the Cl photo...

Laser‐induced fluorescence study of silicon etching process: Detection of SiF2 and CF2 radicals

Using a laser‐induced fluorescence (LIF) technique, SiF2 and CF2 radicals are detected during the downstream etching of silicon with a discharge of CF4 gas. It is confirmed that SiF2 radical is desorbed from the surface in the etching of silicon by fluorine atom. Addition of O2 gas to the CF4 discharge enhances the LIF intensity of SiF2 radical and extinguishes that of CF2. Mechanism of the increase of etching rate of silicon by addition of O2 is discussed on the basis of the results of LIF measurements. The etching rate of silicon is proportional to the LIF intensity of SiF2, when the microwave power of the discharge is changed. The relationship between the intensity of chemiluminescent continuum and the concentration of SiF2 is revealed, which suggests that the chemiluminescence is attributed to the emission of SiF*3 which is produced by the reaction between SiF2 and fluorine atoms in the gas phase. There is no signal of SiF2 during the etching of either SiO2 or SiNx.

TRANSLATIONAL RELAXATION AND ELECTRONIC QUENCHING OF HOT O(1D) BY COLLISIONS WITH N2

Translational relaxation and electronic quenching processes of translationally hot O(1D) atoms by collisions with N2 in a gas cell at room temperature are studied using a vacuum ultraviolet laser induced fluorescence technique. The initial hot O(1D) atoms which have translational energies of 18.2 and 9.8 kcal mol−1 are produced by the photodissociation of N2O at 193 nm and O2 at 157 nm, respectively. The translational relaxation processes are investigated by time resolved measurements of the Doppler profiles for the O(1D) atoms, while the quenching processes are studied by measuring both the decrease of the O(1D) concentration and the increase of the product O(3P) concentration after the photochemical formation of the hot O(1D) atoms. When the initial translational energy of O(1D) is 9.8 kcal mol−1, about 40% of the O(1D) atoms are electronically quenched before the entire thermalization of the hot O(1D) atoms takes place in a gaseous mixture with N2. This indicates that the translational relaxation rate ...

Observation of the spin‐forbidden O(1D)+O2(X 3Σg−) channel in the 317–327 nm photolysis of ozone

The photofragment excitation spectra for O(1D) production from the 317–327 nm photolysis of ozone under supersonic free‐jet and low‐temperature flow conditions show structure superimposed on an underlying continuum. Doppler profiles of the nascent O(1D) photofragments confirm that the O(1D) formed by photolysis at the wavelengths of the peaks in the photofragment excitation spectrum arises from the hitherto unobserved spin‐forbidden predissociation to O(1D)+O2(X 3Σg−) products.