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Photoabsorption and fluorescence cross sections of HCl are investigated in the wavelength region between 105 to 220 nm. The oscillator strengths of discrete structures at wavelengths shorter than 130 nm are measured.
Concern over halogen catalyzed decomposition of O3 in the upper atmosphere has generated need for data on the atomic and molecular species X, HX and XO (where X is Cl and Br). Of special importance are Cl produced from freon decomposition and Cl and Br produced from natural processes and from other industrial and agricultural chemicals. Basic spectral data is provided on HCl, HBr, and BrO necessary to detect specific states and energy levels, to enable detailed modeling of the processes involving molecular dissociation, ionization, etc., and to help evaluate field experiments to check the validity of model calculations for these species in the upper atmosphere. Results contained in four published papers and two major spectral compilations are summarized together with other results obtained.
A crossed target beam-electron beam collision geometry and a quadrupole mass spectrometer have been used to conduct dissociative electron attachment cross section measurements for the case of H(-) and Cl(-) production from HCl. The relative flow technique is used to determine the absolute values of cross sections. A tabulation is given of the attachment energies corresponding to various cross section maxima. Error sources contributing to total errors are also estimated.
The reaction HCl + ClONO2 yields Cl2 + HNO3 has been studied by Fourier transform infrared spectroscopy and by a static wall-less UV absorption technique. An upper limit to the homogeneous bimolecular rate constant of 10 to the -19th cu cm/molecule per sec was established, making the reaction unimportant in the stratosphere.
The absolute rate coefficients and product yields for reactions of O(1D) with HCl(1) and HBr(2) at 287 K are presently determined by means of the time-resolved resonance fluorescence detection of O(3P) and H(2S) in conjunction with pulsed laser photolysis of O3/HX/He mixtures. Total rate coefficients for O(1D) removal are found to be, in units of 10 to the -10th cu cm/molecule per sec, k(1) = 1.50 + or - 0.18 and k(2) 1.48 + or - 0.16; the absolute accuracy of these rate coefficients is estimated to be + or - 20 percent.
Self-broadening in the vibrational fundamental of HCl is inversely proportional to the temperature for transitions which lie near the Boltzmann rotational maximum and becomes monotonically less temperature-dependent as the rotational quantum number increases. The rotationless transition moment was found to have the value of 5.57 + or - 0.13 x 10 to the -3rd (Debye)-squared and the first Herman-Wallis factor, C = -2.543 + or - 0.019 x 10 to the -2nd.
The photoabsorption and fluorescence cross sections of HCl were measured in the 106-185 nm region. Sharp absorption bands appear at wavelengths shorter than 135 nm, and fluorescence occurs at several excited states. The fluorescence cross sections are generally quite small, indicating that the excited states are strongly predissociative. The molecular processes for producing the VUV and UV fluorescences are investigated, and the Rydberg characteristics of the strong absorption bands are discussed.
Chemiluminescent emission from the formation of vibrationally excited OH at an altitude of approximately 85 km presents a barrier to earth-limb measurements of NIR emissions originating in the stratosphere. High-resolution measured spectra of OH airglow have not been reported, and thus it is difficult to assess its impact on moderately-high-resolution earth-limb spectroscopy capable of looking between strong OH lines. Low-resolution rocketborne spectrometer earth-limb measurements of OH airglow are mathematically inverted to recover vibrational-state populations that are used to simulate a higher resolution spectrum in the neighbourhood of 2843/cm. Implications for remote sensing HCl are presented.
Nitric acid and hydrochloric acid vapors may condense in the winter polar stratospheres. Nitric acid clouds, unlike water ice clouds, would form at the temperatures at which polar stratospheric clouds (PSCs) are observed and would have optical depths of the magnitude observed suggesting that HNO3 is a dominant component of PSCs. ClO, N2O5 and ClNO3 may react on cloud particle surfaces yielding additional HNO3, HCl, and HOCL. In the vicinity of PSCs these reactions could deplete the stratosphere of photochemically active NO(x) species. The sedimentation of PSCs may remove these materials from the stratosphere. The loss of vapor phase NO(x) might allow halogen-based chemistry to create the ozone hole.
The resolvent operator formalism of Kolb, Griem (1964), and Baranger (1962) is used to determine the widths and shifts of the fundamental band vibration-rotation lines of HCl under N2 pressure. Time-development operator matrix elements are evaluated accounting for all bilinear and second order anisotropic terms, in addition to isotropic effects to all orders. The method employs the use of a parabolic trajectory model and explicit velocity averaging. The major contributions to the linewidths are found to arise from dipole-quadrupole, quadrupole-quadrupole, and vibrationally dependent isotropic dispersion forces. Good overall agreement is found between calculated and measured widths and linewidths over a 163-295 K temperature range.
A differential-absorption lidar system has been developed which uses a continuously tunable (1.5-2.3 micron) cobalt-doped magnesium fluoride laser as the radiation source. Preliminary atmospheric measurements of water vapor, HCl, and CH4 have been made with this system, including both path-averaged and ranged-resolved DIAL measurements at ranges up to 6 and 3 km, respectively.
Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.
Infrared solar spectra were obtained from the ground at McMurdo, Antarctica, during September and October 1987. Absorption features due to HNO3 and HCl have been analyzed to determine the vertical column content of these compounds for the days when observations were made. The variation of these column amounts with time is presented and discussed.
Measurements were conducted of the N2-broadening coefficients in the vibrational fundamental line of HCl at 160, 182, 216, 255, and 296 K. It is found that the N2 broadening of rovibrational lines in the -6 to +6 range is well described by a simple power-law dependence on temperature. The temperature-interpolation of these results is noted to be in good agreement with previous low-temperature studies.
An interaction potential for HCl-Ar recently derived from spectra of van der Waals complexes (Hutson,1988) has been used to obtain converged close-coupling scattering S matrices from which pressure broadening (linewidth, line shift, and line coupling) cross sections have been computed within the Fano-Ben-Reuven formalism. Linewidths agree well with experimental data with the exception of the 0-1 line at low temperatures (an error of about 15 percent at 125 K). Line shifts, especially the largest, for the 0-1 line, are also in reasonable accord with experimental data. Line coupling is predicted to be quite small. The coupled-states molecular scattering approximation is found to be accurate except at very low collision energies. The infinite-order sudden approximations, on the other hand, is not reliable for this system. Inelastic scattering out of the spectroscopic levels accounts for only a fraction of the linewidth at thermal energies, especially in the lower rotational levels.
Absorption lines from vibrationally excited H2 and from HCl were detected in the ultraviolet spectrum of Zeta Oph with the Hubble Space Telescope (HST). Improved upper limits on NO(+) absorption were obtained as well. The data were analyzed with an updated version of a chemical model for diffuse clouds (van Dishoeck & Black 1986) as a guide to understanding this gaseous environment. The comparisons suggest that the flux of ultraviolet radiation impinging on the cloud surface is approximately 1-2 times the average interstellar radiation field, which is lower than once believed.
We have detected the 626 GHz J = 1 approaches 0 transition of hydrogen chloride (H(sup 35)Cl) in absorption against the blending of the three hyperfine components of this transition by the velocity profile of Sgr B2 observed in other species. The apparent optical depth of the line is tau approximately equal to 1, and the minimum HCl column density is 1.6 x 10(exp 14)/sq cm. A detailed radiative transfer model was constructed which includes collisional and radiative excitation, absorption and emission by dust, and the radial variation of temperature and density. Good agreement between the model and the data is obtained for HCl/H2 approximately 1.1 x 10(exp -9). Comparison of this result to chemical models indicates that the depletion factor of gas-phase chlorine is between 50-180 in the molecular envelope surrounding the SgrB2(N) and (M) dust cores.
A recently developed algorithm, SFIT2, is used to assess profile information available in ground-based FTIR measurements of HCl and HNO3 and to analyze spectra recorded at Lauder, New Zealand, and Arrival Heights, Antarctica. It is shown that the altitude range of HCI retrievals may be extended by using multiple spectral lines. A preliminary analysis of a five year record of HNO3 at Lauder shows that the Pinatubo aerosol caused a large increase of HNO3 in a layer at about 20-30 km while having little effect at lower altitude.