A joint theoretical and experimental investigation is undertaken to study the effects of OH-stretch/HOON torsion coupling and of quantum yield on the previously reported first overtone action spectrum of cis-cis HOONO (peroxynitrous acid). The minimum energy path along the HOON dihedral angle is computed at the coupled cluster singles and doubles with perturbative triples level with correlation consistent polarized quadruple zeta basis set, at the structure optimized using the triple zeta basis set (CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ). The two-dimensional ab initio potential energy and dipole moment surfaces for cis-cis HOONO are calculated as functions of the HOON torsion and OH bond length about the minimum energy path at the CCSD(T)/cc-pVTZ and QCISD/AUG-cc-pVTZ (QCISD-quadratic configuration interaction with single and double excitation and AUG-augmented with diffuse functions) level of theory/basis, respectively. The OH-stretch vibration depends strongly on the torsional angle, and the torsional potential possesses a broad shelf at approximately 90 degrees , the cis-perp conformation. The calculated electronic energies and dipoles are fit to simple functional forms and absorption spectra in the region of the OH fundamental and first overtone are calculated from these surfaces. While the experimental and calculated spectra of the OH fundamental band are in good agreement, significant differences in the intensity patterns are observed between the calculated absorption spectrum and the measured action spectrum in the 2nu(OH) region. These differences are attributed to the fact that several of the experimentally accessible states do not have sufficient energy to dissociate to OH+NO(2) and therefore are not detectable in an action spectrum. Scaling of the intensities of transitions to these states, assuming D(0)=82.0 kJ/mol, is shown to produce a spectrum that is in good agreement with the measured action spectrum. Based on this agreement, we assign two of the features in the spectrum to Deltan=0 transitions (where n is the HOON torsion quantum number) that are blue shifted relative to the origin band, while the large peak near 7000 cm(-1) is assigned to a series of Deltan=+1 transitions, with predominant contributions from torsionally excited states with substantial cis-perp character. The direct absorption spectrum of cis-cis HOONO (6300-6850 cm(-1)) is recorded by cavity ringdown spectroscopy in a discharge flow cell. A single band of HOONO is observed at 6370 cm(-1) and is assigned as the origin of the first OH overtone of cis-cis HOONO. These results imply that the origin band is suppressed by over an order of magnitude in the action spectrum, due to a reduced quantum yield. The striking differences between absorption and action spectra are correctly predicted by the calculations.
Abstract The Cross‐track Infrared Sounder (CrIS) and the Advanced Technology Microwave Sounder (ATMS) instruments aboard the Suomi National Polar‐orbiting Partnership satellite provide high‐quality hyperspectral infrared and microwave observations to retrieve atmospheric vertical temperature and moisture profiles (AVTP and AVMP) and many other environmental data records (EDRs). The official CrIS and ATMS EDR algorithm, together called the Cross‐track Infrared and Microwave Sounding Suite (CrIMSS), produces EDR products on an operational basis through the interface data processing segment. The CrIMSS algorithm group is to assess and ensure that operational EDRs meet beta and provisional maturity requirements and are ready for stages 1–3 validations. This paper presents a summary of algorithm optimization efforts, as well as characterization and validation of the AVTP and AVMP products using the European Centre for Medium‐Range Weather Forecasts (ECMWF) analysis, the Atmospheric Infrared Sounder (AIRS) retrievals, and conventional and dedicated radiosonde observations. The global root‐mean‐square (RMS) differences between the CrIMSS products and the ECMWF show that the AVTP is meeting the requirements for layers 30–300 hPa (1.53 K versus 1.5 K) and 300–700 hPa (1.28 K versus 1.5 K). Slightly higher RMS difference for the 700 hPa‐surface layer (1.78 K versus 1.6 K) is attributable to land and polar profiles. The AVMP product is within the requirements for 300–600 hPa (26.8% versus 35%) and is close in meeting the requirements for 600 hPa‐surface (25.3% versus 20%). After just one year of maturity, the CrIMSS EDR products are quite comparable to the AIRS heritage algorithm products and show readiness for stages 1–3 validations.
Author Institution: Arthur Amos Noyes Laboratory for Chemical Physics, California Institute; of Technology, Pasadena, CA 91125; Department of Chemistry, The Ohio State University, Columbus, OH 43210; Arthur Amos Noyes Laboratory for Chemical Physics, California Institute; of Technology, Pasadena, CA 91125
The reaction of OH and NO(2) to form gaseous nitric acid (HONO(2)) is among the most influential in atmospheric chemistry. Despite its importance, the rate coefficient remains poorly determined under tropospheric conditions because of difficulties in making laboratory rate measurements in air at 760 torr and uncertainties about a secondary channel producing peroxynitrous acid (HOONO). We combined two sensitive laser spectroscopy techniques to measure the overall rate of both channels and the partitioning between them at 25°C and 760 torr. The result is a significantly more precise value of the rate constant for the HONO(2) formation channel, 9.2 (±0.4) × 10(-12) cm(3) molecule(-1) s(-1) (1 SD) at 760 torr of air, which lies toward the lower end of the previously established range. We demonstrate the impact of the revised value on photochemical model predictions of ozone concentrations in the Los Angeles airshed.
Author Institution: Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena CA 91125; Department of Chemistry, Purdue University, West Lafayette, IN, 47907; Department of Chemistry, The Ohio State University, Columbus, OH 43210
Abstract High-accuracy measurement of aerosol optical thickness (AOT) τ a with an elevation-scanning lidar is demonstrated and the results are compared with a collocated Cimel 318 sun photometer. Linear regression of the time-coincident data from a 2-week measurement campaign with the two instruments is found to be τ a lidar = (1.00 ± 0.17) τ a phot + (0.025 ± 0.019) (1σ). The method proved to have sufficient accuracy to measure AOTs of 0.1–0.2 commonly seen in relatively clear atmosphere. The measurement is absolute and thus does not depend on any external calibration standards.
{J. L. Fry, S. A. Nizkorodov, M. Okumura, C. M. Roehl, J. S. Francisco and P. O. Wennberg, J. Chem. Phys. {\bf 121{J. Matthews, A. Sinha and J. S. Francisco, J. Chem. Phys. {\bf 120
