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Pimentel, G. C.

Publications and source records attributed to Pimentel, G. C..

Reaction between nitric oxide and ozone in solid nitrogen

Nitrogen dioxide, NO2, is produced when nitric oxide, NO, and ozone, O3, are suspended in a nitrogen matrix at 11-20 K. The NO2 is formed with first-order kinetics, a 12 K rate constant of (1.4 + or - 0.2) x 0.00001/sec, and an apparent activation energy of 106 + or - 10 cal/mol. Isotopic labeling, variation of concentrations, and cold shield experiments show that the growth of NO2 is due to reaction between ozone molecules and NO monomers, and that the reaction is neither infrared-induced nor does it seem to be a heavy atom tunneling process. Reaction is attributed to nearest-neighbor NO.O3 pairs probably held in a specific orientational relationship that affects the kinetic behavior. When the temperature is raised, more such reactive pairs are generated, presumably by local diffusion. Possible mechanisms are discussed.

Lucas, D.

Chemiluminescent reactions of sulfur /3P2/ atoms in cryogenic matrices - S + O2 yields SO2 /a3 B1/

Results are reported for thermoluminescence studies of reactions of sulfur atoms in cryogenically deposited solid argon through in situ photolysis of OCS. Analysis of the thermoluminescence spectrum that resulted from photolysis and heating of matrices in which O2 was codeposited with an OCS/Ar mixture shows that the emitter contained oxygen derived from the added O2 and that little SO2 accumulated during photolysis. The observed absence of thermoluminescence or fluorescence in either of the allowed transitions of excited SO2 is taken as definitive evidence that ground-state sulfur atoms can insert into the oxygen molecule with effectively zero activation energy.

Long, S. R.

Argon hydrochloride, Ar.HCl, bond energy by infrared spectroscopy

The infrared absorption of argon (200 to 760 torr) and hydrogen chloride (2 to 6 torr) mixtures is reexamined in the missing Q branch region (spectral region between 2860 and 3010 wavelength/cm) at temperatures ranging from 195 to 298 K. The temperature dependence of two absorption features of the argon hydrogen chloride complex, at 2887 and 2879 wavelength/cm, leads to a bond energy estimate that depends on the assumptions made about the internal degrees of freedom of the complex. It is shown that agreement with experiment can be reached for well depths near 1.2 kcal/mole. This result is relatively insensitive to the choice of the vibrational frequencies and anharmonicities, but does depend on the extent to which the energy level manifolds are truncated to avoid molecular excitation in excess of the bond energy. The bond energy is found to deviate from the commonly accepted value of 0.4 kcal/mole. Possible causes for the discrepancy are considered.

Miziolek, A. W.

Evidence about hydrate and solid water in the Martian surface from the 1969 Mariner infrared spectrometer

Results of laboratory simulation studies and comparative computer analyses of infrared spectral data regarding the presence, distribution, and form of condensed-phase water in the Martian surface. The data were obtained with the aid of the Mariner 6 and 7 spacecraft which were equipped with infrared spectrometers recording the infrared spectrum from 1.9 to 14.4 microns. From the analysis of these data evidence is obtained which signifies some sort of compositional and/or particle size variability of the extent and nature of hydration. Changes are noted which could be due to ice thinly covering a small fraction of the planetary surface in particularly cold spots, possibly on partially shaded slopes. At southerly latitudes, the fraction so covered seems to increase as the polar cap edge is approached. It is therefore concluded that there is strong evidence of ice formation on the planetary surface at the edge of the polar cap.

Pimentel, G. C.

The composition of the Martian atmosphere - Minor constituents.

The Mariner 6 and 7 infrared spectrometers provided data which, in principle, determine upper limits on the possible atmospheric abundance of every gaseous substance that was undetected but which has recognized absorptions in the accessible spectral region, 1.9 to 14.4 microns. Through supporting laboratory determinations of curves of growth under pressure-broadening conditions appropriate to Mars, upper limits can be specified (expressed first in cm-atm, STP, for a vertical column and then in parts per million) for NO2, NH3, C3O2, SO2, OCS, NO, O3, CH4, N2O, HCL, HBr, and H2S. In addition, considerations of band contours, moments of inertia, and experimental absorption coefficients make it possible to place useful upper limits on 27 additional substances that were not detected and for which curves of growth have not been measured.

Horn, D.

Infrared spectroscopy

Infrared spectroscopic measurements on Mars atmosphere by Mariners 6 and 7

Herr, K. C.