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Difference spectroscopy, quantum yields in chloroplast reactions as function of wavelength, and analysis of oxygen evolving photoreaction in study of manganese function in photosynthesis
Large deuterium isotope effect on fluorescence emission spectra and quantum yields observed in number of chromospheres that contain proton donor groups
Attenuation length of excited photoelectrons in evaporated potassium bromide films by measuring quantum yield as function of film thickness
Manganese deficiency effect upon oxygen and quantum yields of photosynthesis and quinone photoreduction in Scenedesmus cells
Sulfur trioxide production in photolysis of sulfur dioxide at 1849 angstroms, noting oxygen addition effect on quantum yield
Carbon trioxide formation during ozone photolysis in liquid carbon dioxide and sulfur hexafluoride, noting ozone disappearance quantum yield independence of oxygen/ozone ratio
Sterically hindered aryldiazonium salts absorption spectra and quantum yield data interpretation, considering photochemical properties
Photoemission from evaporated gold films, measuring quantum yield, photoelectric energy distribution curves and optical density states
Acrolein photoisomerization in lower excited states, determining fluorescence and phosphorescence quantum yields
Pressure effects on quantum yields of carbon trioxide formation in gas phase ozone photolysis with carbon dioxide
Quantum yield of carbon dioxide photolysis at 1470 A concerning Mars and Venus atmospheres
The quantum yield for CO2 photodissociation at 25 C was found to be 1.08 + or - 0.12 for direct photolysis at 1849 A and between 200 and 800 torr; 0.48 + or - 0.02 for the Hg 6(1 P 1) sensitized decomposition between 130 and 730 torr; and 0.16 + or - 0.05 for the direct photolysis at 2139 A and between 300 and 600 torr. At these wavelengths, there was insufficient energy found to produce O(1 D). The primary process used is CO2 + hv yields CO + O(3 P).
The photochemistry of two diatomic and eight polyatomic molecules is discussed quantitatively. For an interstellar molecule, the lifetime against photodecomposition depends upon the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. The constant energy density of Habing is used for the unobserved regions of interstellar radiation field, and the field in obscuring clouds is estimated by combining the constant flux with the observed interstellar extinction curve covering the visible and ultraviolet regions. Lifetimes against photodecomposition in the unobscured regions and as a function of increasing optical thickness in obscuring clouds are calculated for the ten species. The results show that, except for CO, all the molecules have comparable lifetimes of less than one hundred years. Thus they can exist only in dense clouds and can never have been exposed to the unobscured radiation. The calculations further show that the lifetimes in clouds of moderate opacity are of the order of one million years.
A Kr resonance lamp was used in the investigations. All experiments were performed at 25 C and 0.2 torr of propyne. Between 5% and 25% of the propyne was decomposed in any one experiment. It was found that the addition of 25% C2D4 had no effect on the quantum yield of molecular hydrogen. This suggests that hydrogen formation in the photolysis of propyne at 1236 A occurs exclusively via a molecular process. Pressure effects on the distribution of isotopic hydrogen formed in the photolysis were also investigated.
Ozone was photolyzed at 25 C with steady illumination at several wavelengths from 2288 to 2850 A, at O3 pressures from 0.1 to 2.7 torr, and at absorbed intensities from 0.15 to 65 microns/min. Experiments were done in pure dry O3, and in the presence of He, CO2, N2, H2O, H2, N2O, He-CO2, He-H2O, CO2-H2O, O2-N2O, CO2-O2, and N2O5-O2-CO2 mixtures. The results show that in the absence of added gases or in the presence of He, the quantum yield of O3 consumption is 5.5 independent of conditions, except at pressures below 0.4 torr. In the presence of CO2 or N2, ozone consumption falls toward 4.0. The primary photolytic act produces O(1 D) and siglet O2, presumably O2(1 delta), at all wavelengths below 3000 A. Relative quenching constants O(1 D) removal by various gases were measured at 2288, 2537, and 2800 A. For O3, CO2, and N2, the relative rates are 1.0/0.4 to 0.5/0.08 to 0.11 at all wavelengths. For H2O the constant at 2537 A is 1.5 relative to that for O3. With N2O, a noticeable wavelength effect is observed and the relative rate constants are 1.5, 2 to 3, 4.0 for O3 compared to N2O at 2800, 2537, and 2288 A, respectively.
The photolysis of CH3ONO, alone and in the presence of NO, NO-N2 mixtures, and NO-CO mixtures was studied between 25 and 150 C. The major products are CH2O, N2O, and H2O. The quantum yields of N2O were measured. The N2O yield is large at low pressures but approaches a high-pressure limiting value of 0.055 at all temperatures as the excited CH3O produced in the primary step is stabilized by collision. In the presence of excess CO, and N2O yield drops, and CO2 is produced (though not in sufficient amounts to account for the drop in N2O). When pure CH2ONO is photolyzed, CO is produced and NO accumulates in the system. Both products are formed in related processes and result from CH3O attack on CH2O.
The reaction of O(3P) with 1-C4H8 was examined in the presence of CO which scavenges HO radicals to produce CO2. From the CO2 quantum yield, an upper limit to the efficiency of HO production in the reaction of O(3P) with 1-C4H8 was found to be 0.020 at both 298 and 473 K.
Relative quantum yields of O(D-1)production, phi, in ozone photolysis from 275 nm to 334 nm were determined in the gas phase at 233 K. The O(D-1) was monitored by means of its reaction with isobutane to form isobutyl alcohol. The light source was a high pressure mercury lamp combined with a monochromator, with a bandwidth of 1.6 nm. The results show a constant phi below 300 nm, which is taken as unity on the basis of previous work. There is a very sharp fall-off in phi which is centered at 308 nm. At 313 nm phi is not greater than 0.1.