Photochemistry of interstellar molecules

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

Role of the methylene amidogen (H2CN) radical in the atmospheres of Titan and Jupiter

The methylene amidogen (H2CN) radical can be shown to be an important intermediate in models for the formation of HCN (via N + CH3) and the recombination of H to H2 (via H + HCN) on Titan as well as in models for the formation of HCN (via NH2 + C2H3) in the atmosphere of Jupiter. Experiments in our laboratory in a discharge flow system with mass spectrometric detection of both reactants and products have established that the major product channel (90 percent for the reaction N + CH3 is that leading to H2CN + H. The same result was obtained for N + CD3 yields D2CN + D. The rate constant for the reaction D + D2CN yields DCN + D2 was measured for the first time and k(298 K) greater than 7 x 10(exp -11) cu cm/s was found. The same result was obtained for the H atom reaction. This is the final step in the reaction sequence leading to HCN on both Titan and Jupiter and to formation of H2 from H on Titan. The first measurement of the ionization potentials for H2CN and D2CN was also made. From electron impact studies I.P. = (9.6 + or - 1.0) eV was obtained for both radicals. An upperlimit of I.P. less than 11.6 eV came from observations of the H2CN radical by photoionization mass spectrometry using an Ar resonance lamp (106.7 nm). Further photoionization experiments are planned using synchrotron radiation plus monochromator as a tunable vacuum UV light source

Absolute rate parameters for the reaction of ground state atomic oxygen with carbonyl sulfide

The rate parameters for the reaction of O(3P) with carbonyl sulfide, O(3P) + OCS yields CO + SO have been determined directly by monitoring O(3P) using the flash photolysis-resonance fluorescence technique. The value for k sub 1 was measured over a temperature range of 263 - 502 K and the data were fitted to an Arrhenuis expression with good linearity

Absolute rate of the reaction of hydrogen atoms with ozone from 219-360 K

Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence technique. The results can be expressed in Arrhenius form by K = (1.33 plus or minus 0.32)x10 to the minus 10 power exp (-449 plus or minus 58/T) cu cm/molecule/s (two standard deviations). The present work is compared to two previous determinations and is discussed theoretically

Absolute rate of the reaction of bromine atoms with ozone from 200-360 K

The rate constant for the reaction Br + O3 yields BrO + O2 was measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at lambda 165nm.O3 was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3, total pressure and limited variations in flash intensity. The measured rate constants obeyed the Arrhenius expression, where the error quoted is two standard deviations. Results are compared with previous determinations which employed the discharge flow-mass spectrometric technique

Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

Absolute rate constants for the reaction OH ? H2CO measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique are given. The results are independent of variations in H2CO concentration, total pressure Ar concentration, and flash intensity (i.e., initial OH concentration). The rate constant is found to be invariant with temperature in this range, the best representation being k sub 1 = (1.05 ? or - 0.11) x 10 to the 11th power cu cm molecule(-1) s(-1) where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k sub 1. The reaction is also discussed from a theoretical point of view

The reaction NH2 + PH3 yields NH3 + PH2: Absolute rate constant measurement and implication for NH3 and PH3 photochemistry in the atmosphere of Jupiter

The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH2 photons is measured by multiscaling techniques. For each of the five temperatures employed in the study, the results are shown to be independent of variations in PH3 concentration, total pressure (argon), and flash intensity. It is found that the rate constant results are best represented for T between 218 and 456 K by the expression k = (1.52 + or - 0.16) x 10 to the -12th exp(-928 + or - 56/T) cu cm per molecule per sec; the error quoted is 1 standard deviation. This is the first determination of the rate constant for the reaction NH2 + PH3. The data are compared with an estimate made in order to explain results of the radiolysis of NH3-PH3 mixtures. The Arrhenius parameters determined here for NH2 + PH3 are then constrasted with those for the corresponding reactions of H and OH with PH3

Upper atmosphere research: Reaction rate and optical measurements

The objective is to provide photochemical, kinetic, and spectroscopic information necessary for photochemical models of the Earth's upper atmosphere and to examine reactions or reactants not presently in the models to either confirm the correctness of their exclusion or provide evidence to justify future inclusion in the models. New initiatives are being taken in technique development (many of them laser based) and in the application of established techniques to address gaps in the photochemical/kinetic data base, as well as to provide increasingly reliable information

Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K

Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant

Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K

Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment