Production of NO2 from Photolysis of Peroxyacetyl Nitrate

Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248 nm, and the NO2 photoproduct was detected by laser-induced fluorescence. The quantum yield for the production of NO2 from PAN photolysis was determined by comparison to HNO3 photolysis data taken under identical experimental conditions. The average of data collected over a range of total pressures, precursor concentrations, and buffer gases was 0.83 +/- 0.09 for the NO2 quantum yield, where the statistical uncertainty is 2 standard deviations

A Bright, Slow Cryogenic Molecular Beam Source for Free Radicals

We demonstrate and characterize a cryogenic buffer gas-cooled molecular beam source capable of producing bright beams of free radicals and refractory species. Details of the beam properties (brightness, forward velocity distribution, transverse velocity spread, rotational and vibrational temperatures) are measured under varying conditions for the molecular species SrF. Under typical conditions we produce a beam of brightness 1.2 x 10^11 molecules/sr/pulse in the rovibrational ground state, with 140 m/s forward velocity and a rotational temperature of approximately 1 K. This source compares favorably to other methods for producing beams of free radicals and refractory species for many types of experiments. We provide details of construction that may be helpful for others attempting to use this method.Comment: 15 pages, 14 figure

Characterization of ion-molecule reactions and rotational relaxation in a free jet expansion.

Our group has recently developed and characterized a novel free jet flow reactor in which molecular reaction dynamics are studied in the c::old c::ore of a pulsed free jet expansion. Extremely low translational temperatures, often less than 1 K, are obtained with no condensation problems that exist in cryogenic cooling techniques. The reaction is initiated in the expansion and the species are monitored in the frame of the flowing free jet as a function of time. Kinetic information is obtained from a temporal profile of the mass and density distributions in the expansion. A free jet expansion is not at thermal equilibrium. The consequence of thermal anisotropy between different degrees of freedom must be addressed when properly analyzing free jet kinetic data. A detailed kinetic treatment has been developed which, within the accurate flow model of the jet adopted, rigorously accounts for the thermal anisotropy in the expansion. Approximations to the convoluted exact expressions are then made to aid in experimental application. Astrophysica1ly important bimolecular reactions of C⁺ were measured. The rate coefficients are reported and compared to current capture models. For the reactions with only two exothermic channels. branching ratios are determined. To understand the realistic flow dynamics present in our free jet flow reactor a solution to the Boltzmann Equation for a multi-component atomic expansion was derived. Both velocity and temperature slip are naturally incorporated into the model. To better understand the internal cooling in molecular expansions. rotational state population distributions were obtained in the core of a free jet for both pure and mixed mixtures of N₂ by means of 2+2 REMPI. Spectral fitting shows no evidence for non-Boltzmann behaviour in the rotational populations. The experimental results fit well to a solution of the generalized Boltzmann equation

NO_2 Quantum Yield from the 248 nm Photodissociation of Peroxynitric Acid (HO_2NO_2)

Peroxynitric acid (PNA) was photolyzed at 248 nm, and the NO_2 photoproduct was detected by laser-induced fluorescence (LIF). The quantum yield for the production of NO_2 was determined by comparison with HNO_3 photolysis data taken under identical experimental conditions. Measurements made over a range of pressures, flows, and precursor concentrations resulted in an NO_2 quantum yield of 0.56 ± 0.17, where the statistical uncertainty is 2 standard deviations. Calculations of potential energy curves for several low-lying singlet and triplet states of PNA are presented. The calculations show that while the singlet excitations occur via an n−π* transition on the NO_2 moiety, the dissociative channels forming OH + NO_3 and HO_2 + NO_2 likely occur via predissocation on different surfaces. Excitation energies at the MRCI and CCSD(T) level of theory show that excited states of PNA are not accessible at wavelengths longer than 407 nm (∼3.0 eV)