State-resolved dynamics of the CN(B2Sigma+) and CH(A2Delta) excited products resulting from the VUV photodissociation of CH3CN.

Fourier transform visible spectroscopy, in conjunction with VUV photons produced by a synchrotron, is employed to investigate the photodissociation of CH3CN. Emission is observed from both the CN(B2Sigma+-X2Sigma+) and CH(A2Delta-X2Pi) transitions; only the former is observed in spectra recorded at 10.2 and 11.5 eV, whereas both are detected in the 16 eV spectrum. The rotational and vibrational temperatures of both the CN(B2Sigma+) and CH(A2Delta) radical products are derived using a combination of spectral simulations and Boltzmann plots. The CN(B2Sigma+) fragment displays a bimodal rotational distribution in all cases. Trot(CN(B2Sigma+)) ranges from 375 to 600 K at lower K' and from 1840 to 7700 K at higher K' depending on the photon energy used. Surprisal analyses indicate clear bimodal rotational distributions, suggesting CN(B2Sigma+) is formed via either linear or bent transition states, respectively, depending on the extent of rotational excitation in this fragment. CH(A2Delta) has a single rotational distribution when produced at 16 eV, which results in Trot(CH(A2Delta))=4895+/-140 K in v'=0 and 2590+/-110 K in v'=1. From thermodynamic calculations, it is evident that CH(A2Delta) is produced along with CN(X2Sigma+)+H2. These products can be formed by a two step mechanism (via excited CH3* and ground state CN(X2Sigma+)) or a process similar to the "roaming" atom mechanism; the data obtained here are insufficient to definitively conclude whether either pathway occurs. A comparison of the CH(A2Delta) and CN(B2Sigma+) rotational distributions produced by 16 eV photons allows the ratio between the two excited fragments at this energy to be determined. An expression that considers the rovibrational populations of both band systems results in a CH(A2Delta):CN(B2Sigma+) ratio of (1.2+/-0.1):1 at 16 eV, thereby indicating that production of CH(A2Delta) is significant at 16 eV.

Dynamics of the CH(A2Delta) product from the reaction of C2H with O2 studied by Fourier transform visible spectroscopy.

The reaction C(2)H + O(2) --> CH(A(2)Delta) + CO(2) is investigated using Fourier transform visible emission spectroscopy. C(2)H radicals, produced by 193 nm photolysis of C(2)H(2), react with O(2) molecules at low total pressures to produce electronically excited CH(A(2)Delta). Observation of the CH(A(2)Delta-X(2)Pi) electronic emission to infer nascent rotational and vibrational CH(A(2)Delta) distributions provides information about energy partitioning in the CH(A(2)Delta) fragment during the reaction. The rotational and vibrational populations of the CH(A(2)Delta) product are determined by fitting the rotationally resolved experimental spectra with simulated spectra. The CH(A(2)Delta) product is found to be rotationally and vibrationally excited with T(rot) congruent with 1150 K and T(vib) congruent with 1900 K. The mechanism for this reaction proceeds through one of two five-atom intermediates and requires a crossing between electronic potential surfaces. The rotational excitation suggests a bent geometry for the final intermediate of this reaction before dissociation to products, and the vibrational excitation involves an elongation of the C-H bond from the compressed transition state to the final CH(A) state.

Light scattering of ultrafine silica particles by VUV synchrotron radiation.

Vacuum ultraviolet (VUV) light scattering from ultrafine silica particles is studied with an aerosol instrument recently established at the Advanced Light Source (ALS) in Berkeley. Silica particles, size-selected by a differential mobility analyzer, are introduced into vacuum through a set of aerodynamic lenses to form a particle beam. The scattered photons from the crossing area of the VUV synchrotron beam and particle beam are detected with a rotatable VUV photon detector. The angular distributions of scattered photons (ADSP) originating from 70, 100, 200 nm diameter silica particles are measured with 145.9 and 118.1 nm synchrotron radiation. These angular distributions show strong forward scattering. The measured ADSPs are consistent with simulation of Mie scattering. The refractive indices of silica particles, 2.6 + 1.1i and 1.6 + 0.0001i for 118.1 and 145.9 nm, respectively, are obtained by fitting the measured ADSPs; the least average percentage deviations are 18% and 6%, respectively. The scattered fluxes at widely different wavelengths (visible versus VUV) also exhibit clear size sensitivity. Under comparable experimental conditions of photon fluxes and detection efficiencies, limits of particle size detection of 70 and 250 nm are obtained, respectively, when using 118.1 and 532 nm illumination. As anticipated, VUV scattering is a more sensitive probe for ultrafine particles, which will find application in detection of these ubiquitous species beyond the confines of a laboratory.