Anomalous Intensities in the 2+1 REMPI Spectrum of the E 1Π-X 1Σ+ Transition of CO.

We report on one-color experiments near 214 nm involving the photodissociation of jet-cooled OCS to produce high rotational states (40 < J < 80) of CO (X 1Σ+, v = 0, 1) which were then ionized by 2+1 resonance-enhanced multiphoton ionization via the E 1Π state. The nominally forbidden Q-branch of the two-photon E 1Π-X 1Σ+ transition is observed with intensity comparable to the allowed R-branch. The bright character of the high- J Q-branch lines can be described quantitatively as intensity borrowing due to mixing of the E 1Π and C 1Σ+ states, using J-dependent mixing coefficients extrapolated from the observed Λ-doubling in the lower rotational levels of the E state. In addition to the significant enhancement of Q-branch intensities above the values predicted by conventional two-photon line strengths for a 1Π-1Σ+ transition, the high- J lines of the R- and P-branches appear to be suppressed in intensity by approximately a factor of 3 compared to the unperturbed low- J line strengths, most likely due to perturbations associated with a 1Σ- state. The E-state rotational term values for J < 80, v = 0 derived from the present spectra agree within our measurement and calibration uncertainties with the extrapolations based on the molecular constants previously derived from rotational levels with J < 50. The E-X transition is attractive for future application to photodissociation dynamics and rotational polarization measurements of CO photofragments, with convenient access to state-selective probing on multiple rotational branches, which exhibit different sensitivity to fragment alignment.

Low-temperature collisional quenching of NO A(2)Σ(+)(v' = 0) by NO(X(2)Π) and O2 between 34 and 109 K.

We present measurements of collisional fluorescence quenching cross sections of NO(A(2)Σ(+), v' = 0) by NO(X(2)Π) and O2 between 34 and 109 K using a pulsed converging-diverging nozzle gas expansion, extending the temperature range of previous measurements. The thermally averaged fluorescence quenching cross sections for both species show a monotonic increase as temperature decreases in this temperature range, consistent with earlier observations. These new measurements, however, allow discrimination between predictions obtained by extrapolating fits of previous data using different functional forms that show discrepancies exceeding 120% for NO and 160% for O2 at 34 K. The measured self-quenching cross section is 52.9 Å(2) near 112 K and increases to 64.1 Å(2) at 35 K, whereas the O2 fluorescence quenching cross section is 42.9 Å(2) at 109 K and increases to 58.3 Å(2) at 34 K. Global fits of the quenching cross section temperature dependence show that, when including our current measurements, the low temperature behavior of the quenching cross sections for NO and O2 is better described by a parameterization that accounts for the long-range interactions leading to the collisional deactivation via an inverse power law model.

A method to analyze molecular tagging velocimetry data using the Hough transform.

The development of a method to analyze molecular tagging velocimetry data based on the Hough transform is presented. This method, based on line fitting, parameterizes the grid lines "written" into a flowfield. Initial proof-of-principle illustration of this method was performed to obtain two-component velocity measurements in the wake of a cylinder in a Mach 4.6 flow, using a data set derived from computational fluid dynamics simulations. The Hough transform is attractive for molecular tagging velocimetry applications since it is capable of discriminating spurious features that can have a biasing effect in the fitting process. Assessment of the precision and accuracy of the method were also performed to show the dependence on analysis window size and signal-to-noise levels. The accuracy of this Hough transform-based method to quantify intersection displacements was determined to be comparable to cross-correlation methods. The employed line parameterization avoids the assumption of linearity in the vicinity of each intersection, which is important in the limit of drastic grid deformations resulting from large velocity gradients common in high-speed flow applications. This Hough transform method has the potential to enable the direct and spatially accurate measurement of local vorticity, which is important in applications involving turbulent flowfields. Finally, two-component velocity determinations using the Hough transform from experimentally obtained images are presented, demonstrating the feasibility of the proposed analysis method.

Transient laser frequency modulation spectroscopy.

Explicitly time-dependent implementations of optical frequency modulation spectroscopy have been recently applied to a wide range of problems in chemical physics. We provide a brief description of the methodology, with an emphasis on its intrinsic advantages for interrogating transient species. Several examples highlight the application of the technique to high-resolution absorption spectra of free radicals, rate measurements for gas-phase reactions, and Doppler spectroscopy of the gas-phase products of photoinitiated reactions.