Luminescence Measurements of the Hyperthermal Reactions of N/N + NH.

Chemiluminescence from a system of collisions, N/N/Kr/Kr/Xe/Xe + NH, at collision energies between 10 and 170 eV (center of mass, COM), was measured in the spectral range 300-1000 nm. The energy dependence of the emission excitation cross sections was quantified, and molecular signatures were fit to known spectroscopic constants to determine vibrational-state populations. For both N and N collision species, the strongest features were assigned to emissions from NH (A-X) and the atomic hydrogen Balmer series.

Luminescence measurements of hyperthermal Xe + O and O + Xe collision systems.

Emission excitation cross sections are recorded for collisions between Xe + O and O + Xe over a collision energy range of approximately 2 to 900 eV in the center-of-mass (E) frame. Emissive products of the O + Xe reaction are examined in the 700-1000 nm optical range and include neutral atomic oxygen emissions and neutral xenon emissions. Atomic emission products of the O + Xe collision appear to have measureable cross sections near E = 14 eV and increase in intensity until about E = 60 eV where they remain approximately constant for the remainder of the measured collision energies.

Integral cross section measurements and product recoil velocity distributions of Xe(2+) + N2 hyperthermal charge-transfer collisions.

Charge exchange from doubly charged rare gas cations to simple diatomics proceeds with a large cross section and results in populations of many vibrational and electronic product states. The charge exchange between Xe(2+) and N2, in particular, is known to create N2 (+) in both the A and B electronic states. In this work, we present integral charge exchange cross section measurements of the Xe(2+) + N2 reaction as well as axial recoil velocity distributions of the Xe(+) and N2 (+) product ions for collision energies between 0.

Doppler-Resolved Kinetics of Saturation Recovery.

Frequency-modulated laser transient absorption has been used to monitor the ground-state rotational energy-transfer rates of CN radicals in a double-resonance, depletion recovery experiment. When a pulsed laser is used to burn a hole in the equilibrium ground-state population of one rotational state without velocity selection, the population recovery rate is found to depend strongly on the Doppler detuning of a narrow-band probe laser. Similar effects should be apparent for any relaxation rate process that competes effectively with velocity randomization.

A guided-ion beam study of the collisions and reactions of I(+) and I2 (+) with I2.

Growing interest in developing and testing iodine Hall effect thrusters requires measurements of the cross sections of reactions that generate low energy plasma following discharge. Limited experimental and theoretical work necessitates a decisive experiment to elucidate the charge exchange and collision-induced dissociation channels. To this end, we have used guided-ion beam techniques to measure cross sections for both I(+) + I2 and I2 (+)+I2 collisions.

Roaming-mediated isomerization in the photodissociation of nitrobenzene.

Roaming reactions comprise a new class of reaction in which a molecule undergoes frustrated dissociation to radicals, followed by an intramolecular abstraction reaction. Nitro compounds have long been known to dissociate to give NO as a major product. However, rates based upon isomerization via calculated tight transition states are implausibly slow, so the key dissociation pathway for this important class of molecules remains obscure.

The photodissociation dynamics of tetrachloroethylene.

We present a direct current slice imaging study of tetrachloroethylene (C(2)Cl(4)) photodissociation, probing the resulting ground state Cl ((2)P(3/2)) and spin-orbit excited state Cl* ((2)P(1/2)) products. We report photofragment images, total translational energy distributions and the product branching ratio of Cl*/Cl following dissociation at 235 and 202 nm, obtained using a two-color reduced-Doppler dissociation/probe. Near 235 nm, the Cl translational energy distribution shows a peak at the limit of the available energy, indicating a direct dissociation through a σ*(C-Cl) ← π (C=C) transition, which is superimposed on a broader underlying distribution.

Sub-Doppler stark spectroscopy in the A-X (1,0) band of CN.

The effect of external electric fields has been measured in hyperfine-resolved sub-Doppler transitions in the A (2)Pi-X (2)Sigma (1,0) band of the CN radical near 10,900 cm(-1). Static electric fields less than 1 kV/cm are sufficient to mix the most closely spaced Lambda-dpublets in the A state, leading to Stark spectra with both new and shifted resonances. Simulations of the saturation-dip Stark spectral line profiles allow extraction of the A-state permanent electric dipole moment with a magnitude of 0.

Dynamics at conical intersections: the influence of O-H stretching vibrations on the photodissociation of phenol.

Comparing the recoil energy distributions of the fragments from one-photon dissociation of phenol-d(5) with those from vibrationally mediated photodissociation shows that initial vibrational excitation strongly influences the disposal of energy into relative translation. The measurements use velocity map ion imaging to detect the H-atom fragments and determine the distribution of recoil energies. Dissociation of phenol-d(5) molecules with an initially excited O-H stretching vibration produces significantly more fragments with low recoil energies than does one-photon dissociation at the same total energy.

Vibrational action spectroscopy of the C-H and C-D stretches in partially deuterated formic acid dimer.

Vibrational action spectroscopy of jet-cooled formic acid dimer measures the frequency of the C-H(D) stretching vibration and its coupling to nearby states. The action spectrum of (DCOOH)2 reveals a specific Fermi resonance between the C-D stretch and two antisymmetric combination states formed from the C-O stretch and DCO bend. A three-state deperturbation analysis shows that there is a relatively strong coupling between the fundamental vibration and each of the combination vibrations (mid R:13 cm(-1)mid R:) as well as between the combination states themselves (mid R:7 cm(-1)mid R:).

Vibrationally mediated photodissociation of ammonia: the influence of N-H stretching vibrations on passage through conical intersections.

Velocity map ion imaging of the H atoms formed in the photodissociation of vibrationally excited ammonia molecules measures the extent of adiabatic and nonadiabatic dissociation for different vibrations in the electronically excited state. Decomposition of molecules with an excited symmetric N-H stretch produces primarily ground state NH(2) along with a H atom. The kinetic energy release distribution is qualitatively similar to the ones from dissociation of ammonia excited to the electronic origin or to several different levels of the bending vibration and umbrella vibration.