The study of gas-phase reaction dynamics has advanced to a point where four-atom reactions are the proving ground for detailed comparisons between experiment and theory. Here, a combined experimental and theoretical study of the dissociation dynamics of the tetra-atomic FH2O system is presented, providing snapshots of the F + H2O → HF + OH reaction. Photoelectron-photofragment coincidence measurements of the dissociative photodetachment (DPD) of the F(-)(H2O) anion revealed various dissociation pathways along different electronic states. A distinct photoelectron spectrum of stable FH-OH complexes was also measured and attributed to long-lived Feshbach resonances. Comparison to full-dimensional quantum calculations confirms the sensitivity of the DPD measurements to the subtle dynamics on the low-lying FH2O potential energy surfaces over a wide range of nuclear configurations and energies.

The electronic spectrum of Ni⁺(H₂O) has been measured from 16200 to 18000 cm⁻¹ using photofragment spectroscopy. Transitions to two excited electronic states are observed; they are sufficiently long-lived that the spectrum is vibrationally and partially rotationally resolved. An extended progression in the metal-ligand stretch is observed, and the absolute vibrational quantum numbering is assigned by comparing isotopic shifts between ⁵⁸Ni⁺(H₂O) and ⁶⁰Ni⁺(H₂O). Time-dependent density functional calculations aid in assigning the spectrum. Two electronic transitions are observed, from the ²A₁ ground state (which correlates to the ²D, 3d⁹ ground state of Ni⁺) to the 3²A₁ and 2²A₂ excited states. These states are nearly degenerate and correlate to the ²F, 3d⁸4s excited state of Ni⁺. Both transitions are quite weak, but surprisingly, the transition to the ²A₂ state is stronger, although it is symmetry-forbidden. The 3d⁸4s states of Ni⁺ interact less strongly with water than does the ground state; therefore, the excited states observed are less tightly bound and have a longer metal-ligand bond than the ground state. Calculations at the CCSD(T)/aug-cc-pVTZ level predict that binding to Ni⁺ increases the H-O-H angle in water from 104.2 to 107.5° as the metal removes electron density from the oxygen lone pairs. The photodissociation spectrum shows well-resolved rotational structure due to rotation about the Ni-O axis. This permits determination of the spin rotation constants ε(αα)'' = -12 cm⁻¹ and ε(αα)' = -3 cm⁻¹ and the excited state rotational constant A' = 14.5 cm⁻¹. This implies a H-O-H angle of 104 ± 1° in the 2²A₂ excited state. The O-H stretching frequencies of the ground state of Ni⁺(H₂O) were measured by combining IR excitation with visible photodissociation in a double resonance experiment. The O-H symmetric stretch is ν₁'' = 3616.5 cm⁻¹; the antisymmetric stretch is ν₅'' = 3688 cm⁻¹. These values are 40 and 68 cm⁻¹ lower, respectively, than those in bare H₂O.

At room temperature, cobalt oxide cations directly convert methane to methanol with high selectivity but very low efficiency. Two potential intermediates of this reaction, the [HO-Co-CH(3)](+) insertion intermediate and [H(2)O-Co=CH(2)](+) aquo-carbene complex are produced in a laser ablation source and characterized by electronic and vibrational spectroscopy. Reaction of laser-ablated cobalt cations with different organic precursors seeded in a carrier gas produces the intermediates, which subsequently expand into vacuum and cool. Ions are extracted into a time-of-flight mass spectrometer and spectra are measured via photofragment spectroscopy. Photodissociation of [HO-Co-CH(3)](+) in the visible and via infrared multiple photon dissociation (IRMPD) makes only Co(+) + CH(3)OH, while photodissociation of [H(2)O-Co=CH(2)](+) produces CoCH(2)(+) + H(2)O. The electronic spectrum of [HO-Co-CH(3)](+) shows progressions in the excited state Co-C stretch (335 cm(-1)) and O-Co-C bend (90 cm(-1)); the IRMPD spectrum gives ν(OH) = 3630 cm(-1). The [HO-Co-CH(3)](+)(Ar) complex has been synthesized and its vibrational spectrum measured in the O-H stretching region. The resulting spectrum is sharper than that obtained via IRMPD and gives ν(OH) = 3642 cm(-1). Also, an improved potential energy surface for the reaction of CoO(+) with methane has been developed using single point energies calculated by the CBS-QB3 method for reactants, intermediates, transition states and products.

Background: Optical access to a travelling ion packet is required in many ion beam experiments that study ion-photon interactions. Methods: An approach is described for carrying out direct infrared excitation of a fast ion beam that uses an optical-quality reflective beam blocker to illuminate a counter propagating pulsed ion beam in a collinear configuration. This arrangement provides optical access along the axis of ion beam propagation by placing a mirror in the beam path at a 25 degree angle. The ion packet is bumped over the mirror, which is also used to block fast neutral particles produced during ion beam acceleration that also propagate along the beam path. Results: The efficiency of this setup is demonstrated in a photodetachment experiment on NO − anions, where a photoinduced depletion of up to 90% of the beam is achieved in a single laser shot. To demonstrate the application of this configuration, the relative photodetachment cross section for NO − has been measured in the range of 2800-7200 cm-1. The measured relative cross section shows a set of sharp peaks that are identified as vibrational autodetachment resonances. Conclusion: The new setup paves the way for future experiments where parent anionic species are vibrationally excited via direct infrared excitation first and undergo photodetachment/photodissociation in a subsequent step.