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.

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The ethoxy radical is an important species in combustion chemistry; however, considerable debate regarding the fragmentation pathways exists. In order to examine the stability and dissociation dynamics of the ethoxy radical in the two lowest electronic states, dissociative photodetachment experiments at 3.20 eV were carried out on the ethoxide anion, CH3CH2O(-), and its per-deuterated isotopologue. Production of excited radicals by photodetachment of the alkoxide anion was found to lead to only CH3 + H2CO products, with no indication of the energetically allowed H-loss channel, H + CH3CHO. Ab initio calculations for the anionic and neutral surfaces, including relevant isomerization and dissociation barriers, were carried out using the CBS-QB3 method to aid in interpretation of the data. The energetics observed in the photoelectron-photofragment coincidence spectra indicate that the calculated barrier (0.70 eV) for the process CH3CH2O → CH3 + H2CO and the stability of the CH3CH2O radical relative to those products are upper limits.

Earlier synchrotron photoionization mass spectrometry experiments suggested a prominent ring-opening channel in the OH-initiated oxidation of cyclohexene, based on comparison of product photoionization spectra with calculated spectra of possible isomers. The present work re-examines the OH + cyclohexene reaction, measuring the isomeric products of OH-initiated oxidation of partially and fully deuterated cyclohexene. In particular, the directly measured photoionization spectrum of 2-cyclohexen-1-ol differs substantially from the previously calculated Franck-Condon envelope, and the product spectrum can be fit with no contribution from ring-opening. Measurements of H(2)O(2) photolysis in the presence of C(6)D(10) establish that the addition-elimination product incorporates the hydrogen atom from the hydroxyl radical reactant and loses a hydrogen (a D atom in this case) from the ring. Investigation of OH + cyclohexene-4,4,5,5-d(4) confirms this result and allows mass discrimination of different abstraction pathways. Products of 2-hydroxycyclohexyl-d(10) reaction with O(2) are observed upon adding a large excess of O(2) to the OH + C(6)D(10) system.

The F + HOCH → HF + OCH reaction is a system with 15 internal degrees of freedom that can provide a benchmark for the development of theory for increasingly complex chemical reactions. The dynamics of this reaction were studied by photoelectron-photofragment coincidence (PPC) spectroscopy carried out on the F(HOCH) anion, aided by a computational study of both the anion and neutral potential energy surfaces, with energies extrapolated to the CCSDT(Q)/CBS level of theory. Photodetachment at 4.80 eV accesses both the reactant and product channels for this reaction. In the product channel (HF + OCH + e) of the neutral potential energy surface, vibrationally excited HF products in addition to the stable product-channel hydrogen-bonded complex (FH-OCH) are observed in the PPC and photoelectron spectra. In addition, experimental evidence is observed for the reactant-channel van der Waals complex (F-HOCH), in good agreement with the theoretical predictions. The relative stability of these long-lived complexes was probed by reducing the ion beam energy, increasing the product time-of-flight, indicating lifetimes on the microsecond timescale for the reactant- and product-channel complexes as well as providing evidence for long-lived vibrational Feshbach resonances associated with the HF(v > 0) + OCH product states. This system will provide a model for extending full-dimensionality quantum dynamics to larger numbers of degrees of freedom.