title: Energetics and transition-state dynamics of the F + HOCH3→ HF + OCH3reaction.
abstract: The F + HOCH3→ HF + OCH3reaction 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-(HOCH3) 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 + OCH3+ e-) of the neutral potential energy surface, vibrationally excited HF products in addition to the stable product-channel hydrogen-bonded complex (FH-OCH3) are observed in the PPC and photoelectron spectra. In addition, experimental evidence is observed for the reactant-channel van der Waals complex (F-HOCH3), 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) + OCH3product states. This system will provide a model for extending full-dimensionality quantum dynamics to larger numbers of degrees of freedom.
authors: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0340, USA. rcontinetti@ucsd.edu.
authors: Amelia W
authors: AW
authors: Ray
authors: Center for Computational Quantum Chemistry, Department of Chemistry, University of Georgia, Athens, GA 30602, USA.
authors: Jay
authors: J
authors: Agarwal
authors: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0340, USA. rcontinetti@ucsd.edu.
authors: Ben B
authors: BB
authors: Shen
authors: Center for Computational Quantum Chemistry, Department of Chemistry, University of Georgia, Athens, GA 30602, USA.
authors: H F
authors: HF
authors: Schaefer
authors: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0340, USA. rcontinetti@ucsd.edu.
authors: Robert E
authors: http://orcid.org/0000-0002-0685-4459
authors: RE
authors: Continetti