The photoionization of methoxymethanol: Fingerprinting a reactive C2 oxygenate in a complex reactive mixture

Hansen, Niko A.; Price, Trevor D.; Filardi, Leah R.; Gurses, Sadi M.; Zhou, Wenqi; Hansen, Nils; Osborn, David L.; Zádor, Judit; Kronawitter, Coleman X.

doi:10.1063/5.0197827

The photoionization of methoxymethanol: Fingerprinting a reactive C₂ oxygenate in a complex reactive mixture

Journal Article · Mon Mar 25 00:00:00 EDT 2024 · The Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0197827· OSTI ID:2589536

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Univ. of California, Davis, CA (United States)
Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Methoxymethanol (CH₃OCH₂OH) is a reactive C₂ ether-alcohol that is formed by coupling events in both heterogeneous and homogeneous systems. It is found in complex reactive environments—for example those associated with catalytic reactors, combustion systems, and liquid-phase mixtures of oxygenates. Using tunable synchrotron-generated vacuum-ultraviolet photons between 10.0 and 11.5 eV, we report on the photoionization spectroscopy of methoxymethanol. We determine that the lowest-energy photoionization process is the dissociative ionization of methoxymethanol via H-atom loss to produce [C₂H₅O₂]⁺, a fragment cation with a mass-to-charge ratio (m/z) = 61.029. Here, we measure the appearance energy of this fragment ion to be 10.24 ± 0.05 eV. The parent cation is not detected in the energy range examined. To elucidate the origin of the m/z = 61.029 (C₂H₅O₂) fragment, we used automated electronic structure calculations to identify key stationary points on the cation potential energy surface and compute conformer-specific microcanonical rate coefficients for the important unimolecular processes. The calculated H-atom dissociation pathway results in a [C₂H₅O₂]⁺ fragment appearance at 10.21 eV, in excellent agreement with experimental results.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: SC0020320; NA0003525; AC02-05CH11231

OSTI ID:: 2589536

Journal Information:: The Journal of Chemical Physics, Journal Name: The Journal of Chemical Physics Journal Issue: 12 Vol. 160; ISSN 1089-7690; ISSN 0021-9606

Publisher:: AIP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

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The photoionization of methoxymethanol: Fingerprinting a reactive C2 oxygenate in a complex reactive mixture

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The photoionization of methoxymethanol: Fingerprinting a reactive C₂ oxygenate in a complex reactive mixture