Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane

Sheps, Leonid; Dewyer, Amanda Lee; Demireva, Maria Plamenova; Zádor, Judit

doi:10.1021/acs.jpca.1c02001

Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane

Journal Article · Tue May 18 00:00:00 EDT 2021 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.1c02001· OSTI ID:1787521

^[1]; Dewyer, Amanda Lee ^[1]; ^[1]; Zádor, Judit ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)

We present a combined experimental and theoretical investigation of the autoignition chemistry of a prototypical cyclic hydrocarbon, cyclopentane. Experiments using a high-pressure photolysis reactor coupled to time-resolved synchrotron VUV photoionization mass spectrometry directly probe the short-lived radical intermediates and products in cyclopentane oxidation reactions. We detect key peroxy radical intermediates ROO and OOQOOH, as well as several hydroperoxides, formed by second O₂ addition. Automated quantum chemical calculations map out the R + O₂ + O₂ reaction channels and demonstrate that the detected intermediates belong to the dominant radical chain-branching pathway: ROO (+ O₂) → γ-QOOH + O₂ → γ-OOQOOH → products. ROO, OOQOOH, and hydroperoxide products of second-O₂ addition undergo extensive dissociative ionization, making their experimental assignment challenging. We use photoionization dynamics calculations to aid in their characterization and report the absolute photoionization spectra of isomerically pure ROO and γ-OOQOOH. Here, a global statistical fit of the observed kinetics enables reliable quantification of the time-resolved concentrations of these elusive, yet critical species, paving the way for detailed comparisons with theoretical predictions from master-equation-based models.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC04-94AL85000; NA0003525

OSTI ID:: 1787521

Report Number(s):: SAND--2021-5038J; 695828

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 20 Vol. 125; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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