Direct frequency comb measurement of OD + CO→DOCO kinetics

Autor(en)

B. J. Bjork, T. Q. Bui, O. H. Heckl, P. B. Changala, B. Spaun, P. Heu, D. Follman, C. Deutsch, G. D. Cole, M. Aspelmeyer, M. Okumura, J. Ye

Abstrakt

The kinetics of the hydroxyl radical (OH) + carbon monoxide (CO) reaction, which is fundamental to both atmospheric and combustion chemistry, are complex because of the formation of the hydrocarboxyl radical (HOCO) intermediate. Despite extensive studies of this reaction, HOCO has not been observed under thermal reaction conditions. Exploiting the sensitive, broadband, and high-resolution capabilities of time-resolved cavity-enhanced direct frequency comb spectroscopy, we observed deuteroxyl radical (OD) + CO reaction kinetics and detected stabilized trans-DOCO, the deuterated analog of trans-HOCO. By simultaneously measuring the time-dependent concentrations of the trans-DOCO and OD species, we observed unambiguous low-pressure termolecular dependence of the reaction rate coefficients for N-2 and CO bath gases. These results confirm the HOCO formation mechanism and quantify its yield.

Organisation(en)

Quantenoptik, Quantennanophysik und Quanteninformation

Externe Organisation(en)

U.S. Department of Commerce, University of Colorado, Boulder, Thorlabs Crystalline Solutions, Crystalline Mirror Solutions GmbH, California Institute of Technology (Caltech)

Journal

Science

Band

354

Seiten

444-448

Anzahl der Seiten

5

ISSN

0036-8075

DOI

https://doi.org/10.1126/science.aag1862

Publikationsdatum

10-2016

Peer-reviewed

Ja

ÖFOS 2012

103006 Chemische Physik, 103021 Optik

Schlagwörter

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/9d35ebf3-dc73-4921-9a5a-ff6a2e62080e