UV + VUV double-resonance studies of autoionizing Rydberg states of the hydroxyl radical

Green, Amy M.; Liu, Fang; Lester, Marsha I.

doi:10.1063/1.4948640

UV + VUV double-resonance studies of autoionizing Rydberg states of the hydroxyl radical

Journal Article · Fri May 13 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4948640· OSTI ID:1471072

Green, Amy M. ^[1]; ^[2]; Lester, Marsha I. ^[2]

Univ. of Pennsylvania, Philadelphia, PA (United States); University of Pennsylvania
Univ. of Pennsylvania, Philadelphia, PA (United States)

Here, the hydroxyl radical (OH) is a key oxidant in atmospheric and combustion chemistry. Recently, a sensitive and state-selective ionization method has been developed for detection of the OH radical that utilizes UV excitation on the A²Σ⁺–X²Π transition followed by fixed 118 nm vacuum ultraviolet (VUV) radiation to access autoionizing. The present study uses tunable VUV radiation generated by four-wave mixing to examine the origin of the enhanced ionization efficiency observed for OH radicals prepared in specific A²Σ⁺ intermediate levels. The enhancement is shown to arise from resonant excitation to distinct rotational and fine structure levels of two newly identified ²Π Rydberg states with an A3Π cationic core and a 3d electron followed by ionization. Spectroscopic constants are derived and effects due to uncoupling of the Rydberg electron are revealed for the OH ²Π Rydberg states. The linewidths indicate a Rydberg state lifetime due to autoionization on the order of a picosecond.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Contributing Organization:: Argonne National Laboratory; Cardiff University

Grant/Contract Number:: FG02-87ER13792

OSTI ID:: 1471072

Alternate ID(s):: OSTI ID: 22657990
OSTI ID: 1253065

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 144; ISSN JCPSA6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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