The near-infrared spectrum of ethynyl radical

Le, Anh T.; Hall, Gregory E.; Sears, Trevor J.

doi:10.1063/1.4961019

Title: The near-infrared spectrum of ethynyl radical

Journal Article · Wed Aug 17 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4961019· OSTI ID:1303024

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Brookhaven National Lab. (BNL), Upton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)

We used transient diode laser absorption spectroscopy to measure three strong vibronic bands in the near infrared spectrum of the C₂H, ethynyl, radical not previously observed in the gas phase. The radical was produced by ultraviolet excimer laser photolysis of either acetylene or (1,1,1)-trifluoropropyne in a slowly flowing sample of the precursor diluted in inert gas, and the spectral resolution was Doppler-limited. The character of the upper states was determined from the rotational and fine structure in the observed spectra and assigned by measurement of ground state rotational combination differences. The upper states include a ²Σ⁺ state at 6696 cm^-1, a second ²Σ⁺ state at 7088 cm^-1, and a ²Π state at 7110 cm^-1. By comparison with published calculations [R. Tarroni and S. Carter, J. Chem. Phys 119, 12878 (2003); Mol. Phys. 102, 2167 (2004)], the vibronic character of these levels was also assigned. Moreover, the observed states contain both X ²Σ⁺ and A ²Π electronic characters. Several local rotational level perturbations were observed in the excited states. Kinetic measurements of the time-evolution of the ground state populations following collisional relaxation and reactive loss of the radicals formed in a hot, non-thermal, population distribution were made using some of the strong rotational lines observed. Finally, the case of C₂H may be a good place to investigate the behavior at intermediate pressures of inert colliders, where the competition between relaxation and reaction can be tuned and observed to compare with master equation models, rather than deliberately suppressed to measure thermal rate constants.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC00112704; SC0012704

OSTI ID:: 1303024

Alternate ID(s):: OSTI ID: 1297263

Report Number(s):: BNL-112520-2016-JA; JCPSA6; R&D Project: CO006; KC0301020

Journal Information:: Journal of Chemical Physics, Vol. 145, Issue 7; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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Cited by: 5 works

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