NOO peroxy isomer exposed with velocity-map imaging

Laws, Benjamin A.

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https://hdl.handle.net/2142/91317 Copy

Description

Title

NOO peroxy isomer exposed with velocity-map imaging

Author(s)

Laws, Benjamin A.

Contributor(s)

• Gibson, Stephen T.
• Lewis, Brenton R.
• Cavanagh, Steven J.

Issue Date

2016-06-23

Keyword(s)

Radicals

Abstract

\begin{wrapfigure}{r}{0pt} \includegraphics[scale=0.125]{NO2-3Dimage-800.eps} \end{wrapfigure} NO$_{2}$, a toxic gas formed in most combustion processes, plays an important role in the Earth's atmosphere due to its role in the production of both photochemical smog and tropospheric ozone. The existence of the peroxy radial, NOO, has been proposed, both as a collision reaction intermediate, and as a negative-ion in some discharge sources, in order to account for extended tails seen in some photoelectron spectra.\footnote{\label{erv88}K. M. Ervin and J. Ho and W. C. Lineberger, \emph{J. Phys. Chem.} \textbf{92}, 5405 (1988). doi:10.1021/j100330a017} In this work a velocity-mapped image of NO$_{2}^{-}$ photodetachment measured at 519~nm, shown, reveals high-energy electron structure, that persists at detachment energies lower than the electron affinity of ONO, 2.273~eV.\textsuperscript{\emph{b}} The central ring has the spectral signature of O$^-$, while the outer-ripples, that appear in character to be similar to NO$-$ detachment, are, we propose due to the NOO$^{-}$ peroxy radical, which is also responsible for the presence of O$^{-}$. The photoelectron spectrum resolves the vibrational structure to characterize the neutral peroxy radical. The identification is further supported by \emph{ab initio} calculations. The photoelectron angular distributions associated with the peroxy radical have a negative anisotropy parameter, opposite in sign to detachment from ONO$^-$.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

En

Permalink

http://hdl.handle.net/2142/91317

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Copyright 2016 by the authors

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