Experimental evidence of the ν3 mode in NO3 via slow photoelectron velocity-map imaging of cold NO3−
Babin, Mark C.
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https://hdl.handle.net/2142/104265
Description
Title
Experimental evidence of the ν3 mode in NO3 via slow photoelectron velocity-map imaging of cold NO3−
Author(s)
Babin, Mark C.
Contributor(s)
Neumark, Daniel
Stanton, John F.
DeVine, Jessalyn A.
Issue Date
2019-06-18
Keyword(s)
Radicals
Abstract
"With five electronic states within 2 eV, the nitrate radical (NO$_3$) has a rich vibronic landscape for which photoelectron spectroscopy is an ideal probe. Here, we use slow photoelectron velocity map imaging of cryogenically cooled anions (cryo-SEVI), a high-resolution variant of anion photoelectron spectroscopy, to investigate the vibronic structure of the $\tilde{X}^2A'_2$ state of NO$_3$. Our cryo-SEVI spectra are in excellent agreement with Franck-Condon simulations produced using a three-state K\""{o}ppel-Domke-Cederbaum (KDC) Hamiltonian constructed for the NO$_3$ radical. Together, the experimental and simulated spectra provide clear evidence that the $\nu_3$ fundamental resides near 1060 cm$^{-1}$, resolving a long-standing controversy surrounding this vibrational fundamental. Further, the appearance of activity along the $\nu_4$ mode in this cryogenically-cold system verifies its activity through a Herzberg-Teller interaction, rather than as a hot band as previously suggested."
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