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Title:VIBRONIC STRUCTURE OF THE NO3 X̃ 2A2′ SYSTEM
Author(s):Fukushima, Masaru
Subject(s):Radicals
Abstract:The $\tilde{X}$ $^2A_2'$ state of NO$_3$ under jet cooled conditions is investigated via laser induced fluorescence (~LIF~) and two-color resonant four-wave mixing (~2C-R4WM~) techniques. The electronic structure of NO$_3$ is thought to be similar to that of BF$_3$, and the latter has been well documented in the literatures\footnote{H.~B.~Gray, Electrons and Chemical Bonding, W.~A.~Benjamin Inc., New York (1965); Open Source Tex Books, https://archive.org/details/ost-chemistry-electrons\_chemical\_bonding (retrieved Feb. 26, 2019).}\footnote{F.~A.~Cotton, Chemical Applications of Group Theory, 2nd ed., Wiley-International, New York (1971).}. The BF$_3$ highest occupied molecular orbital (~HOMO~) possesses peculiar electronic structure with orbital localization on each of three F’s and no contribution on the center atom, B. For NO$_3$, the HOMO corresponds to a singly occupied molecular orbital (~SOMO~), and, in the $\tilde{X}$ $^2A_2'$ state (~$\tilde{A}$ $^2E''$ and $\tilde{B}$ $^2E'$, too~) of NO$_3$, the un-paired electron is localized on the three O’s and has no contribution on N. For this state, the degenerate vibrations are naturally expected to strongly affect the electron motion, which can be referred to as ”degenerate-vibrationally induced vibronic coupling” on the non-degenerate electronic state. The SOMO characteristics of NO$_3$ have been confirmed by high-level quantum chemical computation\footnote{W.~Eisfeld and K.~Morokuma, $J.~Chem.~Phys.$ 113, 5587 (2000).}. The characteristic features of the vibrational structure of the $\tilde{X}$ $^2A_2'$ state may possibly be understood by the vibronic coupling. One feature is an unexpectedly large spin splitting of $1_0$ (~= $N_K$~) of the 3$\nu_4$ ($a_1'$) level observed by 2C-R4WM\footnote{M.~Fukushima and T.~Ishiwata, 73rd ISMS, paper WD02 (2018).}, and this splitting can be understood as the good quantum number behavior of $P$ (~$= K_v + \Sigma = \Lambda + l + \Sigma$~) derived from the coupling.
Issue Date:2019-06-18
Publisher:International Symposium on Molecular Spectroscopy
Genre:Conference Paper / Presentation
Type:Text
Language:English
URI:http://hdl.handle.net/2142/104453
DOI:10.15278/isms.2019.TD07
Rights Information:Copyright 2019 Masaru Fukushima
Date Available in IDEALS:2019-07-15
2020-01-25


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