Electronic Structure of NO2 Studied by Photoelectron and Vacuum-uv Spectroscopy and Gaussian Orbital Calculations

Abstract

The ionization potentials of NO2 up to 28 eV have been measured using He i and He ii high-resolution photoelectron spectroscopy. The assignment of the ionized levels below 16 eV is straightforward, including the singlet–triplet splittings, and allows us to assign Rydberg series in the vacuum uv leading to the first five ionization potentials. Above 16 eV the spectrum is complicated by the absence of obvious singlet–triplet splittings. The assignments we propose fit in with a coherent scheme for the molecular-orbital energy levels of 16-, 17-, and 18-electron triatomic molecules. The SCF calculations have been performed on several states of NO2 and NO2+ (both open shell and closed shell) and the results are in quite good agreement with the experimental ionization potentials.

A Theoretical Study on the Electronic States and O‐Loss Photodissociation of the NO2+ Ion

“…A C H T U N G T R E N N U N G (6a 1 ) 1 . We think that the photoelectron spectrum studies of Brundle et al [1] and of Baltzer et al [2] are important in this field.…”

“…Extensive experimental studies on the electronic states and photodissociation of the NO 2 + ion have been reported in the literature. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] For studying the electronic states of the NO 2 + ion, several experimental groups [1][2][3][4] investigated the photoelectron spectrum of the NO 2 molecule, which has a doublet ground 2 A 1 state with an electronic configuration of …A C H T U N G T R E N N U N G (3b 2 ) 2 …”

1997 Summer Research Program (SRP), Summer Research Extension Program (SREP), Final Report, Volume 2. Phillips Laboratory

“…At the low temperature a long lived complex is formed so that sufficient curve crossing occur to allow the complex to exit in an exothermic channel NO + ('S) + 0( 3 S, 1 D,'P) At higher temperatures (T>300K) the complex is not being formed and the process is a direct one appearing to have an endothermic threshold. This has been rationalized by Ferguson [31] to be a consequence of the correlation of 0 + ( 4 S) and NO ( 2 7t) with the excited states 3 Ai, 3 Bj of N0 2 + which lie slightly above the reactants in energy [32]. The reaction does not i occur via non-adiabatic electron jump due to the low Frank-Condom factor.…”

“…V WSR dC/dt = Z{(dm/dt)j Cj /p} -C QWSR [28] where the summation is over all (32) A numerical scheme to calculate the transient response of the jet ring according to Eqns. [27] and [29] was implemented in the form of an EXCEL™ spreadsheet.…”

“…Also, the retrievals [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] for the noisy cases should be investigated further, in order to determine what modifications to the regularization update criterion are needed to obtain an accurate retrieval.…”