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Photoelectron spectrum of NO 2 − : SAC‐CI gradient study of vibrational‐rotational structures
Author(s) -
Miyahara Tomoo,
Nakatsuji Hiroshi
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25608
Subject(s) - spectral line , chemistry , excited state , atomic physics , anharmonicity , ionization energy , x ray photoelectron spectroscopy , electron affinity (data page) , ionization , ground state , adiabatic process , photoemission spectroscopy , nuclear magnetic resonance , physics , ion , molecule , organic chemistry , quantum mechanics , astronomy , thermodynamics
Three‐dimensional accurate potential energy surfaces around the local minima of NO 2 − and NO 2 were calculated with the SAC/SAC‐CI analytical energy gradient method. Therefrom, the ionization photoelectron spectra of NO 2 − , the equilibrium geometries and adiabatic electron affinity of NO 2 , and the vibrational frequencies including harmonicity and anharmonicity of NO 2 − and NO 2 were obtained. The calculated electron affinity was in reasonable agreement with the experimental value. The SAC‐CI photoelectron spectra of NO 2 − at 350 K and 700 K including the rotational effects were calculated using the Franck–Condon approximation. The theoretical spectra reproduced well the fine experimental photoelectron spectra observed by Ervin et al. (J. Phys. Chem. 1988, 92, 5405). The results showed that the ionizations from many vibrational excited states as well as the vibrational ground state are included in the experimental photoelectron spectra especially at 700 K and that the rotational effects are important to reproduce the experimental photoelectron spectra of both temperatures. The SAC/SAC‐CI theoretical results supported the analyses of the spectra by Ervin et al., except that we could show some small contributions from the asymmetric‐stretching mode of NO 2 − . © 2018 Wiley Periodicals, Inc.