Photoelectron spectrum of NO : SAC-CI gradient study of vibrational-rotational structures.

Three-dimensional accurate potential energy surfaces around the local minima of NO and NO were calculated with the SAC/SAC-CI analytical energy gradient method. Therefrom, the ionization photoelectron spectra of NO , the equilibrium geometries and adiabatic electron affinity of NO , and the vibrational frequencies including harmonicity and anharmonicity of NO and NO were obtained. The calculated electron affinity was in reasonable agreement with the experimental value. The SAC-CI photoelectron spectra of NO 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 . © 2018 Wiley Periodicals, Inc.