Inner-shell photoabsorption spectroscopy of push-pull nitroanilines-Theoretical and experimental studies at N 1s region

• Published in: International journal of quantum chemistry Vol. 108; no. 13; pp. 2340 - 2357
• Main Authors: Guerra, Antonio C. O., Ferreira, Glaucio B., Machado, Sérgio P., Turci, Cássia C.
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 05.11.2008
• Subjects: building block model; EICVOM; inner-shell excitation; IVO; nitroanilines; synchrotron radiation
• ISSN: 0020-7608; 1097-461X
• DOI: 10.1002/qua.21618

Oscillator strengths for N 1s excitation spectra of the gas‐phase aniline and nitrobenzene, and the solid‐phase meta‐ and para‐nitroanilines have been derived from the total electron yield and total ion yield spectra acquired by tunable synchrotron radiation. Ab initio calculations carried out within the improved virtual orbital method and equivalent ionic core virtual orbital model have been used to aid spectral interpretation. The Rydberg‐valency mixture has also been evaluated for all compounds. These results are compared to those acquired with the extended hückel molecular orbital method [Goeta et al., Chem Mater, 2000, 12, 3342]. The building block model has been used to simulate the nitroanilines spectra. The sensitivity of core excitation spectroscopy to intramolecular nitroanilines charge transfer and the N 1s → π* spectral features dependence upon the substitution pattern (meta or para) have been confirmed, as already verified for the gas‐phase inner‐shell energy loss spectra for the same molecules [Turci et al., Can J Chem, 1996, 74, 851]. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008