Electronic spectra of nitroethylene |
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| Authors: | Itamar Borges Jr. Mario Barbatti Adélia J.A. Aquino Hans Lischka |
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| Affiliation: | 1. Departamento de Química, Instituto Militar de Engenharia, Pra?a General Tibúrcio, 80, Rio de Janeiro 22290‐270, Brazil;2. Max‐Planck‐Institut für Kohlenforschung, Kaiser‐Wilhelm‐Platz 1, Mülheim an der Ruhr D‐45470, Germany;3. Institute of Soil Research, University of Natural Resources and Life Sciences Vienna, Peter‐Jordan‐Stra?e 82, Vienna A‐1190, Austria;4. Institute for Theoretical Chemistry, University of Vienna, W?hringerstrasse 17, Wien A‐1090, Austria |
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| Abstract: | A systematic study of the electronic excited states of nitroethylene (C2H3NO2) was carried out using the approximate coupled‐cluster singles‐and‐doubles approach with the resolution of the identity (RI‐CC2), the time dependent density functional theory with the CAMB3LYP functional (TDDFT/CAMB3LYP) and the DFT multireference configuration interaction (DFT/MRCI) method. Vertical transition energies and optical oscillator strengths were computed for a maximum of 20 singlet transitions. Semiclassical simulations of the ultraviolet (UV) spectra were performed at the RI‐CC2 and DFT/MRCI levels. The main features in the UV spectrum were assigned to a weak n‐π* transition, and two higher energy πCC+O‐π* bands. These characteristics are common to molecules containing NO2 groups. Simulated spectra are in good agreement with the experimental spectrum. The energy of the bands in the DFT/MRCI simulation agrees quite well with the experiment, although it overestimates the band intensities. RI‐CC2 produced intensities comparable to the experiment, but the bands were blue shifted. A strong πCC+O‐π* band, not previously measured, was found in the 8–9 eV range. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012 |
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| Keywords: | nitroethylene RI‐CC2 wave function TDDFT CAMB3LYP DFT/MRCI semiclassical spectra excited states UV spectrum gas‐phase energetic materials |
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