Electronic State Spectroscopy of Nitromethane and Nitroethane

Luiz V. S. Dalagnol, Márcio H. F. Bettega, Nykola C. Jones, Søren V. Hoffmann, Alessandra Souza Barbosa, Paulo Limão-Vieira

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Abstract

High-resolution photoabsorption cross-sections in the 3.7-10.8 eV energy range are reinvestigated for nitromethane (CH3NO2), while for nitroethane (C2H5NO2), they are reported for the first time. New absorption features are observed for both molecules which have been assigned to vibronic excitations of valence, Rydberg, and mixed valence-Rydberg characters. In comparison with nitromethane, nitroethane shows mainly broad absorption bands with diffuse structures, which can be interpreted as a result of the side-chain effect contributing to an increased number of internal degrees of freedom. New theoretical quantum chemical calculations performed at the time-dependent density functional theory (TD-DFT) level were used to qualitatively help interpret the recorded photoabsorption spectra. From the photoabsorption cross-sections, photolysis lifetimes in the terrestrial atmosphere have been obtained for both compounds. Relevant internal conversion from Rydberg to valence character is noted for both molecules, while the nuclear dynamics of CH3NO2 and C2H5NO2 along the C-N reaction coordinate have been evaluated through potential energy curves at the TD-DFT level of theory, showing that the pre-dissociative character is more prevalent in nitromethane than in nitroethane.

Original languageEnglish
Pages (from-to)1445-1457
Number of pages13
JournalJournal of Physical Chemistry A
Volume127
Issue number6
Early online date2 Feb 2023
DOIs
Publication statusPublished - 16 Feb 2023

Keywords

  • Molecules
  • Degrees of freedom (mechanics)
  • Density functional theory
  • Photolysis
  • Potential energy
  • Quantum chemistry
  • Rydberg characte
  • Rydberg

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