Ab initio investigation of electric and magnetic dipole electronic transitions in the complex of oxygen with benzene

R. R. Valiev, B. F. Minaev

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The electric dipole transitions between pure spin and mixed spin electronic states are calculated at the XMC-QDPT2 and MCSCF levels of theory, respectively, for different intermolecular distances of the C6H6 and O2 collisional complex. The magnetic dipole transition moment between the mixed-spin ground (“triplet”) and the first excited (“singlet”) states is calculated by quadratic response at MCSCF level of theory. The obtained results confirm the theory of intensity borrowing and increasing the intensity of electronic transitions in the C6H6 + O2 collision. The calculation of magnetically induced current density is performed for benzene molecule being in contact with O2 at the distances from 3.5 to 4.5 Å. The calculation shows that the aromaticity of benzene is rising due to the conjugation of π-MOs of both molecules. The C6H6 + O2 complex becomes nonaromatic at the short distances (r < 3.5 Å). The computation of static polarizability in the excited electronic states of the C6H6 + O2 collisional complex at various distances supports the theory of red solvatochromic shift of the a → X band. [Figure not available: see fulltext.]

Original languageEnglish
Article number214
JournalJournal of Molecular Modeling
Volume22
Issue number9
DOIs
Publication statusPublished - 1 Sep 2016

Keywords

  • Collisional complexes
  • Herzberg bands
  • Magnetic dipole transition
  • Oxygen
  • Singlet oxygen
  • XMC-QDPT2

ASJC Scopus subject areas

  • Catalysis
  • Computer Science Applications
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Computational Theory and Mathematics
  • Inorganic Chemistry

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