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Optics and Spectroscopy

, Volume 117, Issue 4, pp 516–524 | Cite as

Spin populations and free valences in excited molecules and in radicals

  • S. G. Semenov
  • M. E. Bedrina
  • V. A. Klemeshev
  • M. V. Makarova
Spectroscopy of Atoms and Molecules

Abstract

Using the DFT PBE0 quantum-chemical method, we have determined the spin populations and the free valences of atoms in (i) 3,4-dimethylenefuran; (ii) exciplex 3,4-dimethylenefuran · O2; (iii) phthalocyaninates PcCu and PcCo; (iv) cations Pc+Cu, Pc+Co, and Pc+Ni; (v) dication [PcAlOAlPc]2+; and (vi) two excited triplet diketones: fulleroid-type C58(CO)2 and cyclododeca-3,4,9,10-tetraene-1,7-dione. Free valences determine atomic contributions to the doubled variance of the many-electron spin. Unlike spin populations, they are insensitive to the choice of the component of a quasi-degenerate spin state of a chemical compound and account for the regioselectivity of the radical addition to 3,4-dimethylenefuran and the photochemical stability of Pc-containing nanosystems. In a triplet state of C12H12O2, the spin density and the free valence are localized on a single carbonyl group, whereas, in a triplet state of C58(CO)2, they are delocalized.

Keywords

Triplet State Tetraene Spin Population Free Valence Cobalt Phthalocyaninates 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Pleiades Publishing, Ltd. 2014

Authors and Affiliations

  • S. G. Semenov
    • 1
  • M. E. Bedrina
    • 1
  • V. A. Klemeshev
    • 1
  • M. V. Makarova
    • 1
  1. 1.St. Petersburg State UniversitySt. PetersburgRussia

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