Spin populations and free valences in excited molecules and in radicals

S.G. Semenov, M.E. Bedrina, V.A. Klemeshev, M.V. Makarova

Research output: Contribution to journalArticle

8 Scopus citations

Abstract

© 2014, Pleiades Publishing, Ltd. 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.
Original languageEnglish
Pages (from-to)516-524
JournalOptics and Spectroscopy (English translation of Optika i Spektroskopiya)
Issue number4
DOIs
StatePublished - 2014

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