Результаты исследований: Научные публикации в периодических изданиях › статья
Spin populations and free valences in excited molecules and in radicals. / Semenov, S.G.; Bedrina, M.E.; Klemeshev, V.A.; Makarova, M.V.
в: Optics and Spectroscopy (English translation of Optika i Spektroskopiya), № 4, 2014, стр. 516-524.Результаты исследований: Научные публикации в периодических изданиях › статья
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TY - JOUR
T1 - Spin populations and free valences in excited molecules and in radicals
AU - Semenov, S.G.
AU - Bedrina, M.E.
AU - Klemeshev, V.A.
AU - Makarova, M.V.
PY - 2014
Y1 - 2014
N2 - © 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.
AB - © 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.
U2 - 10.1134/S0030400X14100191
DO - 10.1134/S0030400X14100191
M3 - Article
SP - 516
EP - 524
JO - OPTICS AND SPECTROSCOPY
JF - OPTICS AND SPECTROSCOPY
SN - 0030-400X
IS - 4
ER -
ID: 7048323