Spin populations and free valences in excited molecules and in radicals

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Spin populations and free valences in excited molecules and in radicals. / Semenov, S.G.; Bedrina, M.E.; Klemeshev, V.A.; Makarova, M.V.

In: Optics and Spectroscopy (English translation of Optika i Spektroskopiya), No. 4, 2014, p. 516-524.

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Semenov, S.G. ; Bedrina, M.E. ; Klemeshev, V.A. ; Makarova, M.V. / Spin populations and free valences in excited molecules and in radicals. In: Optics and Spectroscopy (English translation of Optika i Spektroskopiya). 2014 ; No. 4. pp. 516-524.

BibTeX

@article{fd8849e6dfd84fed9da3bada6600c242,

title = "Spin populations and free valences in excited molecules and in radicals",

abstract = "{\textcopyright} 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.",

author = "S.G. Semenov and M.E. Bedrina and V.A. Klemeshev and M.V. Makarova",

year = "2014",

doi = "10.1134/S0030400X14100191",

language = "English",

pages = "516--524",

journal = "OPTICS AND SPECTROSCOPY",

issn = "0030-400X",

publisher = "Pleiades Publishing",

number = "4",

}

RIS

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