TY - JOUR

T1 - A quantum-chemical study of intermediates of the 1O2 photogeneration sensitized by buckminsterfullerene and accompanying photochemical reactions

AU - Semenov, S.G.

AU - Bedrina, M.E.

PY - 2014

Y1 - 2014

N2 - The intermediates of hypothetical photochemical reactions that accompany the quenching of the 3C 60 triplet state by triplet oxygen are studied by the (U)PBE0 quantum-chemical method. The diradical C 60-O-O formed from 3O2 and photoexcited buckminsterfullerene 3C 60 is characterized by a negative binding energy -1.11 eV (with respect to C60 and 3O 2), the singlet-triplet splitting ΔE ST of 0.07 eV, and the dipole moment of 3.2 D at the equilibrium internuclear separations 1.522 Å (CO) and 1.294 Å (OO). Its decay produces 1O 2. The formation of a dioxetane circle lowers the energy by 0.8 eV. The ground-state energy of diketone C58(C=O)2 is 2.0 eV lower than the energy of C60-O-O. The metastable centrosymmetric diradical C60-C60, formed upon ineffective light absorption by clusters (C60)N, has a single interpolyhedral C-C bond (1.657 Å). Its triplet state T 1 lies 0.16 eV higher than the S 1 singlet. The S 1 → S 0 relaxation leads to the formation of a stable C60-C 60 dimer with a shorter (1.584 Å) bis-single e

AB - The intermediates of hypothetical photochemical reactions that accompany the quenching of the 3C 60 triplet state by triplet oxygen are studied by the (U)PBE0 quantum-chemical method. The diradical C 60-O-O formed from 3O2 and photoexcited buckminsterfullerene 3C 60 is characterized by a negative binding energy -1.11 eV (with respect to C60 and 3O 2), the singlet-triplet splitting ΔE ST of 0.07 eV, and the dipole moment of 3.2 D at the equilibrium internuclear separations 1.522 Å (CO) and 1.294 Å (OO). Its decay produces 1O 2. The formation of a dioxetane circle lowers the energy by 0.8 eV. The ground-state energy of diketone C58(C=O)2 is 2.0 eV lower than the energy of C60-O-O. The metastable centrosymmetric diradical C60-C60, formed upon ineffective light absorption by clusters (C60)N, has a single interpolyhedral C-C bond (1.657 Å). Its triplet state T 1 lies 0.16 eV higher than the S 1 singlet. The S 1 → S 0 relaxation leads to the formation of a stable C60-C 60 dimer with a shorter (1.584 Å) bis-single e

U2 - 10.1134/S0030400X14020180

DO - 10.1134/S0030400X14020180

M3 - Article

VL - 116

SP - 173

EP - 178

JO - OPTICS AND SPECTROSCOPY

JF - OPTICS AND SPECTROSCOPY

SN - 0030-400X

IS - 2

ER -