Electronic structure of the chlorinated fullerene C₆₀Cl₃₀ studied by quantum chemical modeling of X‐ray absorption spectra

Abstract

Electronic structure of the chlorinated fullerene D 3d -C 60 Cl 30 has been studied using X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), and quantum chemical B3LYP calculations. The calculated shift of the core C 1s lines corresponding to the chlorinated carbon atoms and bare carbon atoms was shown to well agree with the experimental value obtained from the XPS data. This shift was taken into account in the construction of the theoretical XANES spectra near the C K-edge of the molecule. Ground-state calculation of D 3d -C 60 Cl 30 and calculations of C 59 NCl þ 30 and C 60 Cl 29 Ar þ ions simulating the excited states of the chlorinated fullerene (Z þ 1 approximation) were used for modeling of C K-edge and Cl L-edge XANES data. A satisfactory agreement between experiment and theory was obtained in the case of Z þ 1 approximation. Distinctions between the structure of the lowest unoccupied levels in the ground state and the C 1s excited state of D 3d -C 60 Cl 30 have been revealed.

Anisotropy of Chemical Bonding in Semifluorinated Graphite C2F Revealed with Angle-Resolved X-ray Absorption Spectroscopy

“…39 In the case of a carbon structure, one carbon atom should be replaced by one nitrogen atom, while an increase in the total number of electrons is compensated by introduction of an additional positive charge. Efficiency of the Zþ1 approximation has been previously demonstrated for fullerenes C 60 and C 70 , 40 fluorinated and chlorinated fullerenes C 60 F 36 41 and C 60 Cl 30 , 42 graphene, 43 and carbon nanotubes. 44…”

High-Throughput 2D Heteroatom Graphene Bioelectronic Nanosculpture: A Combined Experimental and Theoretical Study

“…The spectrum for the Cl_2p orbital [Figure b­(i)] is deconvoluted into three peaks at the binding energy (BE) (1) 201.94 eV, (2) 200.24 eV, and (3) 198.43 eV. The peaks at BE 201.94 and 200.24 eV (1 and 2) correspond to covalent C–Cl bonds, the Cl_2p peak at BE 198.43 eV is attributed to Cl – inorganic chloride; in the present study, this could indicate an edge attached chlorine to which the hydrogen atom is attached. The BE range for the C_1s orbital is presented in Figure b­(ii), and the spectrum is also deconvoluted into seven peaks [Figure b­(ii)], (1–7).…”

Chlorination of perforated graphite via interaction with thionylchloride

“…b). Early, NEXAFS investigation of chlorinated fullerene C 60 Cl 30 detected the peaks located at 200.0 and 201.6 eV, which were related with electron transitions from Cl 2p 1/2 and Cl 2p 3/2 levels . The shift of A/A′ line in the aPGCl spectrum to higher photon energy could be attributed to strengthening of covalent C–Cl bonding for chlorine attached to the graphene edge as compared to chlorine linked with the fullerene cage.…”

“…Actually, this peak is markedly suppressed in the spectrum of the annealed sample, aPG-Cl, that allows clearly identifying a peak at $287.6 eV corresponding to covalent C-Cl bonding [29]. Two prominent peaks A and A 0 around $200.8 and $202.8 eV are seen in the Cl L-edge spectrum of aPG-Cl sample (Fig.…”