EXPERIMENTAL AND THEORETICAL STUDY OF X-RAY K-EDGES ABSORPTION SPECTRA OF CARBON AND NITROGEN IN MOLECULE PHTHALOCYANINE H2Pc
G. I. Semushkina, L. N. Mazalov, T. V. Basova
1Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: фталоцианин, рентгеновская абсорбционная спектроскопия, стационарная и нестационарная теории функционала плотности, phthalocyanine, X-ray absorption spectroscopy, stationary and time-dependent density functional theory
Abstract
The study of the electronic structure of H2Pc was carried out to examine the structure of the lowest unoccupied molecular orbitals (LUMO) of molecule phthalocyanine by X-ray absorption spectroscopy using quantum-chemical calculations. The theoretical calculations were performed on the stationary theory (frozen orbital approximation, Z +1 model) and time-dependent density functional theory (TDDFT). A consideration of K -edges absorption spectra of carbon and nitrogen in the common scale of binding energies allows estimating the contributions of AO of all phthalocyanine atoms to the LUMO, defining the sequence of levels, the binding energies of the corresponding levels, and also the character of electronic interactions between individual atoms. It was shown that the best agreement between the experimental and theoretical pre-edge structures of the absorption spectra of nitrogen and carbon for H2Pc is observed in the case of the application of stationary density functional theory in Z +1 model to account for an X-ray hole. In this case the 2 p p AO of the Na(1,2) and Сa atoms make a predominant contribution to the LUMO. The 2 p p AO of the Na (1,2) atoms mainly contribute to the boundary LUMO with the energy ~ -2.3 eV.
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