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Experimental and theoretical study of X-ray K edges absorption spectra of carbon and nitrogen in the phthalocyanine H2Pc molecule. / Semushkina, G. I.; Mazalov, L. N.; Basova, T. V.
In: Journal of Structural Chemistry, Vol. 57, No. 7, 01.12.2016, p. 1334-1347.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Experimental and theoretical study of X-ray K edges absorption spectra of carbon and nitrogen in the phthalocyanine H2Pc molecule
AU - Semushkina, G. I.
AU - Mazalov, L. N.
AU - Basova, T. V.
PY - 2016/12/1
Y1 - 2016/12/1
N2 - 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 2pπ AO of the Nα(1,2) and Сα atoms make a predominant contribution to the LUMO. The 2pπ AO of the Nα(1,2) atoms mainly contribute to the boundary LUMO with the energy ~–2.3 eV.
AB - 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 2pπ AO of the Nα(1,2) and Сα atoms make a predominant contribution to the LUMO. The 2pπ AO of the Nα(1,2) atoms mainly contribute to the boundary LUMO with the energy ~–2.3 eV.
KW - phthalocyanine
KW - stationary and time-dependent density functional theory
KW - X-ray absorption spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85009997612&partnerID=8YFLogxK
U2 - 10.1134/S0022476616070064
DO - 10.1134/S0022476616070064
M3 - Article
AN - SCOPUS:85009997612
VL - 57
SP - 1334
EP - 1347
JO - Journal of Structural Chemistry
JF - Journal of Structural Chemistry
SN - 0022-4766
IS - 7
ER -
ID: 25438023