Research output: Contribution to journal › Article › peer-review
Electronic structure and nature of the metal-ligand chemical bond of Be, Mg, and Zn β-diketonates by quantum chemistry methods. / Komissarov, Alexander A. ; Shcheka, Oleg L. ; Tikhonov, Sergey A.; Korochentsev, Vladimir V. ; Samoilov, Ilya S. ; Vovna, Vitaliy I.
In: Journal of Molecular Structure, Vol. 1204, No. 1204, 127540, 15.03.2020.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Electronic structure and nature of the metal-ligand chemical bond of Be, Mg, and Zn β-diketonates by quantum chemistry methods
AU - Komissarov, Alexander A.
AU - Shcheka, Oleg L.
AU - Tikhonov, Sergey A.
AU - Korochentsev, Vladimir V.
AU - Samoilov, Ilya S.
AU - Vovna, Vitaliy I.
N1 - Publisher Copyright: © 2019 Elsevier B.V.
PY - 2020/3/15
Y1 - 2020/3/15
N2 - The electronic structure of Be (II), Mg (II), and Zn (II) acetylacetonates and hexafluoroacetylacetonates was calculated in the DFT approximation. The energies of MOs and ionization energies calculated by the OVGF method were compared with the published data of photoelectron spectroscopy (HeI). The outer valence region of the spectra is equally effectively reproduced by DFT and OVGF methods. The calculations allowed determining the ionization energies of the π2 orbitals of the chelate cycles. It was determined that an increase in the binding energy of the electrons of the valence and core levels upon substitution of CH3>CF3 by 1,7–2,1 eV was correlated with a change of the negative charge of the carbon atom of the substituted groups on positive one. The polarity of M − O bonds increases in the series of Be, Mg, Zn. It was found that in addition to outer valence orbitals, a covalent bonding was also significantly affected by the deep valence σ-orbital 4a1 with a high degree of overlap with metal s-orbitals.
AB - The electronic structure of Be (II), Mg (II), and Zn (II) acetylacetonates and hexafluoroacetylacetonates was calculated in the DFT approximation. The energies of MOs and ionization energies calculated by the OVGF method were compared with the published data of photoelectron spectroscopy (HeI). The outer valence region of the spectra is equally effectively reproduced by DFT and OVGF methods. The calculations allowed determining the ionization energies of the π2 orbitals of the chelate cycles. It was determined that an increase in the binding energy of the electrons of the valence and core levels upon substitution of CH3>CF3 by 1,7–2,1 eV was correlated with a change of the negative charge of the carbon atom of the substituted groups on positive one. The polarity of M − O bonds increases in the series of Be, Mg, Zn. It was found that in addition to outer valence orbitals, a covalent bonding was also significantly affected by the deep valence σ-orbital 4a1 with a high degree of overlap with metal s-orbitals.
KW - Alkaline earth metal β-diketonates
KW - DFT
KW - Photoelectron spectra
KW - Electronic structure
KW - Orbital analysis
KW - Alkaline earth metal β-diketonates
KW - DFT
KW - Photoelectron spectra
KW - electronic structure
KW - Orbital analysis
KW - Electronic structure
KW - Alkaline earth metal beta-diketonates
KW - PHOTOELECTRON-SPECTRA
KW - MOLECULAR-STRUCTURE
KW - GAS-PHASE
KW - DIFFRACTION
KW - GAUSSIAN-BASIS SETS
UR - http://www.scopus.com/inward/record.url?scp=85076084995&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/641585ad-5718-370d-ae46-6c021e1feb78/
U2 - https://doi.org/10.1016/j.molstruc.2019.127540
DO - https://doi.org/10.1016/j.molstruc.2019.127540
M3 - Article
VL - 1204
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
SN - 0022-2860
IS - 1204
M1 - 127540
ER -
ID: 62722442