THEORETICAL INVESTIGATION OF THE INFLUENCE OF ELECTRON SHELLS' REARRANGEMENT ON K-EMISSION SPECTRA INTENSITIES IN 3d -METALS

We show that taking monopole rearrangement of electrons' shells into consideration when calculating K-spectra intensities lead to 15 - 30 % increase of calculated intensity ratio IKβ5/IKβ1 that is being used as a standard value when determining p -electron densities of valency states on 3d metals i n compounds

ON THE NATURE OF NONSTRUCTURAL LOW-R PEAK IN FOURIER TRANSFORMS OF SOME EXAFS-SPECTRA

K-absorption spectra of kripton and zirconium are calculated considering additional monopole excitations of 3d-shell. It is shown that the disturbance of smoothness of the atomic photoionization cross section due to multi-electron excitations including 3d-shells lead to the appearance of low frequency EXAFS-oscillations that do not correspond to the structure of atomic encirclement of the absorber. Such an effect can make data analyses difficult for the spectra with weak structural signal

Effect of the Structure of Carboxylate Ligands on the X-Ray Photoelectron Spectral Parameters of Trinuclear Heterometallic Complexes [Fe2MO(O2CR)6(H2O)3](H2O)3 (M = Co, Ni; R = CH3, CCl3)

An anomalously large difference was found in the energies of the 2p, 3s, and 3p lines in the X-ray photoelectron spectra for all metal ions in complexes [Fe2MO(O2CCH3)6(H2O)3](H2O)3 and [Fe2MO(O2CCCl3)6(H2O)3](H2O)3(M = Co, Ni). The observed line shifts were explained in the framework of an electrostatic model considering the change in the interaction energy of the electrons of metal atoms and the charge distribution of the peripheral fragments of the complexes. © 2016, Springer Science+Business Media New York

Effect of the Structure of Carboxylate Ligands on the X-Ray Photoelectron Spectral Parameters of Trinuclear Heterometallic Complexes [Fe2MO(O2CR)6(H2O)3](H2O)3 (M = Co, Ni; R = CH3, CCl3)

An anomalously large difference was found in the energies of the 2p, 3s, and 3p lines in the X-ray photoelectron spectra for all metal ions in complexes [Fe2MO(O2CCH3)6(H2O)3](H2O)3 and [Fe2MO(O2CCCl3)6(H2O)3](H2O)3(M = Co, Ni). The observed line shifts were explained in the framework of an electrostatic model considering the change in the interaction energy of the electrons of metal atoms and the charge distribution of the peripheral fragments of the complexes. © 2016, Springer Science+Business Media New York

Study of the electronic structure of polynuclear cobalt trimethylacetate complexes by Co3s and Co3p X-Ray photoelectron spectroscopy

The electronic structure of mono-, hexa-, and nonanuclear cobalt trimethylacetate complexes was studied by XPS. The Co3s- and Co3p X-ray photoelectron spectra of the complexes were recorded. The Co3p spectrum of bivalent cobalt was calculated in the isolated-ion intermediate-coupling approximation. Spectrum analysis showed that the [Co(N-Phobsqdi) 2(η'-N-Ph-opda)(OOCCMe3)] complex is a strong-field complex with Co(III) in the diamagnetic state; the [Co(dipy) 2(OOCCMe3)2], [Co(dipyam)(OOCCMe 3)2], and [Co9(μ3-OH) 6(μ-OOCCMe3)12(OCMe2) 4] are high-spin weak-field Co(II) complexes; and the [Co 6(μ4- O)2(OOCCMe3) 10(THF)4] complex contains both the Co(II) and Co(III) atoms. The energy position of major Co3s- and Co3p spectral maxima were found to be sensitive to the nature of the nearest environment of cobalt atoms. The data correlate well with X-ray crystallographic data. © Pleiades Publishing, Ltd., 2011

Study of the electronic structure of polynuclear cobalt trimethylacetate complexes by Co3s and Co3p X-Ray photoelectron spectroscopy

The electronic structure of mono-, hexa-, and nonanuclear cobalt trimethylacetate complexes was studied by XPS. The Co3s- and Co3p X-ray photoelectron spectra of the complexes were recorded. The Co3p spectrum of bivalent cobalt was calculated in the isolated-ion intermediate-coupling approximation. Spectrum analysis showed that the [Co(N-Phobsqdi) 2(η'-N-Ph-opda)(OOCCMe3)] complex is a strong-field complex with Co(III) in the diamagnetic state; the [Co(dipy) 2(OOCCMe3)2], [Co(dipyam)(OOCCMe 3)2], and [Co9(μ3-OH) 6(μ-OOCCMe3)12(OCMe2) 4] are high-spin weak-field Co(II) complexes; and the [Co 6(μ4- O)2(OOCCMe3) 10(THF)4] complex contains both the Co(II) and Co(III) atoms. The energy position of major Co3s- and Co3p spectral maxima were found to be sensitive to the nature of the nearest environment of cobalt atoms. The data correlate well with X-ray crystallographic data. © Pleiades Publishing, Ltd., 2011

X-ray photoelectron Fe3s and Fe3p spectra of polynuclear trimethylacetate iron complexes

X-ray photoelectron Fe3s and Fe3p spectra are employed to study the electron structure and the spin magnetic state of bi-, tri-, and hexa-nuclear trimethylacetate iron complexes. Assignment of the spectra is performed based on an isolated-ion Pauli-Fock calculation of Fe3s and Fe3p spectra of the Fe atoms in bi-and tri-valent states. Nonequivalent FeIII and FeII atoms are detected in tri-and hexa-nuclear complexes. Paramagnetic-limit molecular magnetic moments are calculated using effective atomic magnetic moments obtained from spin-sensitive spectral characteristics. Comparison of those values with the magnetic measurements data demonstrates antiferromagnetic interaction within the complexes. © 2010 Elsevier B.V. All rights reserved

X-ray photoelectron Fe3s and Fe3p spectra of polynuclear trimethylacetate iron complexes

X-ray photoelectron Fe3s and Fe3p spectra are employed to study the electron structure and the spin magnetic state of bi-, tri-, and hexa-nuclear trimethylacetate iron complexes. Assignment of the spectra is performed based on an isolated-ion Pauli-Fock calculation of Fe3s and Fe3p spectra of the Fe atoms in bi-and tri-valent states. Nonequivalent FeIII and FeII atoms are detected in tri-and hexa-nuclear complexes. Paramagnetic-limit molecular magnetic moments are calculated using effective atomic magnetic moments obtained from spin-sensitive spectral characteristics. Comparison of those values with the magnetic measurements data demonstrates antiferromagnetic interaction within the complexes. © 2010 Elsevier B.V. All rights reserved