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Application of DFT for the modeling of the valence region photoelectron spectra of boron and d‐element complexes and macromolecules
Author(s) -
Osmushko Ivan S.,
Vovna Vitaliy I.,
Tikhonov Sergey A.,
Chizhov Yuriy V.,
Krauklis Irina V.
Publication year - 2016
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25011
Subject(s) - x ray photoelectron spectroscopy , density functional theory , valence (chemistry) , chemistry , spectral line , ionization , ionization energy , boron , ultraviolet photoelectron spectroscopy , valence electron , macromolecule , electronic structure , atomic physics , computational chemistry , electron , ion , nuclear magnetic resonance , physics , organic chemistry , biochemistry , quantum mechanics , astronomy
Using density functional theory (DFT) in conjunction with ultraviolet (UPS) and X‐ray photoelectron spectroscopy (XPS), we investigated a number of complexes and macromolecules. We have shown on a large set of UPS, XPS, and DFT data that the calculated Kohn–Sham energies of organic and metalorganic complexes can be used as approximate ionization energies (IEs). It is possible to evaluate IEs with an accuracy of 0.1 eV with the density functional approximation (DFA) defect approach. This method has been successfully tested on a large number of boron β‐diketonates and d‐metal chelate and sandwich complexes. We interpreted the bands in the valence region of the XP spectra of macromolecular organosilicon compounds in the solid state by taking into account the density of states and the ionization cross‐sections. According to DFT calculation results, the one‐electron states in the valence region of the model compounds correlate with the positions of the spectral band maxima. © 2015 Wiley Periodicals, Inc.