Abstract
Unique photophysical properties of lanthanide(III) ions (Ln(III)), such as various waves of their monochromatic luminescence, the peculiarities of its mechanisms and the occurring photophysical process, are an explanation of their introduction into optoelectronic devices and instruments, solar and thermoelectric elements, light emitting diodes, in medicine as tags for marking metabolic processes. At the same time, the significant labor intensity and costs of synthesis and experimental analysis of the Ln(III) compounds' properties make quantum-chemical simulation methods a relevant solution in this situation. In this article approaches for the quantum-chemical simulation of the molecular structure and selected properties of the mesogenic europium(III) (Eu(III)) complex with a substituted β-diketone and a Lewis base were recommended. To carry out the current study, several basis sets and quantum-chemical methods were used to perform the process of optimization of the molecular geometry of the complex, calculating the vibrational frequencies of the IR spectrum and absorption spectrum. The choice of the approach and analysis of the accuracy of the calculated parameters and characteristics were revealed by studying the model Eu(III) compounds with similar ligands, but with a simpler structure. For model complexes, experimental data on X-ray diffraction analysis of their molecular structure were found. For the subsequent calculation of the mesogenic compound, according to the comparison of the simulation results with experimental literature values, the most suitable and accurate approaches were selected. The absorption spectra were calculated in the ORCA 5.0 program using the density functional theory method. The hybrid functional B3LYP with the inclusion of the dispersion correction D3BJ was chosen for the modeling. The DFT-D3 Grimm approach and the Back-Johnson damping scheme made it possible to correct dispersion. The calculations of the vibrational frequencies and IR spectra of complexes were carried out in the Priroda 06 program by the density functional theory with the exchange-correlation functional PBE. At the same time, relativistic effects were taken into account by the use of the appropriate basic set. At the same time, relativistic effects were taken into account by the use of the appropriate basic set. Comparison of simulation results obtained by various approaches with experimental data, as well as the assessment of methods' advantages and disadvantages allowed to select the appropriate methodology for calculations of the mesogenic Eu(III) complex.
Published Version
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