- PII
- 10.31857/S0044451024120046-1
- DOI
- 10.31857/S0044451024120046
- Publication type
- Article
- Status
- Published
- Authors
- Volume/ Edition
- Volume 166 / Issue number 6
- Pages
- 795-812
- Abstract
- Using X-ray diffraction analysis (XRD), Raman spectroscopy (RS), and quantum chemical calculations, the features of temperature behavior of thermally activated conformational disorder of terminal ethylene groups C2H4 of BEDT-TTF (or ET) molecules in crystals of quasi-two-dimensional organic conductor к-(BEDT-TTF)2Cu[N(CN)2]Cl were studied at temperatures from 112 K to 289 K. During slow cooling at a rate of –4 K/hour and steps of 10 K, crystal lattice parameters were measured and complete structural analysis was performed for characteristics temperatures. Crystal structure parameters show anomalous temperature behavior in the interval 175–250 К, in the same region an anomaly is observed in the behavior of intramolecular vibration frequencies of the ET molecule, which is associated with changes in the degree of conformational disorder. Based on the obtained structural data, the influence of the observed disorder on the electronic structure of the conducting layer was analyzed using quantum chemical modeling methods. In particular, the results of calculations using the semi- empirical extended Hückel method with a basis set optimized for the given system allowed determining the nature of electron density distribution both within the dimer and within the layer depending on the configuration of terminal ethylene groups. The main types of charge redistribution between molecules in the dimer ET2 were identified. It is shown how the population of configurations and the degree of dimer polarization affect the stability of different types of charge ordering within the conducting layer and, ultimately, the conductive properties of the crystal.
- Keywords
- Date of publication
- 16.09.2025
- Year of publication
- 2025
- Number of purchasers
- 0
- Views
- 3
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