Density functional theory was used for a quantum chemical study of oligo[methyl(phenyl)silylene] structures containing a conformational defect: a kink in the silicon backbone. Oligomers were studied in the neutral state as well as in the form of positive (P+) and negative (P−) polaron quasiparticles. Computations performed using the B3LYP model and the 6-31G(d) basis set revealed that the charge distribution is not influenced by the presence of the kink, but the positive charge on the Si backbone differs slightly in P+ and P− quasiparticles. On the other hand, the spin density is significantly shifted away from the chain part that contains the kink, and this effect is more intense in P− polarons. Changes in electron density are also evident from the frontier molecular orbital distribution. The deformation energy (which is associated with the relaxation of polarons) decreases with the number of atoms in the oligomer backbone in P+ but shows the opposite behavior for P− quasiparticles.
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This work was supported by the Internal Grant Agency of Tomas Bata University in Zlín (grant no. IGA/FT/2014/006). This paper was written with the support of the Operational Program Research and Development for Innovations, co-funded by the European Regional Development Fund (ERDF) and the national budget of the Czech Republic, within the framework of the Centre of Polymer Systems (reg. number: CZ.1.05/2.1.00/03.0111) project, and with the support of the Operational Program Education for Competitiveness, co-funded by the European Social Fund (ESF) and the national budget of the Czech Republic, within the framework of the Advanced Theoretical and Experimental Studies of Polymer Systems (reg. number: CZ.1.07/2.3.00/20.0104) project.
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Hanulikova, B., Kuritka, I. Theoretical study of polaron binding energy in conformationally disrupted oligosilanes. J Mol Model 20, 2442 (2014). https://doi.org/10.1007/s00894-014-2442-y
- Spin density
- Density functional theory