| Autor: |
Petrova JN; Faculty of Chemistry, University of Sofia, 1 James Bourchier Avenue, 1164 Sofia, Bulgaria., Romanova JR, Madjarova GK, Ivanova AN, Tadjer AV |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. B [J Phys Chem B] 2011 Apr 14; Vol. 115 (14), pp. 3765-76. Date of Electronic Publication: 2011 Mar 21. |
| DOI: |
10.1021/jp111914n |
| Abstrakt: |
Calculations for model oligomers of the emeraldine salt with UBLYP/6-31G*/PCM are performed. The models differ in number of monomers, in the position of the counterions (Cl(-)), and in multiplicity. The molecular features affected most prominently by the protonation, namely, structure, energetics, and electron and spin density partitioning are analyzed. The results show unequivocally that the studied molecular characteristics are essentially size independent. The octamer profiles of all parameters are repeated in the dodecamer and the hexadecamer. The bipolaronic forms are energetically more favorable than the polaronic ones within the chosen protocol. The electronic structure in the intermediate multiplicities differs from the bipolaronic and polaronic periodicity. The geometrical changes and electron density redistribution upon increase of multiplicity illustrate the pathway of intramolecular bipolaron-polaron conversion. The orbital analysis rationalizes the observed behavior of the oligomers. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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