Modelling of poly(4-vinyl pyridine) and poly(4-vinyl pyridine)/pyridine composites: Structural and optical properties

E. Vaganova*, N. Berestetsky, S. Yitzchaik, A. Goldberg

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Scopus citations


The interactions of the polymer poly(4-vinyl pyridine) moieties with free pyridine molecules in concentrated solution develop protonated and hydrogen-bonded species on the polymer backbone and turn the viscous solution to gel. Direct irradiation at proton transfer centre on the protonated polymer moiety promotes an amorphous-to-crystalline transition. The polymer crystals exhibit completely different optical properties when compared to the amorphous material. The proposed mechanism of the photoinduced crystallisation is the following: direct excitation to the proton transfer centre generates in abundance protonated polymer moieties, which have rigid quinone structure. Rigid quinone conformations stimulate the crystallisation of the polymer chains; in their turn, increasing polymer ordering stabilises the photoinduced protonated species. Photoinduced phase transition is reversible, meaning, that crystalline phase is metastable. To clarify the mechanism of the phase transition, in the present issue, using molecular modelling, we investigate the conformational behaviour of the polymer species depending on the state of protonation, interaction with adjacent solvent molecules and polymer side-chain units. The Density Functional Theory (DFT) calculations show the protonated pyridine moiety as a quinone structure that is clearly stable, thus emphasising the ability of such structure to play a key role as a 'working' species.

Original languageAmerican English
Pages (from-to)981-987
Number of pages7
JournalMolecular Simulation
Issue number10-15
StatePublished - Sep 2008

Bibliographical note

Funding Information:
E.V. thanks the Israel Ministry of Absorption for financial support and Prof. N. Agmon for illuminating discussions.


  • DFT calculations
  • General gradient approximation
  • Polymer
  • Pyridine
  • Self-consistent field
  • ZINDO semiempirical approximation


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