Electronic and optical excitations in crystalline conjugated polymers

Article

关键词: DENSITY-FUNCTIONAL THEORY;    EXCITON BINDING-ENERGY;    AB-INITIO CALCULATION;    MOLECULAR-DYNAMICS;    EXCHANGE ENERGY;    1ST PRINCIPLES;    SEMICONDUCTORS;    POLYTHIOPHENE;    SPECTRA;    1ST-PRINCIPLES;   

DOI  :  10.1103/PhysRevB.66.035206

来源: SCIE

【 摘 要 】

We calculate the electronic and optical excitations of crystalline polythiophene and polyphenylenevinylene, using the GW approximation for the electronic self-energy and including excitonic effects by solving the electron-hole Bethe-Salpeter equation. We compare with our earlier calculations on an isolated polythiophene chain and polymer chains embedded in a dielectric medium. Surprisingly, we find for the crystalline calculations optical gaps and exciton binding energies that are significantly smaller than present experimental values. We attribute the disagreement to the fact that the quantum-mechanical coherence between polymer chains, present in the calculations, is absent in most experimental situations. We discuss possible reasons for this absence. Our general conclusion is that the picture of a polymer chain in a dielectric medium is most appropriate in describing the present experimental data on electronic and optical excitations in conjugated polymers.

【 授权许可】

Free