Back to Search
Start Over
Metal/conjugated polymer interfaces: A local density functional study of aluminum/polyene interactions.
- Source :
-
Journal of Chemical Physics . 6/15/1994, Vol. 100 Issue 12, p9258. 7p. - Publication Year :
- 1994
-
Abstract
- The interactions between aluminum atoms and model molecules representing trans-polyacetylene are studied quantum chemically by a local density functional method. We focus on the chemical and electronic structure of the organoaluminum complexes. Special emphasis is put on a comparison between results at the local spin density approximation and ab initio Hartree–Fock levels. In unmetallized polyenes, the density functional method provides a very good description of the carbon–carbon bond lengths of conjugated systems; in the case of hexatriene, it reproduces the bond dimerization in very good agreement with experimental measurements. Upon metallization, a strong covalent interaction between aluminum and carbon is found. The Al–C bond formation induces an interruption of the bond alternation pattern and reduces the π-conjugation in the oligomer, in qualitative agreement with photoelectron spectroscopy data and previous theoretical results at the Hartree–Fock level. Notably, the π-electron levels in the organoaluminum complexes maintain delocalization. In contrast to Hartree–Fock results where an aluminum atom binds to a single carbon, the interactions calculated with the local spin density approximation lead to (i) formation of multicenter aluminum–carbon bonding; (ii) near planarity of the polyene molecule; and (iii) a lower degree of charge transfer from the metal atom to the polymer. [ABSTRACT FROM AUTHOR]
- Subjects :
- *ATOMS
*MOLECULES
*POLYACETYLENES
*DENSITY functionals
*POLYMERS
Subjects
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 100
- Issue :
- 12
- Database :
- Academic Search Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 7641810
- Full Text :
- https://doi.org/10.1063/1.466678