Metal/conjugated polymer interfaces: A local density functional study of aluminum/polyene interactions

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.