Ab initio investigations of the electric field dependence of the geometric and electronic structures of molecular wires

Theoretical investigations on the typical molecular wire, polyacetylene, which bridges two chemically inert electrodes, have been carried out at the Hartree-Fock level by incorporating the external electric field into the calculations. The results demonstrate that both the geometric and the electronic structures of the conjugated molecular wires are sensitive to the electric field. When the electric field increases, the carbon-carbon single bonds become shorter and the double bonds become longer, leading to a higher conjugation. The electric field reduces the HOMO-LUMO gap and increases the dipole moment. The spatial distributions of the molecular orbitals are used to analyze the electrical properties of the molecular wire. All of these features are more pronounced with increasing conjugation chain length. Quantitative correlations between most of these features and the electric field have been discussed as well.