Molecular Conductance:  Chemical Trends of Anchoring Groups

Combining density functional theory calculations for molecular electronic structure with a Green
function method for electron transport, we calculate from first principles the molecular conductance of
benzene connected to two Au leads through different anchoring atomssS, Se, and Te. The relaxed atomic
structure of the contact, different lead orientations, and different adsorption sites are fully considered. We
find that the molecule-lead coupling, electron transfer, and conductance all depend strongly on the
adsorption site, lead orientation, and local contact atomic configuration. For flat contacts the conductance
decreases as the atomic number of the anchoring atom increases, regardless of the adsorption site, lead
orientation, or bias. For small bias this chemical trend is, however, dependent on the contact atomic
configuration: an additional Au atom at the contact with the (111) lead changes the best anchoring atom
from S to Se, although for large bias the original chemical trend is recovered.