Electronic Structure of Metal/Molecule//Metal Junctions: A Density Functional Theory Study of the Influence of the Molecular Terminal Group

Abstract

We report on density functional theory calculations of the electronic structure of Au(111)/molecule//Au(111) junctions in which thiol molecules are chemically bound at one end to a gold electrode (the "substrate"), while the other end has a separation of a few to several angstroms from a second gold electrode (the "tip"). Our goal is to investigate the role of different molecular terminal groups and of the tip-molecule distance either on the spatial dependence of the local density of states (LDOS) at the Fermi energy E(f) or on the energy dependence of the projected density of states onto different molecular subunits. We consider conjugated diphenylthiol (SPh2R) molecules with terminal groups R = H, SH, CH3, or CF3 as well as "mixed" conjugated-saturated phenylthiol-pentane (SPhC4CH3) and butanethiol-toluene (SC4PhCH3) molecules. For SPh2R molecules, the LDOS at E(f) exhibits an oscillatory exponential decay along the molecule, with an average decay constant that depends weakly on the R terminal group. For the mixed aromatic-aliphatic molecules instead, there are large differences in the LDOS at E(f), with SC4PhCH3 showing a much larger LDOS in the proximity of the terminal CH3 group than SPhC4CH3.