  We measure the low bias conductance of a series of substituted benzene
diamine molecules while breaking a gold point contact in a solution of the
molecules. Transport through these substituted benzenes is by means of
nonresonant tunneling or superexchange, with the molecular junction conductance
depending on the alignment of the metal Fermi level to the closest molecular
level. Electron-donating substituents, which drive the occupied molecular
orbitals up, increase the junction conductance, while electron-withdrawing
substituents have the opposite effect. Thus for the measured series,
conductance varies inversely with the calculated ionization potential of the
molecules. These results reveal that the occupied states are closest to the
gold Fermi energy, indicating that the tunneling transport through these
molecules is analogous to hole tunneling through an insulating film.
