A Comparative Computational Study of the Adsorption of TCNQ and F4-TCNQ on the Coinage Metal Surfaces

[Image: see text] The adsorption of tetracyanoquinodimethane and of the closely related derivative tetrafluorotetracyanoquinodimethane on the (111) surfaces of the coinage metals, namely, copper, silver, and (unreconstructed) gold, has been studied by dispersion-corrected ab initio density functional theory calculations. In order to separate the molecule–substrate interaction from the effects of molecule–molecule interaction, only the isolated molecules are considered. The results show that, in this case, the strength of the interaction of both molecules with the surfaces decreases in the expected order Cu > Ag > Au. The total amount of charge transfer, however, behaves in a different way, being larger for Ag and smaller for Cu and Au. This trend can be explained by a combination of the differences in the work functions of the three metals and the amount of backdonation between the molecule and the metal.