  We have experimentally determined the lateral registry and geometric
structure of free-base porphine (2H-P) and copper-metalated porphine (Cu-P)
adsorbed on Cu(111), by means of energy-scanned photoelectron diffraction
(PhD), and compared the experimental results to density functional theory (DFT)
calculations that included van der Waals corrections within the
Tkatchenko-Scheffler approach. Both 2H-P and Cu-P adsorb with their center
above a surface bridge site. Consistency is obtained between the experimental
and DFT-predicted structural models, with a characteristic change in the
corrugation of the four N atoms of the molecule's macrocycle following
metalation. Interestingly, comparison with previously published data for cobalt
porphine adsorbed on the same surface evidences a distinct increase in the
average height of the N atoms above the surface through the series 2H-P, Cu-P,
cobalt porphine. Such an increase strikingly anti-correlates the DFT-predicted
adsorption strength, with 2H-P having the smallest adsorption height despite
the weakest calculated adsorption energy. In addition, our findings suggest
that for these macrocyclic compounds, substrate-to-molecule charge transfer and
adsorption strength may not be univocally correlated.
