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Near Edge X-ray Absorption, Valence and Core-level Photoemission and DensityFunctional Theory calculations are used to study molecular levels oftetracyano-2,3,5,6-tetrafluoroquinodimethane (F$_4$TCNQ) deposited on Ag(111)and BiAg$_2$/Ag(111). The high electron affinity of F$_4$TCNQ triggers a largestatic charge transfer from the substrate, and, more interestingly,hybridization with the substrate leads to a radical change of symmetry, shapeand energy of frontier molecular orbitals. The Lowest Unoccupied MolecularOrbital (LUMO) shifts below the Fermi energy, becoming the new Highest OccupiedMolecular Orbital ($n$-HOMO), whereas the $n$-LUMO is defined by a hybrid bandwith mixed $\pi^*$ and $\sigma^*$ symmetries, localized at quinone rings andcyano groups, respectively. The presence of Bi influences the way the moleculecontacts the substrate with the cyano group. The molecule/surface distance iscloser and the bond more extended over substrate atoms in F$_4$TCNQ/Ag(111),whereas in F$_4$TCNQ/BiAg$_2$/Ag(111) the distance is larger and the contactmore localized on top of Bi. This does not significantly alter molecularlevels, but it causes the respective absence or presence of optical excitationsin F$_4$TCNQ core-level spectra.

Symmetry, Shape and Energy Variations in Frontier Molecular Orbitals at Organic/Metal Interfaces: the Case of F$_4$TCNQ