We have used scanning tunneling spectroscopy to spatially map the energy‐resolved local density of states of C60molecules in the monomer and monolayer regimes on the Ag(001) surface. Spectral maps were obtained for molecular states derived from the C60HOMO, LUMO, and LUMO+1 orbitals. An unexpected density inversion is observed between the spectral maps of the LUMO and LUMO+1 states. The observed spatial inhomogeneities and density inversion are explained usingab initiopseudopotential density functional calculations. These calculations demonstrate the need for explicitly including the STM tip trajectory when interpreting STM images of electronically inhomogeneous systems. © 2003 American Institute of Physics