  The in-plane effective mass of quantum well states in thin Pb films on a Bi
reconstructed Si(111) surface is studied by angle-resolved photoemission
spectroscopy. It is found that this effective mass is a factor of three lower
than the unusually high values reported for Pb films grown on a Pb
reconstructed Si(111) surface. Through a quantitative low-energy electron
diffraction analysis the change in effective mass as a function of coverage and
for the different interfaces is linked to a change of around 2% in the in-plane
lattice constant. To corroborate this correlation, density functional theory
calculations were performed on freestanding Pb slabs with different in-plane
lattice constants. These calculations show an anomalous dependence of the
effective mass on the lattice constant including a change of sign for values
close to the lattice constant of Si(111). This unexpected relation is due to a
combination of reduced orbital overlap of the 6p_z states and altered
hybridization between the 6p_z and 6p_xy derived quantum well states.
Furthermore it is shown by core level spectroscopy that the Pb films are
structurally and temporally stable at temperatures below 100 K.
