  We obtain parameters for non-orthogonal and orthogonal TB models from
two-atomic molecules for all combinations of elements of period 1 to 6 and
group 3 to 18 of the periodic table. The TB bond parameters for 1711 homoatomic
and heteroatomic dimers show clear chemical trends. In particular, using our
parameters we compare to the rectangular d-band model, the reduced sp TB model
as well as canonical TB models for sp- and d-valent systems which have long
been used to gain qualitative insight into the interatomic bond. The
transferability of our dimer-based TB bond parameters to bulk systems is
discussed exemplarily for the bulk ground-state structures of Mo and Si. Our
dimer-based TB bond parameters provide a well-defined and promising starting
point for developing refined TB parameterizations and for making the insight of
TB available for guiding materials design across the periodic table.
