The interplay between local atomic environment and phase stability properti
es for tetrahedrally close packed (tcp) structures in transition metals has
been examined using first-principles methods. The most probable transitory
metastable tcp phases solidifying from undercooled transition metal melts
and the sequence as a function of composition of tcp phases observed in the
phase diagrams of many transition metal alloys are shown to have a common
origin. These phenomena are explained in terms of atomic coordination and l
evel splitting of the d-like states.