First-principles theory of tetrahedral bonding and crystal structure of lead

From linear muffin-tin-orbital calculations using suitable basis sets we derive, from first principles, sp³ bonding characteristics for group-IV elements. Particular attention is paid to lead, for which the importance of relativistic effects in determining the most stable structure is examined. The mass-velocity shift of the Pb 6s state is so large that the s-p hybridization in a hypothetical diamond structure is too weak to allow the formation of sufficiently strong sp³ bonding. Omission of relativistic effects would make the diamond structure of Pb more stable than the observed (fcc).