Abstract:
Nonrelativistic, relativistic, and semiempirical pseudopotentials for the Pb atom have been generated to replace the chemically inert core electrons for investigating the effects of relativity and correlation on molecular properties of PbH+, PbH, PbH2, and PbH4. Spin-orbit effects are taken into account by using a quasirelativistic two-spinor pseudopotential. The relativistic bond contraction is found to be dependent on the Pb(6s) orbital participation in the Pb-H bond (?relr e: 0.04 A for PbH+, PbH, and PbH2 and 0.07 A for PbH4). The calculated and measured values agree excellently [e.g., re (PbH) = 1.839 A expt. 1.839 A]. The inert pair effect for the lead hydrides will be discussed.