Assessment of B3LYP combined with various ECP basis sets for systems containing Pd, Sn, and Pb

Abstract

An assessment of the performance of various effective core potential (ECP) basis sets for Pd, Sn, and Pb has been presented in this work. In order to carry out this assessment, for a series of diatomic molecules containing Pd, Sn, Pb (the mono- and bimetallic diatomics, as well as the monohydrides and monocarbides of these metals) the values of their three fundamental spectroscopic constants (bond length, harmonic vibrational frequency, dissociation energy) were calculated using the B3LYP density functional combined with nineteen mixtures of ECP basis sets for Pd, Sn, and Pb and with 6-311G(d,p) for H and C. The statistical comparison of the calculated values with the experimental data available allowed us to assess the performance of the considered mixtures of ECP basis sets assigned to the Pd, Sn, and Pb atoms. B3LYP in conjunction with LANL2TZ(f) for Pd, LANL08d for Sn and Pb, and 6-311G(d,p) for H and C provides a sensible compromise between accuracy and computational cost. We believe that this computational approach will be suitable for the future investigations of the semihydrogenation of alkynes on the Pd–Sn and Pd–Pb catalysts.