Relativistic effects on geometry and electronic structure of small Pdn species (n=1, 2, 4)

Abstract

Relativistic effects on the properties of small neutral Pdn species (n=1, 2, 4) and Pd2− have been examined for the first time at the all-electron level by performing scalar-relativistic and nonrelativistic density functional calculations using a gradient-corrected density functional. Relativistic effects are found to be important: They lead to a contraction of bond lengths, increase of vibrational frequencies, and a significant enhancement of binding energies. While relativistic effects are quite uniform for several states of Pd4, they vary for the states examined for Pd2, leading to a change of ground state due to relativity. The calculated relativistic properties of Pd2 and Pd2− are in good agreement with available experimental data from mass spectrometry and photoelectron spectroscopy. For Pd4 three-dimensional structures are found to be preferred to planar ones and many nearly isoenergetic isomers exist. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 74: 405–416, 1999