Electronic structures of Pd4 and Pt4

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Abstract
Complete active space multiconfiguration self‐consistent field (CAS‐MCSCF) followed by multireference configuration interaction computations which included up to 4.1 million configurations and correlated all 40 electrons of Pd4 and Pt4 were made. Relativistic effective core potentials (RECPS) were employed for both Pt and Pd atoms. We found 44 electronic states for Pd4 within the 2.2 eV region and 51 electronic states for Pt4 within 1.2 eV. Two nearly‐degenerate electronic states with tetrahedral geometries were found as candidates for the ground states of Pd4 and Pt4 with 3 T 1 and 1 A 1 symmetries at the highest level of theory. The metal–metal bond lengths for Pd4 and Pt4 were found to be 2.686 and 2.602 Å for the 3 T 1 state and 2.696 and 2.595 Å for the 1 A 1 state, respectively. The atomization energies of Pd4 and Pt4 were computed as 5.63 and 11.8 eV, respectively, suggesting that Pt4 is considerably more bound compared to Pd4. Relativistic effects are attributed to the enhanced stability of Pt4. The Mulliken population analysis reveals enhanced Pt(6s) and reduced Pt(5d) populations for the electronic states of Pt4 while the electronic states of Pd4 exhibit the opposite trend.

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