All-electron CPF calculations including relativistic effects have been performed for PdCO and Pd2CO. The carbonyl binding energies are found to be surprisingly large, 33 kcal/mol for PdCO and 55 kcal/mol for Pd2CO, which for the latter case is much larger than the value for nickel. The non-relativistic SCF binding energies are small, 0 for PdCO and 3 kcal/mol for Pd2CO, showing that correlation and relativity are important for describing the bonding. The relativistic contributions to the binding energies for the two systems are 11 and 14 kcal/mol, and originate directly from the decrease in the splitting between the 4d10 and the 4d95s states of the palladium atom. The present results deviate strongly from two recent calculations for Pd2CO (one gave a small binding energy, 16 kcal/mol and another gave a large binding energy 111 kcal/mol).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Condensed Matter Physics
- Atomic and Molecular Physics, and Optics
- Surfaces and Interfaces