Abstract:

Several ab initio methods were employed to investigate the structures and electronic properties of PdO0,±1, PdH0,±1, and PdOH. Two states (3∏and 3∑-) with similar energies were found for PdO. Energetically, the 3∏ state is more favored compared to the 3∑- state. At the coupled-cluster method with single and double excitations (CCSD) level of theory, the 3∑- state is 0.286 eV higher in total energy than the 3∏state. Based on the favored structures, we calculated the adiabatic ionization energies (AIE) and electronic affinities (AEA) of the PdO and PdH molecules. Our calculated values of AIE and AEA are in good agreement with the available experimental values. Geometry optimization result showed the ground state of PdOH to be a non-linear Pd—OH (2A') structure with Cs symmetry. In addition, we obtained two metastable structures Pd—OH (2A'') and O—Pd—H (2A''). We optimized the transition state connecting these two metastable states and calculated the corresponding energy barrier.

Key words: Ab initio, Transition state, Electronic property, Molecular orbital, Energy barrier, Internal reaction coordinate calculation