Reaction pathways for palladium(I) reduction in laser-induced particle formation of Pd: An ab initio molecular orbital study

Abstract

Previously, we have theoretically shown that the UV irradiation can decompose the PdCl42- anion into PdCl2- + Cl + Cl-, in which palladium is reduced from Pd(II) to Pd(I). In this work we perform ab initio calculations to investigate reactions that can immediately follow this reaction in aqueous alcohol solution. Geometry optimizations and harmonic vibrational analyses are done for the species pertinent to the Pd(I) reduction with the MP2(full) method. The employed basis sets are aug-cc-pVTZ-PP for Pd and aug-cc-pVTZ for other elements. Single-point energies at higher-levels of theory are obtained with the MP4(SDTQ) and QCISD(T) methods with the same basis sets. Solvent effects are also included in all calculations using the polarizable continuum model and water is used as the solvent. Based on the energetics of the relevant reactions, we find likely pathways leading to the formation of Pd(0) species.