Ab initio MRCI study on potential energy curves for a single Cl loss from the palladium tetrachloride anion PdCl42

Abstract We theoretically investigate a single Cl loss from the PdCl42- anion, which is a candidate for key processes in the laser-induced particle formation of Pd in aqueous/EtOH solution proposed recently by Saeki et al. (M. Saeki et al., J. Phys. Chem. C 123 (2019) 817). We calculate low-lying potential energy curves (PECs) of PdCl42- as a function of a Pd-Cl bond length with the MRCI method. It is found that PdCl42- is excited to a 1Eu state by UV irradiation, followed by a Pd-Cl bond elongation on the repulsive 21A1 and/or 21B1 PECs, leading adiabatically to the Cl- formation.