Solvent effects on photodissociation of nCl (n=1,2) loss from PdCl₄^2-by DFT calculation

Recently, Saeki et al. succeeded in measuring the concentration of ¹⁰⁷Pd by precipitating Pd from spent fuel of a nuclear power plant using the laser induced particle formation method.  According to reaction formula, ????????_??^??−+????_??????_??????+????→????^??+????_????????+????++??????⁻ , PdCl₄^2- can be irradiated with a 266 nm UV laser to reduce Pd²⁺ in aqueous EtOH solution, which has a charge transfer absorption band in the UV region, and neutralize Pd²⁺ to Pd⁰ [1].

The photodissociation process of PdCl₄^2- is very important. Kurosaki et al. calculated the potential energy curve of Cl dissociation of PdCl₄^2- by MRCI calculation and clarified the possibility of 2Cl dissociation process, in which a neutral Cl atom and an anionic Cl- atom are formed from PdCl₄^2- in the photodissociation process of PdCl₄^2- [2]. In this study, we focused on the solvation effect in the Cl photodissociation process of PdCl₄^2- by using the density functional theory, and clarified the mechanism of the photodissociation reaction between Pd and Cl.

[1] M. Saeki,et al., J. Phys. Chem. 123 (2019) 817-842

[2] Y. Kurosaki et al. Chem. Phys. Lett. 764, (2021) 138247.