Abstract:
Reaction of laser ablated zinc and cadmium atoms with SO
2 molecules was studied by low temperature matrix isolation infrared spectroscopy. Cyclic M(SO
2) and anion M(SO
2)
- (M=Zn, Cd) were produced in excess argon and neon, which were identified by
34SO
2 and S
18O
2 isotopic substitutions. The observed infrared spectra and molecular structures were confirmed by density functional theoretical calculations. Natural charge distributions indicated significant electron transfer from s orbitals of zinc or cadmium metal atom to SO
2 ligand and cyclic M(SO
2) complexes favored “ion pair” M
+(SO
2)
- formation, which were trapped in low temperature matrices. In addition Zn-O or Cd-O bond in M(SO
2) exhibited strong polarized covalent character. Reaction of Hg atom with SO
2 was also investigated, but no reaction product was observed, due to the relativistic effect that resulted in the contraction of 6s valence shell and high ionization potential of Hg atom