Laser ablated boron atoms have been reacted with hydrogen sulfide and the reaction products condensed with argon at 4 K, which gave BS2, BS2-, HSBS, and HBS molecules. Reagent isotopic substitution （H2S, H234S, D2S, ...Laser ablated boron atoms have been reacted with hydrogen sulfide and the reaction products condensed with argon at 4 K, which gave BS2, BS2-, HSBS, and HBS molecules. Reagent isotopic substitution （H2S, H234S, D2S, 10 B, 11B） and variation of boron and hydrogen sulfide concentrations have been used to identify the major products. Both BS2-- and BS2 were identified as linear molecules with no significant difference in the structure parameters, but the B-S anti-symmetric stretching vibration of BS2 is significantly lower than that of BS2-, which is ascribed to pseudo Jahn-Teller effect. Theoretical calculation was employed to have an insight into the interaction nature of the bonds in the corresponding products.展开更多
Reaction of laser ablated zinc and cadmium atoms with SO2 molecules was studied by low temperature matrix isolation infrared spectroscopy. Cyclic M（SO2） and anion M（SO2）-（M=Zn, Cd） were produced in excess argon ...Reaction of laser ablated zinc and cadmium atoms with SO2 molecules was studied by low temperature matrix isolation infrared spectroscopy. Cyclic M（SO2） and anion M（SO2）-（M=Zn, Cd） were produced in excess argon and neon, which were identified by 34SO2 and S18O2 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 S02 ligand and cyclic M（SO2） complexes favored ＂ion pair＂ M＋（SO2）-formation, which were trapped in low temperature matrices. In addition Zn-O or Cd-O bond in M（SO2） exhibited strong polarized covalent character. Reaction of Hg atom with SO2 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.展开更多
文摘Laser ablated boron atoms have been reacted with hydrogen sulfide and the reaction products condensed with argon at 4 K, which gave BS2, BS2-, HSBS, and HBS molecules. Reagent isotopic substitution （H2S, H234S, D2S, 10 B, 11B） and variation of boron and hydrogen sulfide concentrations have been used to identify the major products. Both BS2-- and BS2 were identified as linear molecules with no significant difference in the structure parameters, but the B-S anti-symmetric stretching vibration of BS2 is significantly lower than that of BS2-, which is ascribed to pseudo Jahn-Teller effect. Theoretical calculation was employed to have an insight into the interaction nature of the bonds in the corresponding products.
文摘Reaction of laser ablated zinc and cadmium atoms with SO2 molecules was studied by low temperature matrix isolation infrared spectroscopy. Cyclic M（SO2） and anion M（SO2）-（M=Zn, Cd） were produced in excess argon and neon, which were identified by 34SO2 and S18O2 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 S02 ligand and cyclic M（SO2） complexes favored ＂ion pair＂ M＋（SO2）-formation, which were trapped in low temperature matrices. In addition Zn-O or Cd-O bond in M（SO2） exhibited strong polarized covalent character. Reaction of Hg atom with SO2 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.
