Photodissociative experiments were performed on Cu+-C5H5N and Ag+-C5H5N complexes in the gas phase. The dissociative ligand-to-metal charge-transfer fragments, pyridine+, were observed for both complexes. Photodissociation spectra were recorded as a function of laser wavelength. Two continuous, structureless bands were investigated in each complex. Because of the low-energy 2D state of the Cu atom, the Cu+ pyridine dissociative process is more complicated. Several possible mechanisms for this process have been discussed. The binding energies were determined experimentally to be 65.5 and 45.2 kcal/mol for Cu+ -pyridine and Ag+-pyridine, respectively. M+-C5H5N (M = Cu or Ag) complexes also were studied theoretically using the HF, MP2, and B3LYP methods. All complexes under study show C2v, symmetry. The binding energies predicted from the theoretical calculations were less than the experimental values, which were derived from the onset of the charge-transfer appearance combined with the IP (ionization potential). The complexes containing Cu+ and Ag+ are characterized predominantly by electrostatic interactions.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry