Vibrationally resolved electronic spectra are reported for the metal dimer-rare gas complexes Ag2-Ar and Ag2-Kr. These spectra are obtained using resonant two-photon photoionization in the energy region near the Ag2 B←X electronic transition (280-285 nm). Both complexes exhibit extensive activity in three vibrational modes, making it possible to determine vibrational constants, anharmonicities, and cross-mode couplings. An unusual cancellation of factors results in the Kr complex (ω′ e = 72.6 cm-1) having nearly the same metal-rare gas stretching frequency as the Ar complex (ω′e = 73.9 cm-1). Progressions extending over a significant range of the excited state potential surfaces make it possible to derive the excited state dissociation energies (D′0 = 755 and 1205 cm-1 for Ar and Kr, respectively). Combination with the red-shifted electronic state origins yields the corresponding ground state dissociation energies (D″0 = 275 and 394 cm-1 for Ar and Kr, respectively). Potential energy surfaces are investigated for excited and ground states of both complexes.
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry