A vibrationally resolved electronic spectrum is reported for the metal dimer-rare gas complex Ag2-Xe. The spectrum is obtained using resonant two-photon photoionization in the energy region near the Ag2 B ← X electronic transition (292-280 nm). The complex exhibits 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 Ag2-Xe complex having nearly the same rare gas stretching frequency (ωe′ = 79.9 cm-1) as the corresponding krypton (ωe′ = 72.6 cm-1) and Ar complexes (ωe′ = 73.9 cm-1) which have been studied previously. Progressions extending over a significant range of the excited-state potential surface make it possible to derive the excited-state dissociation energy (D0′ = 2761 cm-1). Combination with the red-shifted electronic state origin yields the corresponding ground-state dissociation energy (D0″ = 1233 cm-1). These binding energies, when compared to those for similar argon and krypton complexes with Ag2, are greater than would be expected on the basis of the rare gas polarizability trend.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry