Empirical Jahn-Teller potential surfaces for silver doped xenon matrices

Potential energy surfaces for 5s and 5p states of Ag atoms in the vibration ally distorted O-h symmetry of a Xe matrix are constructed by numerical dia gonalization of the Hamiltonian and using coupling parameters derived from experimental absorption and emission spectra. The 5p state exhibits both sp in-orbit and Jahn-Teller coupling. The large structural relaxation after ex citation indicated by the large Stokes shift of the emission necessitates h igher-order terms in both the vibrational potentials and the Jahn-Teller co upling. Only the two E-g modes are considered. With this restriction the ex perimental and calculated spectra agree very well. We discuss implications for dynamical studies of wave packet motions. (C) 1999 American Institute o f Physics. [S0021-9606(99)70629-X].