Jahn-Teller and related effects in the silver trimer. I. The ab initio calculation of spectroscopically observable parameters for the X 2E' and A 2E" electronic states.
Extensive ab initio calculations were performed for the X2E' and A2E" states of Ag3, using a newly constructed basis set for Ag. An important goal of these calculations is to guide the analysis of the experimentally observed A 2E"-X2E' electronic spectrum. Vibrational frequencies of Ag(3) for both the X and A states are reported. Spectroscopically obtainable parameters describing the Jahn-Teller effect are calculated for the X and A states. The magnitude of the spin-orbit effects for this relativistic system was also calculated for the X2E' and A 2E" states. Using all this information, the X-A electronic spectrum is predicted for Ag(3). Additionally, the geometries and symmetries of the global minima and saddle points as well as the barrier to pseudorotation around the moat of the potential energy surface are determined for both states.
Sioutis
Ilias
I
Department of Chemistry, The Ohio State University, 120 West 18th Avenue, Columbus, Ohio 43210, USA.
Stakhursky
Vadim L
VL
Pitzer
Russell M
RM
Miller
Terry A
TA