Journal of Physical Chemistry A, Vol.123, No.6, 1198-1207, 2019
Potential Energy Surface of Group 11 Trimers (Cu, Ag, Au): Bond Angle Isomerism in Au-3
Potential energy surfaces for the group 11 trimers were generated at various levels of coupled-cluster theory to examine the effects of Jahn-Teller distortions. Our calculations show that the lowest-energy conformer for Cu-3, Ag-3, and Au-3 is the B-2(2) (similar to 65 degrees isomer) without spin-orbit corrections. Spin-orbit corrections have negligible contributions to the relative energies for the angle dependence of the potential energy surfaces for Cu-3 and Ag-3. The inclusion of spin-orbit corrections for Au-3 makes the B-2(2) (similar to 65 degrees) and (2)A(1) (similar to 55 degrees) states approximately degenerate. A novel B-2(2) isomer of Au-3 at an obtuse angle of,similar to 125 degrees was also characterized, providing evidence for bond angle isomerism on the same B-2(2) potential energy surface. Spin-orbit corrections increase the barrier height between the B-2(2) (65) and B-2(2) (125) bond angle isomers of Au-3. The calculated symmetric stretch vibrational frequencies are in good agreement with the available experimental values. All frequencies calculated for the Au-3 B-2(2) (similar to 125 degrees) state are real, and there is at least one bound bending vibration for this state. Jahn-Teller parameters. Ca are also derived for each trimer.