Potential Energy Surface of Group 11 Trimers (Cu, Ag, Au): Bond Angle Isomerism in Au₃

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 Cu₃, Ag₃, and Au₃ is the ²B₂ (∼65° 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 Cu₃ and Ag₃. The inclusion of spin-orbit corrections for Au₃ makes the ²B₂ (∼65°) and ²A₁ (∼55°) states approximately degenerate. A novel ²B₂ isomer of Au₃ at an obtuse angle of ∼125° was also characterized, providing evidence for bond angle isomerism on the same ²B₂ potential energy surface. Spin-orbit corrections increase the barrier height between the ²B₂ (65°) and ²B₂ (125°) bond angle isomers of Au₃. The calculated symmetric stretch vibrational frequencies are in good agreement with the available experimental values. All frequencies calculated for the Au₃ ²B₂ (∼125°) state are real, and there is at least one bound bending vibration for this state. Jahn-Teller parameters are also derived for each trimer.