Support effects on conical intersections of Jahn-Teller fluxional metal clusters on the sub-nanoscale.

Abstract

The concept of fluxionality has been invoked to explain the enhanced catalytic properties of atomically precise metal clusters of subnanometer size. Cu3 isolated in the gas phase is a classical case of a fluxional metal cluster where a conical intersection leads to a Jahn-Teller (JT) distortion resulting in a potential energy landscape with close-lying multiminima and, ultimately, fluxional behavior. In spite of the role of conical intersections in the (photo)stability and (photo)catalytic properties of surface-supported atomic metal clusters, they have been largely unexplored. In this work, by applying a high-level multi-reference ab initio method aided with dispersion corrections, we analyze support effects on the conical intersection of Cu3 considering benzene as a model support molecule of carbon-based surfaces. We verify that the region around the conical intersection and the associated Jahn-Teller (JT) distortion is very slightly perturbed by the support when the Cu3 cluster approaches it in a parallel orientation: Two electronic states remain degenerate for a structure with C3 symmetry consistent with the D3h symmetry of unsupported Cu3 at the conical intersection. It extends over a one-dimensional seam that characterizes a physisorption minimum of the Cu3-benzene complex. The fluxionality of the Cu3 cluster, reflected in large fluctuations of relaxed Cu-Cu distances as a function of the active JT mode, is kept unperturbed upon complexation with benzene as well. In stark contrast, for the energetically favored perpendicular orientation of the Cu3 plane to the benzene ring plane, the conical intersection (CI) is located 12 100 cm-1 (∼1.5 eV) above the chemisorption minimum, with the fluxionality being kept at the CI's nearby and lost at the chemisorption well. The first excited state at the perpendicular orientation has a deep well (>4000 cm-1), being energetically closer to the CI. The transition dipole moment between ground and excited states has a significant magnitude, suggesting that the excited state can be observed through direct photo-excitation from the ground state. Besides demonstrating that the identity of an isolated Jahn-Teller metal cluster can be preserved against support effects at a physisorption state and lifted out at a chemisorption state, our results indicate that a correlation exists between conical intersection topography and fluxionality in the metal cluster's Cu-Cu motifs.