CO Inversion on a NaCl(100) Surface: A Multireference Quantum Embedding Study

[Image: see text] We develop a multireference quantum embedding model to investigate a recent experimental observation of the isomerization of vibrationally excited CO molecules on a NaCl(100) surface [Science2020, 367, 175–178]. To explore this mechanism, we built a reduced potential energy surface of CO interacting with NaCl(100) using a second-order multireference perturbation theory, modeling the adsorbate–surface interaction with our previously developed active space embedding theory (ASET). We considered an isolated CO molecule on NaCl(100) and a high-coverage CO monolayer (1/1), and for both we generated potential energy surfaces parametrized by the CO stretching, adsorption, and inversion coordinates. These surfaces are used to determine stationary points and adsorption energies and to perform a vibrational analysis of the states relevant to the inversion mechanism. We found that for near-equilibrium bond lengths, CO adsorbed in the C-down configuration is lower in energy than in the O-down configuration. Stretching of the C–O bond reverses the energetic order of these configurations, supporting the accepted isomerization mechanism. The vibrational constants obtained from these potential energy surfaces show a small (< 10 cm(–1)) blue- and red-shift for the C-down and O-down configurations, respectively, in agreement with experimental assignments and previous theoretical studies. Our vibrational analysis of the monolayer case suggests that the O-down configuration is energetically more stable than the C-down one beyond the 16th vibrational excited state of CO, a value slightly smaller than the one from quasi-classical trajectory simulations (22nd) and consistent with the experiment. Our analysis suggests that CO–CO interactions in the monolayer play an important role in stabilizing highly vibrationally excited states in the O-down configuration and reducing the barrier between the C-down and O-down geometries, therefore playing a crucial role in the inversion mechanism.