Potential Energy Landscape of CO Adsorbates on NaCl(100) and Implications in Isomerization of Vibrationally Excited CO

Several full-dimensional potential energy surfaces (PESs) are reported for vibrating CO adsorbates at two coverages on a rigid NaCl(100) surface based on first principles calculations. These PESs reveal a rather flat energy landscape for physisorption of vibrationless CO on NaCl(100), evidenced by various C-down adsorption patterns within a small energy range. Agreement with available experimental results is satisfactory, although quantitative differences exist. These PESs are used to explore isomerization pathways between the C-down and higher energy O-down configurations, which reveal a significant isomerization barrier. As CO vibration is excited, however, the energy order of the two isomer changes, which helps to explain the experimental observed flipping of vibrationally excited CO adsorbates.