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

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journal contribution
posted on 25.08.2020, 14:38 by Jun Chen, Seenivasan Hariharan, Jörg Meyer, Hua Guo
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 the 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.