Elucidating the structure and dynamics of CO ad-layers on MgO surfaces
Literature Information
Jefferson Maul, Giuseppe Spoto, Lorenzo Mino, Alessandro Erba
The combination of quantum-mechanical simulations and infrared absorption spectroscopy measurements provides a clear picture for a long standing puzzle in surface science: the actual structure and vibrational dynamics of the low-temperature ordered CO monolayer adsorbed on (001) MgO surfaces. The equilibrium structure of the commensurate (4 × 2) adsorbed phase consists of three CO molecules per primitive cell (surface coverage of 75%) located at two inequivalent sites: one molecule seats upright on top of a Mg site while two molecules, tilted off the normal to the surface, are symmetrically positioned relative to the upright one with anti-parallel projections on the surface. This configuration, long believed to be incompatible with measured polarization infrared spectra, is shown to reproduce all observed spectral features, including a new, unexpected one: the vanishing anharmonicity of CO stretching modes in the monolayer.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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