  This work addresses a longstanding theoretical discrepancy using Density
Functional Theory (DFT) with experimental observations of CO binding trends on
electrocatalytically relevant metals for the CO2 reduction reaction (CO2RR). By
introducing thermal fluctuations using appropriate statistical mechanical NVT
and NPT ensembles, we show that DFT with universal dispersion interactions
yields qualitatively better metal surface strain trends and CO binding
energetics, consistently predicts the correct site preference for all metals
due to thermally induced surface distortions that preferentially exposes the
undercoordinated atop site for Cu(111) and Pt(111), and for the weak binding
Ag(111) and Au(111) surfaces at finite temperatures shows CO-metal interactions
that are a mixture of chemisorbed and physisorbed species. This study better
places theory as an equal partner to experimental heterogeneous catalysis by
demonstrating the need to fully account for finite temperature fluctuations to
make contact with surface science experiments.
