Assessment of mBEEF and RPBE exchange-correlation functionals for describing the adsorption of C2H2 and C2H4 on transition-metal surfaces

24 May 2024, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Describing the interaction between reactive species and surfaces is crucial for designing catalyst materials. Density-functional approximation is able to quantitatively model such interaction, but its accuracy strongly depends on the choice of exchange-correlation (XC) functional approximation. In this work, we assess the performance of mBEEF and RPBE functionals for describing the interaction of C2H2 and C2H4 with (111) surfaces of Cu, Pt, Pd, and Rh face-center-cubic transition metals. In particular, we study the geometry and the vibrational frequencies associated with the adsorbed molecules, as well as the adsorption energies. Crucially, experimental values for vibrational frequencies of molecules adsorbed on the metal surfaces are available for more system compared to physical quantities typically used to benchmark of XC functionals, such as adsorption energies. Thus, vibrational frequencies can be utilized as reference to assess the reliability of the exchange-correlation functionals. We find that the mean percentage errors (MPEs) of RPBE and mBEEF with respect to reported experimental values of vibrational frequencies are 0.64% and -3.88 %, respectively (36 data points). For adsorption enthalpy, RPBE and mBEEF provide MPEs of 27.61 and -59.81%, respectively, with respect to reported experimental values (7 data points). Therefore, the performance of RPBE is superior to that of mBEEF for the considered systems.


Vibrational frequency


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