Hybrid RPA:DFT Approach for Adsorption on Transition Metal Surfaces: Methane and Ethane on Platinum (111)
Sheldon C, Paier J, Usvyat D, Sauer J (2024)
Publication Type: Journal article
Publication year: 2024
Journal
Book Volume: 20
Pages Range: 2219-2227
Journal Issue: 5
Abstract
The hybrid QM:QM approach is extended to adsorption on transition metal surfaces. The random phase approximation (RPA) as the high-level method is applied to cluster models and, using the subtractive scheme, embedded in periodic models which are treated with density functional theory (DFT) that is the low-level method. The PBE functional, both without dispersion and augmented with the many-body dispersion (MBD), is employed. Adsorption of methane and ethane on the Pt(111) surface is studied. For methane in a 2 × 2 surface cell, the hybrid RPA:PBE and RPA:PBE+MBD results, −14.3 and −16.0 kJ mol-1, respectively, are in close agreement with the periodic RPA value of −13.8 kJ mol-1 at significantly reduced computational cost (factor of ∼50). For methane and ethane, the RPA:PBE results (−14.3 and −17.8 kJ mol-1, respectively) indicate underbinding relative to energies derived from experimental desorption barriers for relevant loadings (−15.6 ± 1.6 and −27.2 ± 2.9 kJ mol-1, respectively), whereas the hybrid RPA:PBE+MBD results (−16.0 and −24.9 kJ mol-1, respectively) agree with the experiment well within experimental uncertainty limits (deviation of −0.4 ± 1.5 and +2.3 ± 2.9 kJ mol-1, respectively). Finding a cluster that adequately and robustly represents the adsorbate at the bulk surface is important for the success of the RPA-based QM:QM scheme for metals.
Involved external institutions
Germany (DE)How to cite
APA:
Sheldon, C., Paier, J., Usvyat, D., & Sauer, J. (2024). Hybrid RPA:DFT Approach for Adsorption on Transition Metal Surfaces: Methane and Ethane on Platinum (111). Journal of Chemical Theory and Computation, 20(5), 2219-2227. https://dx.doi.org/10.1021/acs.jctc.3c01308
MLA:
Sheldon, Christopher, et al. "Hybrid RPA:DFT Approach for Adsorption on Transition Metal Surfaces: Methane and Ethane on Platinum (111)." Journal of Chemical Theory and Computation 20.5 (2024): 2219-2227.
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