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Density Functional Theory for Molecule-Metal Surface Reactions: When Does the Generalized Gradient Approximation Get
Nick Gerrits1, Egidius W F Smeets1, Stefan Vuckovic2
1Leiden Institute of Chemistry, Leiden University, Gorlaeus Laboratories, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
The Journal of Physical Chemistry Letters
|December 9, 2020
Summary
Generalized gradient approximation density functional theory (GGA-DFT) accurately predicts molecule-metal reactions when the work function-electron affinity difference exceeds ~7 eV. For challenging cases like O2 on Al(111), hybrid functionals with long-range screening offer a solution.
Area of Science:
- Computational chemistry
- Materials science
- Surface science
Background:
- Density functional theory (DFT) is widely used in chemistry but has limitations.
- Generalized gradient approximation (GGA) functionals in DFT often fail for gas-phase reaction barriers and some molecule-metal surface reactions.
- Predicting the accuracy of GGA-DFT for molecule-metal surface reactions has been challenging.
Purpose of the Study:
- To identify criteria for the success or failure of GGA-DFT in describing molecule-metal surface reactions.
- To investigate methods for improving the accuracy of DFT calculations for challenging systems, such as the sticking of O2 on Al(111).
- To explore computationally efficient approaches for calculating potential energy surfaces.
Main Methods:
- Analysis of the relationship between GGA-DFT performance and the difference between metal work function and molecule electron affinity.
- Dynamics calculations using hybrid functionals with long-range screening for the O2 + Al(111) system.
- Computation of potential energy surfaces using nonself-consistent hybrid functional calculations on GGA densities.
Main Results:
- GGA-DFT accuracy for molecule-metal surface reactions correlates with the work function-electron affinity difference, generally succeeding when the difference is > ~7 eV.
- The sticking of O2 on Al(111) is accurately described by hybrid functionals with long-range screening, suggesting GGA-DFT errors are functional-driven.
- Nonself-consistent hybrid functional calculations on GGA densities provide a computationally cheap method for treating difficult systems.
Conclusions:
- A clear criterion for GGA-DFT applicability in molecule-metal surface reactions is established based on electronic properties.
- Hybrid functionals with long-range screening are effective for accurately describing problematic molecule-metal interactions.
- A practical approach is proposed for accurate and efficient computation of potential energy surfaces in challenging chemical systems.
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