463728 A New DFT-Based Approach That More Accurately Predicts Adsorption Energies

Tuesday, November 15, 2016: 3:45 PM
Franciscan D (Hilton San Francisco Union Square)
Alyssa Hensley1, Kushal Ghale2, Carolin Rieg1, Thanh Dang2, Emily Anderst1, Felix Studt3, Charles T. Campbell4, Jean-Sabin McEwen1 and Ye Xu2, (1)The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA, (2)Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA, (3)Karlsruhe Institute of Technology, Karlsruhe, Germany, (4)Chemistry and Chemical Engineering Departments, University of Washington, Seattle, WA

The development of density functional theory (DFT) functionals which accurately predict the energetics of heterogeneous catalytic processes, such as adsorption/desorption and bond breaking/forming, is crucial to the design and optimization of heterogeneous catalysts. For adsorption systems, the current DFT functionals give reasonable accuracy for selected classes of adsorbates, but far less than desired when looking at systems across the spectrum from strongly chemisorbed to strongly van der Waals bonded [1-7]. Improved accuracy across this whole spectrum could have tremendous impact on catalysis research and discovery. In this contribution, we present a new method for accurately predicting both molecular and dissociative adsorption energies based on DFT calculations with periodic boundary conditions. This method was benchmarked against a set of 39 experimental adsorption reactions with corresponding accurate calorimetric measurements. Our results show that our proposed method has a mean absolute error (MAE) and root mean squared error (RMSE) of 15 and 20 kJ/mol, respectively, making this method more accurate than the BEEF-vdW functional [3], which is the most accurate known DFT method for adsorbates, with a MAE and RMSE of 20 and 26 kJ/mol [3]. As such, this method accurately predicts adsorption energies for processes regardless of whether they are dominated by charge transfer or dispersion forces, and produces superior accuracy to any current standard DFT functional alone.


[1] J. Wellendorff, T. L. Silbaugh, D. Garcia-Pintos, J. K. Nørskov, T. Bligaard, F. Studt, C. T. Campbell, Surf. Sci. 640 (2015) 36-44.

[2] A. J. Cohen, P. Mori-Sanchez, W. Yang, Chem. Rev. 112 (2012) 289-320.

[3] J. Wellendorff, K. T. Lundgaard, A. Møgelhøj, V. Petzold, D. D. Landis, J. K. Nørskov, T. Bligaard, K. W. Jacobsen, Phys. Rev. B 85 (2012) 235149.

[4] J. Klimeš, D. R. Bowler, A. Michaelides, Phys. Rev. B 83 (2011) 195131.

[5] J. Klimeš, D. R. Bowler, A. Michaelides, J. Phys.: Condens. Matter 22 (2010) 022201.

[6] M. Dion, H. Rydberg, E. Schröder, D. C. Langreth, B. I. Lundqvist, Phys. Rev. Lett. 92 (2004) 246401.

[7] A. V. Krukau, O. A. Vydrov, A. F. Izmaylov, G. E. Scuseria, J. Chem. Phys. 125 (2006) 224106.

Extended Abstract: File Not Uploaded