Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 136, Issue 5, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.3679167
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Funding
- Department of Energy, Office of Basic Energy Sciences, Catalysis Science Division [DE-FG02-03ER15478]
- U.S. Department of Energy (DOE) [DE-FG02-03ER15478] Funding Source: U.S. Department of Energy (DOE)
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We investigated the molecular binding of n-alkanes on Pd(111) and PdO(101) using conventional density functional theory (DFT) and the dispersion-corrected DFT-D3 method. In agreement with experimental findings, DFT-D3 predicts that the n-alkane desorption energies scale linearly with the molecule chain length on both surfaces, and that n-alkanes bind more strongly on PdO(101) than on Pd(111). The desorption energies computed using DFT-D3 are slightly higher than the measured values for n-alkanes on Pd(111), though the agreement between computation and experiment is a significant improvement over conventional DFT. The measured desorption energies of n-alkanes on PdO(101) and the energies computed using DFT-D3 agree to within better than 2.5 kJ/mol (<5%) for chain lengths up to n-butane. The DFT-D3 calculations predict that the molecule-surface dispersion energy for a given n-alkane is similar in magnitude on Pd(111) and PdO(101), and that dative bonding between the alkanes and coordinatively unsaturated Pd atoms is primarily responsible for the enhanced binding of n-alkanes on PdO(101). From analysis of the DFT-D3 results, we estimate that the strength of an alkane eta(2)(H, H) interaction on PdO(101) is similar to 16 kJ/mol, while a single eta(1) H-Pd dative bond is worth about 10 kJ/mol. (C) 2012 American Institute of Physics. [doi:10.1063/1.3679167]
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