Journal article
DFT-GGA errors in NO chemisorption energies on (111) transition metal surfaces
Surface science, Vol.621, pp.23-30
03/2014
DOI: 10.1016/j.susc.2013.09.024
Abstract
We investigate whether well-known DFT-GGA errors in predicting the chemisorption energy (Echem) of CO on transition metal surfaces manifest in analogous NO chemisorption systems. While widely investigated in the case of CO/metal, analogous DFT-GGA errors have long been claimed to be absent in NO/metal chemisorption. Here, we provide theoretical evidence of systematic enhanced back-donation in NO/metal chemisorption at the DFT-GGA level. We use electronic structure analysis to show that the partially filled molecular NO 2π⁎ orbital rehybridizes with the transition metal d-band to form new bonding and anti-bonding states. We relate the back-donation charge transfer associated with chemisorption to the promotion of an electron from the 5σ orbital to the 2π⁎ orbital in the gas-phase NO G2Σ−←X2Π excitation. We establish linear relationships between Echem and ΔEG←X and formulate an Echem correction scheme in the style of Mason et al. [Physical Review B 69, 161401(R)]. We apply the NO Echem correction method to the (111) surfaces of Pt, Pd, Rh, and Ir, with NO chemisorption modeled at a coverage of 0.25ML. We note that the slope of Echemvs. ΔEG←X and the dipole moment depend strongly on adsorption site for each metal, and we construct an approximate correction scheme which we test using NO/Pt(100) chemisorption. •Similar to CO, NO chemisorption on metal surfaces can be overestimated by DFT-GGA.•The NO chemisorption mechanism relates to transitions in gas-phase NO.•A correction scheme based on chemisorption and excitation energies is established.•Post-correction chemisorption energies decrease up to 18%, relative values change.•An approximate dipole-based correction scheme requires less DFT calculations.
Details
- Title: Subtitle
- DFT-GGA errors in NO chemisorption energies on (111) transition metal surfaces
- Creators
- Xu HuangSara E Mason
- Resource Type
- Journal article
- Publication Details
- Surface science, Vol.621, pp.23-30
- DOI
- 10.1016/j.susc.2013.09.024
- ISSN
- 0039-6028
- eISSN
- 1879-2758
- Publisher
- Elsevier B.V
- Grant note
- name: University of Iowa College of Liberal Arts and Sciences; name: Iowa Center for Research by Undergraduates
- Language
- English
- Date published
- 03/2014
- Academic Unit
- Chemistry
- Record Identifier
- 9983985855302771
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