کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5422250 | 1507908 | 2014 | 8 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
DFT-GGA errors in NO chemisorption energies on (111) transition metal surfaces
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
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چکیده انگلیسی
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 2Ïâ 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 5Ï orbital to the 2Ïâ orbital in the gas-phase NO G2Σâ â X2Î excitation. We establish linear relationships between Echem and ÎEG â 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 0.25 ML. We note that the slope of Echemvs. ÎEG â 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.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Surface Science - Volume 621, March 2014, Pages 23-30
Journal: Surface Science - Volume 621, March 2014, Pages 23-30
نویسندگان
Xu Huang, Sara E. Mason,