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Updated: Oct 19, 2026

Experimental Methods for Spin- and Angle-Resolved Photoemission Spectroscopy Combined with Polarization-Variable Laser
Published on: June 28, 2018
Toward resolving the RuO2/IrO2 oxygen evolution activity puzzle: critical roles of spin polarization and
Xiaokun Xie1, Jiashun Wu1, Zhenbin Wang1,2
1Department of Materials Science and Engineering, City University of Hong Kong Hong Kong SAR 999077 China zwan22@cityu.edu.hk.
Abstract:
The oxygen evolution reaction (OER) activity ordering of RuO2 and IrO2 is well established experimentally, yet density functional theory calculations have persistently failed to reproduce this trend, undermining computational catalyst design. Here, we investigate this discrepancy by evaluating OER thermodynamic and kinetic activities of IrO2 and RuO2 using four exchange-correlation (XC) functionals (PBE, RPBE, r2SCAN, and MS2-rVV10) under spin-polarized and spin-unpolarized conditions. Spin polarization selectively stabilizes the O* intermediate on IrO2 while leaving RuO2 comparatively unaffected, and neglecting spin effects yields unphysically low kinetic barriers for IrO2. Among the four functionals, only MS2-rVV10 reproduces the experimentally observed activity trend in both thermodynamic and kinetic analyses. We trace these failures to a systematic correlation between adsorption-energy errors and deviations in the predicted activity trend. Notably, the OOH*-OH* scaling offset and theoretical limiting potential are themselves XC-functional dependent, cautioning against cross-functional comparison of overpotentials. Cross-code benchmarks rule out numerical implementation as the error source, while higher-rung functionals progressively overestimate Ru local magnetic moments in RuO2, introducing additional errors. This work establishes accurate exchange-correlation functionals and proper spin-polarization treatment as prerequisites for reliable OER catalyst design.
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