Here, we calculate the free energy interaction between adsorbed *OH and K+/Li+ situated at the liquid water–Pt(111) interface using ab initio molecular dynamics (AIMD) and metadynamics. Li+ stabilizes *OH by 0.1 ± 0.1 eV and K+ destabilizes *OH by 0.1 ± 0.1 eV, in qualitative agreement with experimental cyclic voltammogram (CV) measurements. In contrast, the internal energy of *OH is stabilized by 0.3 eV and 0.4 eV for Li+ and K+, respectively. This demonstrates that entropy significantly destabilizes cation–*OH interactions and is vital in order to understand even the relative influence of cations at interfaces.
Henrik H. Kristoffersen, Karen Chan, Tejs Vegge and Heine Anton Hansen
CHEMICAL COMMUNICATIONS, Volume: 56 Issue: 3 Pages: 427-430
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