2008/12/31 by Ismaila Dabo, Éric Cancès, Dabo, I. +5
Chemistry · Energy · Engineering · #Electrocatalysts for Energy Conversion #Electrochemical Analysis and Applications #FOS: Physical sciences #Materials Science (cond-mat.mtrl-sci) #Molecular Junctions and Nanostructures #Other Condensed Matter (cond-mat.other)
paper · pdf · doi:10.48550/arxiv.0901.0096
openalex publication_date 2008/12/31 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
Chemisorbed molecules at a fuel cell electrode are a very sensitive probe of\nthe surrounding electrochemical environment, and one that can be accurately\nmonitored with different spectroscopic techniques. We develop a comprehensive\nelectrochemical model to study molecular chemisorption at either constant\ncharge or fixed applied voltage, and calculate from first principles the\nvoltage dependence of vibrational frequencies -- the vibrational Stark effect\n-- for CO adsorbed on close-packed platinum electrodes. The predicted\nvibrational Stark slopes are found to be in very good agreement with\nexperimental electrochemical spectroscopy data, thereby resolving previous\ncontroversies in the quantitative interpretation of in-situ experiments and\nelucidating the relation between canonical and grand-canonicaldescriptions of\nvibrational surface phenomena.\n