Resilience of gas-phase anharmonicity in the vibrational response of adsorbed carbon monoxide and breakdown under electrical conditions

TL;DR

This study investigates the persistence of anharmonic vibrational properties of adsorbed CO on metal surfaces and reveals that electrical conditions can disrupt established vibrational correlations, challenging finite-cluster modeling approaches.

Contribution

It demonstrates that Badger's rule, relating vibrational frequency and bond length, holds for isolated CO but breaks down under electrical conditions in periodic slab models, highlighting modeling limitations.

Findings

Badger's rule applies to isolated CO molecules.

Electrical conditions can cause breakdown of Badger's rule in periodic models.

Finite-cluster models may not accurately capture electrical effects at electrodes.

Abstract

In surface catalysis, the adsorption of carbon monoxide on transition-metal electrodes represents the prototype of strong chemisorption. Notwithstanding significant changes in the molecular orbitals of adsorbed CO, spectroscopic experiments highlight a close correlation between the adsorbate stretching frequency and equilibrium bond length for a wide range of adsorption geometries and substrate compositions. In this work, we study the origins of this correlation, commonly known as Badger's rule, by deconvoluting and examining contributions from the adsorption environment to the intramolecular potential using first-principles calculations. Noting that intramolecular anharmonicity is preserved upon CO chemisorption, we show that Badger's rule for adsorbed CO can be expressed solely in terms of the tabulated Herzberg spectroscopic constants of isolated CO. Moreover, although it had been previously established using finite-cluster models that Badger's rule is not affected by electrical conditions, we find here that Badger's rule breaks down when the electrified surface is represented as a periodic slab. Examining this breakdown in terms of anharmonic contributions from the effective surface charge reveals limitations of conventional finite-cluster models in describing electrical conditions at metal electrodes.