Orbital-Specific Modeling of CO Chemisorption

TL;DR

This paper introduces an orbital-specific tight-binding model that accurately predicts CO chemisorption energies across various metals, surface terminations, and strain conditions by decomposing the d-band into atomic orbitals.

Contribution

It presents a novel orbital-specific modeling approach that captures chemisorption energy variations by analyzing substrate electronic structure changes.

Findings

Model accurately predicts chemisorption trends across different conditions.

Decomposition of the d-band into atomic orbitals is crucial for predictions.

Density functional theory data supports the model's validity.

Abstract

We demonstrate that variations in molecular chemisorption energy on different metals, different surface terminations, and different strain conditions can be accounted for by orbital-specific changes in the substrate electronic structure. Our density functional theory data set, spanning three metals, two surface terminations, and five strain states, is fit to a single model based on tight binding. A crucial aspect of the model is decomposition of the $d$-band into contributions from the five $d$ atomic orbitals. This provides a representation of the energy levels of the substrate that are directly relevant to the chemisorption bond, leading to accurate prediction of chemisorption trends.