Density Functional Theory for Molecule-Metal Surface Reactions: When Does the Generalized Gradient Approximation Get It Right, and What to Do If It Does Not.

ABSTRACT: While density functional theory (DFT) is perhaps the most used electronic structure theory in chemistry, many of its practical aspects remain poorly understood. For instance, DFT at the generalized gradient approximation (GGA) tends to fail miserably at describing gas-phase reaction barriers, while it performs surprisingly well for many molecule-metal surface reactions. GGA-DFT also fails for many systems in the latter category, and up to now it has not been clear when one may expect it to work. We show that GGA-DFT tends to work if the difference between the work function of the metal and the molecule's electron affinity is greater than ∼7 eV and to fail if this difference is smaller, with sticking of O₂ on Al(111) being a spectacular example. Using dynamics calculations we sho

SUBMITTER: Gerrits N 

PROVIDER: S-EPMC7751010 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature