s-d Electronic interactions induced H2 dissociation on the \gamma-U(100) surface and influences of niobium doping

TL;DR

This study uses density functional theory to show that hydrogen molecules can dissociate without barriers on both clean and niobium-doped b5-U(100) surfaces, highlighting the role of electronic interactions in the process.

Contribution

It reveals the electronic mechanisms behind barrierless hydrogen dissociation on b5-U(100) surfaces and the effect of Nb doping on this process.

Findings

Hydrogen dissociates without barriers on clean b5-U(100) surface.

Nb doping maintains barrierless dissociation and accelerates electronic energy lowering.

Charge transfer and hybridization involving hydrogen s and uranium d or niobium d states are key factors.

Abstract

The dissociation of hydrogen molecules on the \gamma-U(100) surface is systematically studied with the density functional theory method. Through potential energy surface calculations, we find that hydrogen molecules can dissociate without any barriers on the clean \gamma-U(100) surface. After careful electronic analysis, it is found that charge transfer between the hydrogen s and uranium d electronic states causes the dissociation, which is quite different from the dissociation of hydrogen molecules on other actinide metal surfaces. Considering that doping of 3d transition metal atoms can stabilize the \alpha phase of U, we also study the influences of Nb-doping on the hydrogen dissociation process. We find that the 3d electronic states of Nb also take part in the hybridization with hydrogen s electronic states, which leads to the result that hydrogen molecules also dissociate without any energy barriers on the doped U surface. In addition, the free electronic energy lowers down more quickly for a hydrogen molecule approaching the doped U surface.