A Relativistic DFT Study of Water Adsorption on delta-Plutonium (111) Surface

TL;DR

This study uses relativistic DFT-GGA to investigate how water adsorbs on delta-Plutonium (111) surfaces, revealing different behaviors for molecular and dissociative states and their electronic interactions.

Contribution

It provides new insights into water adsorption mechanisms on delta-Plutonium (111), highlighting the role of orbital interactions and electron localization.

Findings

Water is physisorbed in a flat orientation at on-top sites.

Dissociative adsorption leads to chemisorption and surface rumpling.

Pu-5f electrons remain inert during molecular adsorption.

Abstract

Scalar-relativistic DFT-GGA has been used to study adsorption of water in molecular and dissociative configurations on delta-Plutonium (111) surface. In molecular state, water is physisorbed in an almost flat-lying orientation at a one-fold coordinated on-top site. The interaction of the water 1b1 orbital and the Pu-6d orbital provides the stability of water on the surface, implying that the Pu-5f electrons remain chemically inert. The co-adsorption cases of partially dissociated and fully dissociated products at the three-fold hollow sites yield chemisorption, coupled with rumpling of the surface layer and delocalization of the Pu-5f electrons and formation of strong ionic bonds.