The 5f localization/delocalization in square and hexagonal americium monolayers: A FP-LAPW electronic structure study

TL;DR

This study uses FP-LAPW calculations to explore how spin polarization, spin-orbit coupling, and exchange-correlation approximations influence the electronic and geometric properties of americium monolayers and bulk, revealing potential 5f electron delocalization effects.

Contribution

It provides a detailed first-principles analysis of americium monolayers, highlighting the impact of various approximations and the possibility of surface 5f delocalization, which is novel.

Findings

Spin polarization and spin-orbit coupling significantly affect properties.

LDA underestimates lattice constants compared to GGA.

Potential 5f delocalization at americium surfaces suggested.

Abstract

The electronic and geometrical properties of bulk americium and square and hexagonal americium monolayers have been studied with the full-potential linearized augmented plane wave (FP-LAPW) method. The effects of several common approximations are examined: (1) non-spin polarization (NSP) vs. spin polarization (SP); (2) scalar-relativity (no spin-orbit coupling (NSO)) vs. full-relativity (i.e., with spin-orbit (SO) coupling included); (3) local-density approximation (LDA) vs. generalized-gradient approximation (GGA). Our results indicate that both spin polarization and spin orbit coupling play important roles in determining the geometrical and electronic properties of americium bulk and monolayers. A compression of both americium square and hexagonal monolayers compared to the americium bulk is also observed. In general, the LDA is found to underestimate the equilibrium lattice constant and give a larger total energy compared to the GGA calculations. While spin orbit coupling shows a similar effect on both square and hexagonal monolayer calculations regardless of the model, GGA versus LDA, an unusual spin polarization effect on both square and hexagonal monolayers is found in the LDA results as compared with the GGA results. The 5f delocalization transition of americium is employed to explain our observed unusual spin polarization effect. In addition, our results at the LDA level of theory indicate a possible 5f delocalization could happen in the americium surface within the same Am II (fcc crystal structure) phase, unlike the usually reported americium 5f delocalization which is associated with crystal structure change. The similarities and dissimilarities between the properties of an Am monolayer and a Pu monolayer are discussed in detail.