Energetics and Electronic Structure of Plutonium

TL;DR

This paper provides a comprehensive first-principles analysis of plutonium's phases, explaining its unique energetics and electronic structure, and aligning well with experimental data.

Contribution

It offers the first unified theoretical description of all plutonium phases' energetics and $f$ electronic structure based on fundamental principles.

Findings

Good quantitative agreement with experimental energetics

Clarifies the role of $f$-electron correlations

Describes the pressure-volume phase diagram of Pu

Abstract

Plutonium is the most exotic and mysterious element in the periodic table. It has 6 metallic phases and peculiar physical properties not yet understood. One of the most intriguing properties of Pu is that relatively small changes of temperature can induce transitions between different structures, that are accompanied by very large changes of equilibrium volumes. This fact has stimulated extensive theoretical and experimental studies. In spite of this, a convincing explanation of the metallurgic properties of Pu based on fundamental principles is still lacking, and none of the previous theories has been able to describe simultaneously the energetics and the $f$ electronic structure of all of the phases of Pu on the same footing. Here we provide a bird's eye view of Pu by studying the zero-temperature pressure-volume phase diagram and the $f$ electronic structure of all of its crystalline phases from first principles. In particular, we clarify the way in which the $f$-electron correlations determine its unusual energetics. Our theoretical energetics and ground-state $f$ electronic structure are both in good quantitative agreement with the experiments.