Quantitative theory of magnetic properties of elemental praseodymium

TL;DR

This paper develops an ab-initio theoretical model combining density-functional theory and dynamical mean-field theory to explain the non-magnetic ground state of elemental praseodymium, a rare-earth metal with a unique crystal structure.

Contribution

It constructs a realistic effective magnetic Hamiltonian for praseodymium, predicting singlet crystal-field ground states and analyzing surface effects with potential for exotic orders.

Findings

Pr exhibits a singlet crystal-field ground state at both lattice sites.

Intersite exchange interactions are too weak to induce magnetism.

Surface effects reduce the gap, enabling possible multipolar orders.

Abstract

Elemental Pr metal crystallizes in the double hexagonal close packed (dhcp) structure and is unique among rare-earth elements in featuring a localized partially filled 4f shell without ordered magnetism. Experimental evidence attributes this absence of magnetism to a singlet crystal-field (CF) ground state of the Pr 4f$^2$ configuration, which is energetically well isolated from excited magnetic doublets. Here, we construct a realistic effective magnetic Hamiltonian for dhcp Pr, by combining density-functional theory with dynamical mean-field theory, in the quasiatomic Hubbard-I approximation. Our calculations fully determine the CF potential and predict singlet CF ground states at both inequivalent sites of the dhcp lattice. The intersite exchange interactions, obtained from the magnetic force theorem, are found to be insufficient to close the CF gap to the magnetic doublets. Hence, ab-initio theory is demonstrated to explain the unusual, non-magnetic state of elemental Pr. Extending this analysis to the (0001) surface of Pr, we find that the singlet ground state remains robust preventing conventional magnetic orders. Nevertheless, the gap between the ground state and the lowest excited singlet is significantly reduced at the surface, opening the possibility for exotic two-dimensional multipolar orders to emerge within this two-singlet manifold.