Generalized Hund's rule for two-atom systems

TL;DR

This paper investigates how Hund's rule is modified in two-atom systems with three t2g orbitals, revealing conditions where spin-orbit interactions are enhanced by Hund's coupling, bridging band theory and strong correlation physics.

Contribution

It introduces a new approach to study the interplay between transfer integral and Hund's coupling in two-atom systems, generalizing Hund's third rule with focus on spin-orbit interaction enhancement.

Findings

Effective spin-orbit interactions can be significantly enhanced by Hund's coupling.

The crossover from molecular orbital to strong correlation limit depends on the competition between t and J.

Enhancement occurs notably with intermediate Hund's coupling and specific electron fillings.

Abstract

Hund's rule is one of the fundamentals of the correlation physics at the atomic level, determining the ground state multiplet of the electrons. It consists of three laws: (i) maximum $S$ (total spin), (ii) maximum $L$ (total orbital angular momentum) under the constraint of (i), and (iii) the total angular momentum $J$ is $|L-S|$ for electron number less than half, while $J=L+S$ for more than half due to the relativistic spin-orbit interaction (SOI). In real systems, the electrons hop between the atoms and gain the itinerancy, which is usually described by the band theory. The whole content of theories on correlation is to provide a reliable way to describe the intermediate situation between the two limits. Here we propose an approach toward this goal, i.e., we study the two-atom systems of three $t_{2g}$ orbitals and see how the Hund's rule is modified by the transfer integral $t$ between them. It is found that the competition between $t$ and the Hund's coupling $J$ at each atom determines the crossover from the molecular orbital limit to the strong correlation limit. Especially, the focus is on the generalization of the third rule, i.e., the inter-and intra-atomic SOI's in the presence of the correlation. We have found that there are cases where the effective SOI's are appreciably enhanced by the Hund's coupling. The conditions for the enhancement are the intermediate Hund's coupling and the filling of four or five electrons.