Maximally localized Wannier function within linear combination of pseudo-atomic orbital method: Implementation and applications to transition-metal-benzene complex

TL;DR

This paper implements maximally localized Wannier functions within the LCPAO method and applies it to analyze transition-metal-benzene complexes, revealing insights into ferromagnetic stability and orbital energy differences.

Contribution

It introduces a new implementation of MLWFs within the LCPAO method and applies it to complex materials, providing novel insights into their magnetic properties.

Findings

Confirmed the mechanism of FM stability in the infinite chain.

Revealed the role of orbital energy differences in FM stability of V2Bz3.

Analyzed electronic structure of benzene and related complexes.

Abstract

Construction of maximally localized Wannier functions (MLWFs) has been implemented within the linear combination of pseudo-atomic orbital (LCPAO) method. Detailed analysis using MLWFs is applied to three closely related materials, single benzene (Bz) molecule, organometallic Vanadium-Bz infinite chain, and V$_2$Bz$_{3}$ sandwich cluster. Two important results come out from the present analysis: 1) for the infinite chain, the validity of the basic assumption in the mechanism of Kanamori and Terakura for the ferromagnetic (FM) state stability is confirmed; 2) for V$_2$Bz$_3$, an important role played by the difference in the orbital energy between the edge Bzs and the middle Bz is newly revealed: the on-site energy of p$\delta$ states of edge Bzs is higher than that of middle Bz, which further reduces the FM stability of V$_2$Bz$_3$.