Electronic Structure of Cu(tmdt)2 Studied with First-Principles Calculations

Shoji Ishibashi,Kiyoyuki Terakura

doi:10.3390/cryst2031210

Abstract

We have studied the electronic structure of Cu(tmdt)2, a material related to single-component molecular conductors, by first-principles calculations. The total energy calculations for several different magnetic configurations show that there is strong antiferromagnetic (AFM) exchange coupling along the crystal a-axis. The electronic structures are analyzed in terms of the molecular orbitals near the Fermi level of isolated Cu(tmdt)2 molecule. This analysis reveals that the system is characterized by the half-filled pdσ(−) band whose intermolecular hopping integrals have strong one-dimensionality along the crystal a-axis. As the exchange splitting of the band is larger than the band width, the basic mechanism of the AFM exchange coupling is the superexchange. It will also be shown that two more ligand orbitals which are fairly insensitive to magnetism are located near the Fermi level. Because of the presence of these orbitals, the present calculation predicts that Cu(tmdt)2 is metallic even in its AFM state, being inconsistent with the available experiment. Some comments will be made on the difference between Cu(tmdt)2 and Cu(dmdt)2.

Highlights

Since the successful synthesis of Ni(tmdt)2 which is the first single-component molecular conductor [1], related materials such as Au(tmdt)2 [2], Cu(dmdt)2 [3] and Zn(tmdt)2 [4] have been subsequently synthesized
Zn(tmdt)2 is a semiconductor though there is a temperature-independent paramagnetic component in magnetic susceptibility measurements
We investigate the electronic structure of this novel single-component molecular crystal Cu(tmdt)2 by means of first-principles calculations

Summary

Introduction

Since the successful synthesis of Ni(tmdt) (tmdt = trimethylenetetrathiafulvalenedithiolate) which is the first single-component molecular conductor [1], related materials such as Au(tmdt)2 [2], Cu(dmdt) (dmdt = dimethyltetrathiafulvalenedithiolate) [3] and Zn(tmdt)2 [4] have been subsequently synthesized. Their electronic properties observed experimentally are wide-ranging. Au(tmdt) undergoes a magnetic phase transition around 110 K At low temperature, it is an antiferromagnetic metal [5]. Zn(tmdt) is a semiconductor though there is a temperature-independent paramagnetic component in magnetic susceptibility measurements

Methods

Results

Conclusion