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Ab initio study of the vanadium-based half Heusler alloys VRhZ (Z=Ge,Si,Sn) as potential thermoelectric materials

Winfred M. Mulwa1,2,*, Mark Pederson1, Eunja Kim1, and Bernard Aduda2

  • *Contact author: wmmulwa@utep.edu; winfred.mulwa@ egerton.ac.ke
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Phys. Rev. B 113, 024104 – Published 9 January, 2026

DOI: https://doi.org/10.1103/dy2n-c3px

Abstract

We embrace a high-throughput investigation strategy beginning from the electronic structure properties to examine three vanadium-based half Heusler alloys with 18 valence electrons, VRhZ (Z=Ge,Si, and Sn), for thermoelectric application. This work is inspired by expected contrasting electrical transport essentials, particularly high electrical conductivity σ and high Seebeck coefficient S for attaining enhanced figure of merit (ZT) performance. We employ the electronic fitness function (EFF), which evaluates the magnitude of decoupling σ and S for high ZT by a distinct band structure. The impact of varying the Fermi level on the power factor, electrical conductivity, and Seebeck coefficient is explored. The effects of exchange correlation are reported by use of the Perdew-Burke-Ernzerhof (PBE) functional in line with the framework of the generalized gradient approximation (GGA), as implemented in the ab initio density functional theory. To rigorously assess the reliability of the GGA-PBE functional, subsequent electronic structure calculations are carried out on the three compounds using the GW approximation. We obtain lattice constants of a0=5.79Å,a0=5.76Å, and a0=6.09Å for VRhGe, VRhSi, and VRhSn, respectively. All materials exhibit ductility as indicated by their values of Cauchy pressure, as well as Poisson's ratio and Pugh's ratio values. The VRhSn machinability index is the highest at 2.2456. The highest hardness is realized in VRhSi, which is at 7.9957 GPa. Based on the Kleinman parameter, bond stretching is negligible in all VRhZ materials. VRhZ spatial dependence plots indicate that all investigated compounds are anisotropic. In this study, dynamic stability is observed in all compounds due to the nonexistence of phonon modes that correspond to imaginary frequencies. The derived electronic energy band structure reveals that all three alloys exhibit semiconductor properties with band gap energies of 0.50, 0.32, and 0.42 eV in VRhGe, VRhSi, and VRhSn, respectively, corresponding to indirect transitions. The maximum values realized for the EFF when T=1000K using GW are 0.69×10−19W53ms−13K−2, 0.66×10−19W53ms−13K−2, 0.79×10−19W53ms−13K−2 for VRhGe, VRhSi, and VRhSn, respectively. The observed ZT values at 1000 K using GW are 0.91, 0.99, and 0.99 for VRhGe, VRhSi, and VRhSn, respectively. These results of ZT as well as EFF suggest that VRhZ (Z=Ge, Si, and Sn) compounds are promising high-temperature thermoelectric materials.

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Phys. Rev. B 113, 024104– Published 9 January, 2026
  • Received 28 May 2025
  • Revised 5 September 2025
  • Accepted 24 October 2025
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