Simulation of crystal and electronic structures of octahedral molybdenum cluster complex compound Cs-2[Mo6Cl14] using various DFT functionals

Abstract : The electronic and structural characteristics of the octahedral molybdenum cluster-based ternary compound, Cs2[Mo6Cl14], were investigated based on density functional theory (DFT) and subsequent comparisons with experimentally observed results. The geometry optimization and band structure calculations of Cs-2[Mo6Cl14] were performed using three standard functionals: local density approximation, Perdew-Burke-Ernzerhof (PBE) as a generalized gradient approximation, and PBE revised for solid compounds (PBEsol). The validity of the calculated results was experimentally examined via X-ray powder diffraction, ultravioletvisible (UV-vis) diffuse reflection, and X-ray photoemission spectra (XPS) measurements. PBEsol was found to show the best performance in terms of reproducing the experimentally refined lattice structure of the compound. The calculated band gap energy (E-g) was consistent with the value evaluated from the UV-vis measurement. Furthermore, the XPS valence spectrum of the compound was well reproduced by the calculated projected density of state weighted with the photoionization probabilities of Al K-alpha. Although the spectral shapes simulated using the three functionals were similar, PBEsol reproduced the energy levels of the electronic states of both [Mo6Cl14](2-) and Cs+ ion with greater consistency. Therefore, it was concluded that PBEsol is the most appropriate functional for DFT calculations of the metal cluster-based lattice system. (C) 2017 The Ceramic Society of Japan. All rights reserved.
Type de document :
Article dans une revue
Journal of the Ceramic Society of Japan, 2017, 125 (10), pp.753-759 〈10.2109/jcersj2.17039〉
Domaine :
Liste complète des métadonnées

https://hal-univ-rennes1.archives-ouvertes.fr/hal-01631918
Contributeur : Laurent Jonchère <>
Soumis le : jeudi 9 novembre 2017 - 17:40:20
Dernière modification le : samedi 24 mars 2018 - 01:35:40

Lien texte intégral

Identifiants

Citation

Norio Saito, Pierric Lemoine, Stéphane Cordier, Takeo Ohsawa, Yoshiki Wada, et al.. Simulation of crystal and electronic structures of octahedral molybdenum cluster complex compound Cs-2[Mo6Cl14] using various DFT functionals. Journal of the Ceramic Society of Japan, 2017, 125 (10), pp.753-759 〈10.2109/jcersj2.17039〉. 〈hal-01631918〉

Partager

Métriques

Consultations de la notice

62