Lithium-richest phase of lithium tetrelides Li17TT4 (TT = Si, Ge, Sn, and Pb) as an electride

Yuta Tsuji, Wataru Hashimoto, Kazunari Yoshizawa

Research output: Contribution to journalArticle

Abstract

The lithium-richest phase in the binary Li-Tt system (Tt = Si, Ge, Sn, and Pb) has a stoichiometry of Li17Tt4. In the beginning of this paper, the structural complexity of Li17Tt4 is gradually stripped away using the concept of the M26 cluster found in γ-brass structures and a Tt-centered polyhedral representation. By means of the first-principles electronic structure calculations, which are followed by the analyses of the electron localization function (ELF), Bader charges, and spin density, we observe non-nuclear maxima of the ELF, electron density, and spin density. Since the electron densities off the atoms are confined in crystalline voids, separated from each other, and behaving as an anion, Li17Tt4 can be identified as a potential zero-dimensional electride. This finding agrees with a simple Zintl picture, which suggests a valence electron count of [(Li+)17(Tt41)4¢e1]. Detailed analyses on the band structures, the projected density of states, and crystal orbitals at the ¥ point in the reciprocal space hint at the potential of forming a bond between the non-nuclear electron density and the neighboring atoms. Signatures of bonding and anti-bonding orbital interactions can be witnessed.

Original languageEnglish
Pages (from-to)1154-1169
Number of pages16
JournalBulletin of the Chemical Society of Japan
Volume92
Issue number7
DOIs
Publication statusPublished - Jan 1 2019

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Lithium
Carrier concentration
Electrons
Atoms
Stoichiometry
Band structure
Electronic structure
Anions
Crystalline materials
Crystals

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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Lithium-richest phase of lithium tetrelides Li17TT4 (TT = Si, Ge, Sn, and Pb) as an electride. / Tsuji, Yuta; Hashimoto, Wataru; Yoshizawa, Kazunari.

In: Bulletin of the Chemical Society of Japan, Vol. 92, No. 7, 01.01.2019, p. 1154-1169.

Research output: Contribution to journalArticle

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