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 language | English |
|---|---|
| Pages (from-to) | 1154-1169 |
| Number of pages | 16 |
| Journal | Bulletin of the Chemical Society of Japan |
| Volume | 92 |
| Issue number | 7 |
| DOIs | |
| Publication status | Published - Jan 1 2019 |
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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 journal › Article
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TY - JOUR
T1 - Lithium-richest phase of lithium tetrelides Li17TT4 (TT = Si, Ge, Sn, and Pb) as an electride
AU - Tsuji, Yuta
AU - Hashimoto, Wataru
AU - Yoshizawa, Kazunari
PY - 2019/1/1
Y1 - 2019/1/1
N2 - 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.
AB - 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.
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U2 - 10.1246/bcsj.20190040
DO - 10.1246/bcsj.20190040
M3 - Article
AN - SCOPUS:85069564306
VL - 92
SP - 1154
EP - 1169
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 7
ER -