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
N1 - Funding Information:
This work was supported by KAKENHI Grant numbers JP17K14440 and JP17H03117 from Japan Society for the Promotion of Science (JSPS) and the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT), the MEXT Projects of ?Integrated Research Consortium on Chemical Sciences?, ?Cooperative Research Program of Network Joint Research Center for Materials and Devices?, ?Elements Strategy Initiative to Form Core Research Center?, and JST-CREST ?Innovative Catalysts?. The computation was mainly carried out using the computer facilities at Research Institute for Information Technology, Kyushu University. Y.T. is grateful for a JSPS Grant-in-Aid for Scientific Research on Innovative Areas ?Discrete Geometric Analysis for Materials Design?: Grant Number JP18H04488.
Funding Information:
This work was supported by KAKENHI Grant numbers JP17K14440 and JP17H03117 from Japan Society for the Promotion of Science (JSPS) and the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT), the MEXT Projects of “Integrated Research Consortium on Chemical Sciences”, “Cooperative Research Program of Network Joint Research Center for Materials and Devices”, “Elements Strategy Initiative to Form Core Research Center”, and JST-CREST “Innovative Catalysts”. The computation was mainly carried out using the computer facilities at Research Institute for Information Technology, Kyushu University. Y.T. is grateful for a JSPS Grant-in-Aid for Scientific Research on Innovative Areas “Discrete Geometric Analysis for Materials Design”: Grant Number JP18H04488.
PY - 2019
Y1 - 2019
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 -