AUTHOR=Peng Wanyue , Baranets Sviatoslav , Bobev Svilen 

TITLE=Synthesis, crystal and electronic structure of BaLixCd13–x (x ≈ 2)

JOURNAL=Frontiers in Chemistry

VOLUME=10

YEAR=2022

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2022.991625

DOI=10.3389/fchem.2022.991625

ISSN=2296-2646

ABSTRACT=<p>A new ternary phase has been synthesized and structurally characterized. BaLi<sub><italic>x</italic></sub>Cd<sub>13–<italic>x</italic></sub> (<italic>x</italic> ≈ 2) adopts the cubic NaZn<sub>13</sub> structure type (space group <italic>Fm</italic><inline-formula id="inf1"><mml:math id="m1" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mover accent="true"><mml:mn>3</mml:mn><mml:mo stretchy="true">¯</mml:mo></mml:mover></mml:mrow></mml:math></inline-formula><italic>c</italic>, Pearson symbol <italic>cF</italic>112) with unit cell parameter <italic>a</italic> = 13.5548 (10) Å. Structure refinements from single-crystal X-ray diffraction data demonstrate that the Li atoms are exclusively found at the centers of the Cd<sub>12</sub>-icosahedra. Since a cubic BaCd<sub>13</sub> phase does not exist, and the tetragonal BaCd<sub>11</sub> is the most Cd-rich phase in the Ba–Cd system, BaLi<sub><italic>x</italic></sub>Cd<sub>13–<italic>x</italic></sub> (<italic>x</italic> ≈ 2) has to be considered as a true ternary compound. As opposed to the typical electron count of ca. 27<italic>e</italic>-per formula unit for many known compounds with the NaZn<sub>13</sub> structure type, BaLi<sub><italic>x</italic></sub>Cd<sub>13–<italic>x</italic></sub> (<italic>x</italic> ≈ 2) only has ca. 26<italic>e</italic>-, suggesting that both electronic and geometric factors are at play. Finally, the bonding characteristics of the cubic BaLi<sub><italic>x</italic></sub>Cd<sub>13–<italic>x</italic></sub> (<italic>x</italic> ≈ 2) and tetragonal BaCd<sub>11</sub> are investigated using the TB-LMTO-ASA method, showing metallic-like behavior.</p>