Abstract
The binary Ru4Si3 remained the only compound in its structure type for more than 60 years. Herein, we report the synthesis and crystal structure of the first ternary silicide (Ir4−xCuSi2) in the Ru4Si3-type structure, which can be derived from RuSi by unit cell twinning. According to single-crystal X-ray diffraction, Ir vacancies exist along the twin boundary. Ir4−xCuSi2 exhibits a distorted structure compared to Ru4Si3, as the larger Cu selectively replaces Si on only one of three possible sites, leading to zigzag chains with short Cu–Cu distances. Furthermore, DFT calculations show that the rigid band approximation does not apply to this structure type, but the similarities of electronic structures of the ideal binary and ternary compositions suggest that this structure type can accommodate a large variety of elemental substitutions without a significant change of its electronic structure if a similar valence electron count is maintained, hinting at a potentially rich substitutional chemistry.
Dedicated to Professor Dr. Ulrich Müller on the occasion of his 80th birthday.
Funding source: University of California, Riverside
Acknowledgments
The authors would like to acknowledge the financial support by UC Riverside (Dissertation Year Award for J.P.S and start-up funding for B.P.T.F). Furthermore, the authors thank Sarah Hoang, Alexis Puente, Nicole Zuno and Kellie Albright, who are students of the Valley View Highschool in Moreno Valley, CA, for their help preparing the samples and sealing them in quartz tubes. Finally, the authors acknowledge the support by the San Diego Supercomputing Center, where the DFT calculations were carried out.
Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: UC Riverside (Dissertation Year Award for J.P.S and start-up funding for B.P.T.F).
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
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