Title: Computationally Directed Discovery of MoBi₂

Abstract

Incorporating bismuth, the heaviest element stable to radioactive decay, into new materials enables the creation of emergent properties such as permanent magnetism, superconductivity, and nontrivial topology. Understanding the factors that drive Bi reactivity is critical for the realization of these properties. Using pressure as a tunable synthetic vector, we can access unexplored regions of phase space to foster reactivity between elements that do not react under ambient conditions. Furthermore, combining computational and experimental methods for materials discovery at high-pressures provides broader insight into the thermodynamic landscape than can be achieved through experiment alone, informing our understanding of the dominant chemical factors governing structure formation. Herein, we report our combined computational and experimental exploration of the Mo–Bi system, for which no binary intermetallic structures were previously known. Using the ab initio random structure searching (AIRSS) approach, we identified multiple synthetic targets between 0–50 GPa. Highpressure in situ powder X-ray diffraction experiments performed in diamond anvil cells confirmed that Mo–Bi mixtures exhibit rich chemistry upon the application of pressure, including experimental realization of the computationally predicted CuAl₂-type MoBi₂ structure at 35.8(5) GPa. Electronic structure and phonon dispersion calculations on MoBi₂ revealed a correlation between valence electron count and bonding in high-pressure transitionmore » metal–Bi structures as well as identified two dynamically stable ambient pressure polymorphs. Our study demonstrates the power of the combined computational–experimental approach in capturing highpressure reactivity for efficient materials discovery.« less

Authors:

Altman, Alison B.  ^[1];

• Search DOE PAGES for author "Altman, Alison B."
• Search DOE PAGES for ORCID "0000-0002-4975-5004"

Tamerius, Alexandra D. ^[1]; Koocher, Nathan Z. ^[1]; Meng, Yue ^[2]; Pickard, Chris J. ^[3]; Walsh, James S.  ^[4];

• Search DOE PAGES for author "Walsh, James S."
• Search DOE PAGES for ORCID "0000-0003-3454-3428"

Rondinelli, James M.  ^[1];

• Search DOE PAGES for author "Rondinelli, James M."
• Search DOE PAGES for ORCID "0000-0003-0508-2175"

Jacobsen, Steven D.  ^[1];

• Search DOE PAGES for author "Jacobsen, Steven D."
• Search DOE PAGES for ORCID "0000-0002-9746-958X"

Freedman, Danna E.  ^[1]

• Search DOE PAGES for author "Freedman, Danna E."
• Search DOE PAGES for ORCID "0000-0002-2579-8835"

---

+ Show Author Affiliations

1. Northwestern Univ., Evanston, IL (United States)
2. Argonne National Lab. (ANL), Argonne, IL (United States)
3. Univ. of Cambridge (United Kingdom); Tohoku Univ., Sendai (Japan)
4. Univ. of Massachusetts, Amherst, MA (United States)

Publication Date:

Tue Dec 29 00:00:00 EST 2020

Research Org.:

Northwestern Univ., Evanston, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

OSTI Identifier:

1756915

Alternate Identifier(s):

OSTI ID: 1780653

Grant/Contract Number:  

AC02-06CH11357; DMR-1508577

Resource Type:

Accepted Manuscript

Journal Name:

Journal of the American Chemical Society

Additional Journal Information:

Journal Volume: 143; Journal Issue: 1; Journal ID: ISSN 0002-7863

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Elements; Chemical structure; Energy; Electronic structure; Materials