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Title: Combined computational and experimental investigation of the La2CuO4-xSx (0 ≤ x ≤ 4) quaternary system

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
 [1];  [2];  [3];  [4];  [1];  [1];  [3];  [3];  [3];  [5];  [5];  [5];  [2];  [1]
  1. Texas A&M Univ., College Station, TX (United States). Dept. of Physics and Astronomy
  2. Rutgers Univ., Piscataway, NJ (United States). Dept. of Physics and Astronomy
  3. Stony Brook Univ., NY (United States). Dept. of Physics and Astronomy
  4. Farmingdale State College, Farmingdale, NY (United States). Dept. of Physics
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
+ Show Author Affiliations

The lack of a mechanistic framework for chemical reactions forming inorganic extended solids presents a challenge to accelerated materials discovery. We demonstrate here a combined computational and experimental methodology to tackle this problem, in which in situ X-ray diffraction measurements monitor solid-state reactions and deduce reaction pathways, while theoretical computations rationalize reaction energetics. The method has been applied to the La2CuO4-xSx (0 ≤ x ≤ 4) quaternary system, following an earlier prediction that enhanced superconductivity could be found in these new lanthanum copper(II) oxysulfide compounds. In situ diffraction measurements show that reactants containing Cu(II) and S(2-) ions undergo redox reactions, leaving their ions in oxidation states that are incompatible with forming the desired new compounds. Computations of the reaction energies confirm that the observed synthetic pathways are indeed favored over those that would hypothetically form the suggested compounds. The consistency between computation and experiment in the La2CuO4-xSx system suggests a role for predictive theory: to identify and to explicate new synthetic routes for forming predicted compounds.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Emergent Superconductivity (CES); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1462408
Report Number(s):
BNL-207879-2018-JAAM
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Vol. 115, Issue 31; ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)Copyright Statement
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE
Materials by Design
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