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Title: Combined computational and experimental investigation of the La 2CuO 4-xS x (0 ≤ x ≤ 4) quaternary system

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 La 2CuO 4-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 La 2CuO 4-xS x system suggests a role for predictive theory: to identify and to explicate new synthetic routes for forming predicted compounds.
Authors:
 [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)
Publication Date:
Report Number(s):
BNL-207879-2018-JAAM
Journal ID: ISSN 0027-8424
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 115; Journal Issue: 31; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Materials by Design; in situ X-ray studies; electronic structure calculations
OSTI Identifier:
1462408

He, Hua, Yee, Chuck-Hou, McNally, Daniel E., Simonson, Jack W., Zellman, Shelby, Klemm, Mason, Kamenov, Plamen, Geschwind, Gayle, Zebro, Ashley, Ghose, Sanjit, Bai, Jianming, Dooryhee, Eric, Kotliar, Gabriel, and Aronson, Meigan C.. Combined computational and experimental investigation of the La2CuO4-xSx (0 ≤ x ≤ 4) quaternary system. United States: N. p., Web. doi:10.1073/pnas.1800284115.
He, Hua, Yee, Chuck-Hou, McNally, Daniel E., Simonson, Jack W., Zellman, Shelby, Klemm, Mason, Kamenov, Plamen, Geschwind, Gayle, Zebro, Ashley, Ghose, Sanjit, Bai, Jianming, Dooryhee, Eric, Kotliar, Gabriel, & Aronson, Meigan C.. Combined computational and experimental investigation of the La2CuO4-xSx (0 ≤ x ≤ 4) quaternary system. United States. doi:10.1073/pnas.1800284115.
He, Hua, Yee, Chuck-Hou, McNally, Daniel E., Simonson, Jack W., Zellman, Shelby, Klemm, Mason, Kamenov, Plamen, Geschwind, Gayle, Zebro, Ashley, Ghose, Sanjit, Bai, Jianming, Dooryhee, Eric, Kotliar, Gabriel, and Aronson, Meigan C.. 2018. "Combined computational and experimental investigation of the La2CuO4-xSx (0 ≤ x ≤ 4) quaternary system". United States. doi:10.1073/pnas.1800284115.
@article{osti_1462408,
title = {Combined computational and experimental investigation of the La2CuO4-xSx (0 ≤ x ≤ 4) quaternary system},
author = {He, Hua and Yee, Chuck-Hou and McNally, Daniel E. and Simonson, Jack W. and Zellman, Shelby and Klemm, Mason and Kamenov, Plamen and Geschwind, Gayle and Zebro, Ashley and Ghose, Sanjit and Bai, Jianming and Dooryhee, Eric and Kotliar, Gabriel and Aronson, Meigan C.},
abstractNote = {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.},
doi = {10.1073/pnas.1800284115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 31,
volume = 115,
place = {United States},
year = {2018},
month = {7}
}

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