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Title: Local orbital degeneracy lifting as a precursor to an orbital-selective Peierls transition

Abstract

Fundamental electronic principles underlying all transition metal compounds are the symmetry and filling of the d-electron orbitals and the influence of this filling on structural configurations and responses. Here we use a sensitive local structural technique, x-ray atomic pair distribution function analysis, to reveal the presence of fluctuating local-structural distortions at high temperature in one such compound, CuIr 2S 4. We show that this hitherto overlooked fluctuating symmetry-lowering is electronic in origin and will modify the energy-level spectrum and electronic and magnetic properties. The explanation is a local, fluctuating, orbital-degeneracy-lifted state. The natural extension of our result would be that this phenomenon is likely to be widespread amongst diverse classes of partially filled nominally degenerate d-electron systems, with potentially broad implications for our understanding of their properties.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [2];  [2];  [1];  [1];  [2];  [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Columbia Univ., New York, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1560035
Alternate Identifier(s):
OSTI ID: 1543404
Report Number(s):
BNL-211872-2019-JAAM
Journal ID: ISSN 2041-1723
Grant/Contract Number:  
SC0012704; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Bozin, Emil S., Yin, W. G., Koch, R. J., Abeykoon, M., Hor, Y. S., Zheng, H., Lei, H. C., Petrovic, C., Mitchell, J. F., and Billinge, S. J. L. Local orbital degeneracy lifting as a precursor to an orbital-selective Peierls transition. United States: N. p., 2019. Web. doi:10.1038/s41467-019-11372-w.
Bozin, Emil S., Yin, W. G., Koch, R. J., Abeykoon, M., Hor, Y. S., Zheng, H., Lei, H. C., Petrovic, C., Mitchell, J. F., & Billinge, S. J. L. Local orbital degeneracy lifting as a precursor to an orbital-selective Peierls transition. United States. doi:10.1038/s41467-019-11372-w.
Bozin, Emil S., Yin, W. G., Koch, R. J., Abeykoon, M., Hor, Y. S., Zheng, H., Lei, H. C., Petrovic, C., Mitchell, J. F., and Billinge, S. J. L. Mon . "Local orbital degeneracy lifting as a precursor to an orbital-selective Peierls transition". United States. doi:10.1038/s41467-019-11372-w. https://www.osti.gov/servlets/purl/1560035.
@article{osti_1560035,
title = {Local orbital degeneracy lifting as a precursor to an orbital-selective Peierls transition},
author = {Bozin, Emil S. and Yin, W. G. and Koch, R. J. and Abeykoon, M. and Hor, Y. S. and Zheng, H. and Lei, H. C. and Petrovic, C. and Mitchell, J. F. and Billinge, S. J. L.},
abstractNote = {Fundamental electronic principles underlying all transition metal compounds are the symmetry and filling of the d-electron orbitals and the influence of this filling on structural configurations and responses. Here we use a sensitive local structural technique, x-ray atomic pair distribution function analysis, to reveal the presence of fluctuating local-structural distortions at high temperature in one such compound, CuIr2S4. We show that this hitherto overlooked fluctuating symmetry-lowering is electronic in origin and will modify the energy-level spectrum and electronic and magnetic properties. The explanation is a local, fluctuating, orbital-degeneracy-lifted state. The natural extension of our result would be that this phenomenon is likely to be widespread amongst diverse classes of partially filled nominally degenerate d-electron systems, with potentially broad implications for our understanding of their properties.},
doi = {10.1038/s41467-019-11372-w},
journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

FIG. 1 FIG. 1: Observation of high temperature fluctuating ODL state in CuIr2S4. a, Temperature waterfall stack of xPDFs measured on warming from 10 K (bottom) to 500 K (top) in 2 K increments. $T$MI is the MIT transition temperature (226 K). The dimer peak at ∼3 Å (marked by arrow) ismore » only seen in the insulating phase, and disappears above $T$MI. b, Fit of the undistorted cubic $F$d$\bar{3}$m model (red line) to the 500 K data (blue open circles) and their difference (green line, offset for clarity) unmask the footprint of the localized ODL state at ∼3.5 Å. c, Simulated $F$d$\bar{3}$m total xPDF of CuIr2S4 (blue line), decomposed into Ir-Ir partial xPDF (green line) and its complement (red line). Shaded peaks in total xPDF are sensitive to $t$2g orbital overlaps (sketched) and their spatial correlations. Inset: $t$2g-derived molecular orbitals discussed in the main text. d,e, Section of Ir pyrochlore sublattice of corner shared Ir4 tetrahedra for undistorted (cubic) and distorted (tetragonal) spinel structure, respectively. The strongest $t$2g orbital overlaps (e.g. xy with xy, etc.) are along the chains formed by the tetrahedral edges of the Ir sublattice.« less

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