skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Accurate X-Ray Spectral Predictions: An Advanced Self-Consistent-Field Approach Inspired by Many-Body Perturbation Theory

Abstract

Constrained-occupancy delta-self-consistent-field (ΔSCF) methods and many-body perturbation theories (MBPT) are two strategies for obtaining electronic excitations from first principles. Using the two distinct approaches, we study the O 1s core excitations that have become increasingly important for characterizing transition-metal oxides and understanding strong electronic correlation. The ΔSCF approach, in its current single-particle form, systematically underestimates the pre-edge intensity for chosen oxides, despite its success in weakly correlated systems. By contrast, the Bethe-Salpeter equation within MBPT predicts much better line shapes. This motivates one to reexamine the many-electron dynamics of x-ray excitations. We find that the single-particle ΔSCF approach can be rectified by explicitly calculating many-electron transition amplitudes, producing x-ray spectra in excellent agreement with experiments. This study paves the way to accurately predict x-ray near-edge spectral fingerprints for physics and materials science beyond the Bethe-Salpether equation.

Authors:
 [1];  [2];  [1];  [1];  [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1398466
Alternate Identifier(s):
OSTI ID: 1345695
Grant/Contract Number:  
AC02-05CH11231; SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 118; Journal Issue: 9; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS

Citation Formats

Liang, Yufeng, Vinson, John, Pemmaraju, Sri, Drisdell, Walter S., Shirley, Eric L., and Prendergast, David. Accurate X-Ray Spectral Predictions: An Advanced Self-Consistent-Field Approach Inspired by Many-Body Perturbation Theory. United States: N. p., 2017. Web. doi:10.1103/PhysRevLett.118.096402.
Liang, Yufeng, Vinson, John, Pemmaraju, Sri, Drisdell, Walter S., Shirley, Eric L., & Prendergast, David. Accurate X-Ray Spectral Predictions: An Advanced Self-Consistent-Field Approach Inspired by Many-Body Perturbation Theory. United States. doi:10.1103/PhysRevLett.118.096402.
Liang, Yufeng, Vinson, John, Pemmaraju, Sri, Drisdell, Walter S., Shirley, Eric L., and Prendergast, David. Fri . "Accurate X-Ray Spectral Predictions: An Advanced Self-Consistent-Field Approach Inspired by Many-Body Perturbation Theory". United States. doi:10.1103/PhysRevLett.118.096402. https://www.osti.gov/servlets/purl/1398466.
@article{osti_1398466,
title = {Accurate X-Ray Spectral Predictions: An Advanced Self-Consistent-Field Approach Inspired by Many-Body Perturbation Theory},
author = {Liang, Yufeng and Vinson, John and Pemmaraju, Sri and Drisdell, Walter S. and Shirley, Eric L. and Prendergast, David},
abstractNote = {Constrained-occupancy delta-self-consistent-field (ΔSCF) methods and many-body perturbation theories (MBPT) are two strategies for obtaining electronic excitations from first principles. Using the two distinct approaches, we study the O 1s core excitations that have become increasingly important for characterizing transition-metal oxides and understanding strong electronic correlation. The ΔSCF approach, in its current single-particle form, systematically underestimates the pre-edge intensity for chosen oxides, despite its success in weakly correlated systems. By contrast, the Bethe-Salpeter equation within MBPT predicts much better line shapes. This motivates one to reexamine the many-electron dynamics of x-ray excitations. We find that the single-particle ΔSCF approach can be rectified by explicitly calculating many-electron transition amplitudes, producing x-ray spectra in excellent agreement with experiments. This study paves the way to accurately predict x-ray near-edge spectral fingerprints for physics and materials science beyond the Bethe-Salpether equation.},
doi = {10.1103/PhysRevLett.118.096402},
journal = {Physical Review Letters},
number = 9,
volume = 118,
place = {United States},
year = {2017},
month = {3}
}

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

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Calculated electronic structure and x-ray magnetic circular dichroism of CrO 2
journal, May 2006

  • Kanchana, V.; Vaitheeswaran, G.; Alouani, M.
  • Journal of Physics: Condensed Matter, Vol. 18, Issue 22
  • DOI: 10.1088/0953-8984/18/22/015

Coulomb repulsion and correlation strength in LaFeAsO from density functional and dynamical mean-field theories
journal, January 2009


Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries
journal, January 2016


Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution
journal, September 2013

  • Grimaud, Alexis; May, Kevin J.; Carlton, Christopher E.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3439

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Optical Absorption of Insulators and the Electron-Hole Interaction: An Ab Initio Calculation
journal, May 1998


X-Ray Absorption Spectra Reveal the Inapplicability of the Single-Band Hubbard Model to Overdoped Cuprate Superconductors
journal, August 2009


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Ab initio calculation of the core-hole effect in the electron energy-loss near-edge structure
journal, September 2000


Electron correlation in semiconductors and insulators: Band gaps and quasiparticle energies
journal, October 1986


X-Ray Absorption Spectra of Water from First Principles Calculations
journal, May 2006


Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li 2 MnO 3 −LiCo 1/3 Ni 1/3 Mn 1/3 O 2
journal, March 2011

  • Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek
  • Journal of the American Chemical Society, Vol. 133, Issue 12
  • DOI: 10.1021/ja108588y

Electronic excitations: density-functional versus many-body Green’s-function approaches
journal, June 2002


Theoretical x-ray absorption fine structure standards
journal, July 1991

  • Rehr, J. J.; Mustre de Leon, J.; Zabinsky, S. I.
  • Journal of the American Chemical Society, Vol. 113, Issue 14
  • DOI: 10.1021/ja00014a001

Direct Observation of Electrostatically Driven Band Gap Renormalization in a Degenerate Perovskite Transparent Conducting Oxide
journal, January 2016


Transfer of Spectral Weight and Symmetry across the Metal-Insulator Transition in VO 2
journal, September 2006


Control of the metal–insulator transition in vanadium dioxide by modifying orbital occupancy
journal, September 2013

  • Aetukuri, Nagaphani B.; Gray, Alexander X.; Drouard, Marc
  • Nature Physics, Vol. 9, Issue 10
  • DOI: 10.1038/nphys2733

High-Resolution X-ray Emission and X-ray Absorption Spectroscopy
journal, June 2001


Oxygen 1 s x-ray-absorption edges of transition-metal oxides
journal, September 1989


Half or full core hole in density functional theory X-ray absorption spectrum calculations of water?
journal, January 2005

  • Cavalleri, Matteo; Odelius, Michael; Nordlund, Dennis
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 15
  • DOI: 10.1039/b505723j

Theory of oxygen K edge x-ray absorption spectra of cuprates
journal, March 2010


Bethe-Salpeter equation calculations of core excitation spectra
journal, March 2011


Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts
journal, April 2010

  • Strasser, Peter; Koh, Shirlaine; Anniyev, Toyli
  • Nature Chemistry, Vol. 2, Issue 6
  • DOI: 10.1038/nchem.623

Efficient implementation of core-excitation Bethe–Salpeter equation calculations
journal, December 2015


FinalState Rule vs the BetheSalpeter Equation for DeepCore Xray Absorption Spectra
journal, January 2005


Doping evolution of the oxygen K -edge x-ray absorption spectra of cuprate superconductors using a three-orbital Hubbard model
journal, April 2013


Titanium dx y ferromagnetism at the LaAlO3/SrTiO3 interface
journal, June 2013

  • Lee, J. -S.; Xie, Y. W.; Sato, H. K.
  • Nature Materials, Vol. 12, Issue 8
  • DOI: 10.1038/nmat3674

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016

  • Luo, Kun; Roberts, Matthew R.; Hao, Rong
  • Nature Chemistry, Vol. 8, Issue 7
  • DOI: 10.1038/nchem.2471

Oxygen vacancy effect on room-temperature ferromagnetism of rutile Co:TiO2 thin films
journal, January 2009

  • Yan, Wensheng; Sun, Zhihu; Pan, Zhiyun
  • Applied Physics Letters, Vol. 94, Issue 4
  • DOI: 10.1063/1.3075844

Infrared Catastrophe in Fermi Gases with Local Scattering Potentials
journal, June 1967


Bonding and structure of a reconstructed (001) surface of SrTiO3 from TEM
journal, October 2012

  • Zhu, Guo-zhen; Radtke, Guillaume; Botton, Gianluigi A.
  • Nature, Vol. 490, Issue 7420
  • DOI: 10.1038/nature11563

The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy
journal, October 2014


Enhancing Photocatalytic Activity of LaTiO 2 N by Removal of Surface Reconstruction Layer
journal, January 2014

  • Matsukawa, Michinori; Ishikawa, Ryo; Hisatomi, Takashi
  • Nano Letters, Vol. 14, Issue 2
  • DOI: 10.1021/nl404688h

Effects of vibrational motion on core-level spectra of prototype organic molecules
journal, December 2008


Angular dependence of core hole screening in LiCoO 2 : A DFT + U calculation of the oxygen and cobalt K -edge x-ray absorption spectra
journal, March 2010


Optimal basis sets for detailed Brillouin-zone integrations
journal, December 1996


Core-hole effects on theoretical electron-energy-loss near-edge structure and near-edge x-ray absorption fine structure of MgO
journal, January 2000


Origin of additional capacities in metal oxide lithium-ion battery electrodes
journal, November 2013

  • Hu, Yan-Yan; Liu, Zigeng; Nam, Kyung-Wan
  • Nature Materials, Vol. 12, Issue 12
  • DOI: 10.1038/nmat3784

Singularities in the X-Ray Absorption and Emission of Metals. III. One-Body Theory Exact Solution
journal, February 1969


Calculation of near-edge x-ray-absorption fine structure at finite temperatures: Spectral signatures of hydrogen bond breaking in liquid water
journal, May 2004

  • Hetényi, Balázs; De Angelis, Filippo; Giannozzi, Paolo
  • The Journal of Chemical Physics, Vol. 120, Issue 18
  • DOI: 10.1063/1.1703526

Surface Engineered Doping of Hematite Nanorod Arrays for Improved Photoelectrochemical Water Splitting
journal, October 2014

  • Shen, Shaohua; Zhou, Jigang; Dong, Chung-Li
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep06627

X-ray absorption near-edge structure calculations with the pseudopotentials: Application to the K edge in diamond and α -quartz
journal, November 2002

  • Taillefumier, Mathieu; Cabaret, Delphine; Flank, Anne-Marie
  • Physical Review B, Vol. 66, Issue 19
  • DOI: 10.1103/PhysRevB.66.195107

XANES and ELNES in Ceramic Science: XANES and ELNES in Ceramic Science
journal, July 2005


Theory of the soft-x-ray edge problem in simple metals: historical survey and recent developments
journal, October 1990


X-ray absorption spectroscopy of vanadium dioxide thin films across the phase-transition boundary
journal, May 2007

  • Ruzmetov, Dmitry; Senanayake, Sanjaya D.; Ramanathan, Shriram
  • Physical Review B, Vol. 75, Issue 19
  • DOI: 10.1103/PhysRevB.75.195102

Oxidation energies of transition metal oxides within the GGA + U framework
journal, May 2006


Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries
journal, June 2011

  • Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki
  • Nature Chemistry, Vol. 3, Issue 7, p. 546-550
  • DOI: 10.1038/nchem.1069

Core-hole effects on energy-loss near-edge structure
journal, February 2001


Electronic states in La 2 x Sr x CuO 4 + δ probed by soft-x-ray absorption
journal, January 1991


Orbital character of O 2 p unoccupied states near the Fermi level in CrO 2
journal, April 2000


Many-body aspects of the near-edge structure in x-ray absorption
journal, March 1983


Electron-hole excitations and optical spectra from first principles
journal, August 2000


Experimental and theoretical investigation of the electronic structure of Cu 2 O and CuO thin films on Cu(110) using x-ray photoelectron and absorption spectroscopy
journal, January 2013

  • Jiang, Peng; Prendergast, David; Borondics, Ferenc
  • The Journal of Chemical Physics, Vol. 138, Issue 2
  • DOI: 10.1063/1.4773583

    Works referencing / citing this record:

    Evidence of a second-order Peierls-driven metal-insulator transition in crystalline NbO 2
    journal, July 2019


    Evidence of a second-order Peierls-driven metal-insulator transition in crystalline NbO 2
    journal, July 2019