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:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- 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. https://doi.org/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. https://doi.org/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 = {Fri Mar 03 00:00:00 EST 2017},
month = {Fri Mar 03 00:00:00 EST 2017}
}
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