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

Title: Investigation of the multiplet features of SrTiO3 in X-ray absorption spectra based on configuration interaction calculations

Abstract

Synchrotron-based L2,3-edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here in this study using the experimental Ti L2,3-edges absorption spectrum of SrTiO3as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L3 and L2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature are further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non-linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO3-based thin films and heterostructures is offered. Finally, detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the eg crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.

Authors:
ORCiD logo [1];  [2];  [3];  [1];  [1];  [1]; ORCiD logo [4];  [4]
  1. Xiamen University (China). Fujian Provincial Key Laboratory of Semiconductors and Applications, Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Department of Physics
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Chinese Academy of Sciences (CAS), Beijing (China). Beijing Synchrotron Radiation Facility, Institute of High Energy Physics
  4. Xiamen University (China). Fujian Provincial Key Laboratory of Semiconductors and Applications, Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Department of Physics; Xiamen University Malaysia, Selangor (Malaysia)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1456895
Report Number(s):
BNL-205779-2018-JAAM
Journal ID: ISSN 1600-5775; JSYRES; TRN: US1901254
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Synchrotron Radiation (Online)
Additional Journal Information:
Journal Name: Journal of Synchrotron Radiation (Online); Journal Volume: 25; Journal Issue: 3; Journal ID: ISSN 1600-5775
Publisher:
International Union of Crystallography
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; X ray absorbance spectra; soft X‐ray absorption; configuration interaction cluster calculation; 3 d transition metal oxide; crystal field effect

Citation Formats

Wu, M., Xin, Houlin L., Wang, J. O., Li, X. J., Yuan, X. B., Zeng, H., Zheng, J. -C., and Wang, H. -Q. Investigation of the multiplet features of SrTiO3 in X-ray absorption spectra based on configuration interaction calculations. United States: N. p., 2018. Web. https://doi.org/10.1107/S160057751800423X.
Wu, M., Xin, Houlin L., Wang, J. O., Li, X. J., Yuan, X. B., Zeng, H., Zheng, J. -C., & Wang, H. -Q. Investigation of the multiplet features of SrTiO3 in X-ray absorption spectra based on configuration interaction calculations. United States. https://doi.org/10.1107/S160057751800423X
Wu, M., Xin, Houlin L., Wang, J. O., Li, X. J., Yuan, X. B., Zeng, H., Zheng, J. -C., and Wang, H. -Q. Tue . "Investigation of the multiplet features of SrTiO3 in X-ray absorption spectra based on configuration interaction calculations". United States. https://doi.org/10.1107/S160057751800423X. https://www.osti.gov/servlets/purl/1456895.
@article{osti_1456895,
title = {Investigation of the multiplet features of SrTiO3 in X-ray absorption spectra based on configuration interaction calculations},
author = {Wu, M. and Xin, Houlin L. and Wang, J. O. and Li, X. J. and Yuan, X. B. and Zeng, H. and Zheng, J. -C. and Wang, H. -Q.},
abstractNote = {Synchrotron-based L2,3-edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here in this study using the experimental Ti L2,3-edges absorption spectrum of SrTiO3as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L3 and L2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature are further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non-linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO3-based thin films and heterostructures is offered. Finally, detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the eg crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.},
doi = {10.1107/S160057751800423X},
journal = {Journal of Synchrotron Radiation (Online)},
number = 3,
volume = 25,
place = {United States},
year = {2018},
month = {4}
}

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

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Comparison between the experimental x-ray absorption spectrum for a STO single crystal (miscut angle <0.05, purchased from Crystec) and the calculated spectrum of STO (bottom line).

Save / Share:

Works referenced in this record:

L 2 , 3 x-ray-absorption edges of d 0 compounds: K + , Ca 2 + , Sc 3 + , and Ti 4 + in O h (octahedral) symmetry
journal, January 1990


Room-temperature ferroelectricity in strained SrTiO3
journal, August 2004

  • Haeni, J. H.; Irvin, P.; Chang, W.
  • Nature, Vol. 430, Issue 7001, p. 758-761
  • DOI: 10.1038/nature02773

Theory of x-ray absorption and linear dichroism at the Ca L 23 -edge of CaCO 3
journal, May 2016


A non-empirical calculation of 2p core-electron excitation in compounds with 3d transition metal ions using ligand-field and density functional theory (LFDFT)
journal, January 2017

  • Ramanantoanina, Harry; Daul, Claude
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 31
  • DOI: 10.1039/c7cp03140h

Impact of local strain on Ti-L 2,3 electron energy-loss near-edge structures of BaTiO 3 : a first-principles multiplet study
journal, April 2014


Ferroelectricity: Octahedral Rotation-Induced Ferroelectricity in Cation Ordered Perovskites (Adv. Mater. 15/2012)
journal, April 2012


Semiconductor Composites: Strategies for Enhancing Charge Carrier Separation to Improve Photocatalytic Activity
journal, December 2013


Satellite structure in photoelectron and Auger spectra of copper dihalides
journal, May 1981


Multiplet ligand-field theory using Wannier orbitals
journal, April 2012


Simplified LCAO Method for the Periodic Potential Problem
journal, June 1954


Oxide Nanoelectronics on Demand
journal, February 2009


Resonant inelastic scattering at the L edge of Ti in Barium Strontium Titanate by soft X-ray fluorescence spectroscopy
journal, August 1997

  • Uehara, Y.; Lindle, D. W.; Callcott, T. A.
  • Applied Physics A: Materials Science & Processing, Vol. 65, Issue 2
  • DOI: 10.1007/s003390050562

Structural, electronic, and magnetic properties of Sr Ru O 3 under epitaxial strain
journal, September 2006


Time-dependent density functional theory applied to x-ray absorption spectroscopy
journal, April 2012


Electronic structure of early 3 d -transition-metal oxides by analysis of the 2 p core-level photoemission spectra
journal, January 1996


Understanding the L 2 , 3 x-ray absorption spectra of early 3 d transition elements
journal, November 2010


Emergent phenomena at oxide interfaces
journal, January 2012

  • Hwang, H. Y.; Iwasa, Y.; Kawasaki, M.
  • Nature Materials, Vol. 11, Issue 2
  • DOI: 10.1038/nmat3223

Resonant 3 d , 3 p and 3 s Photoemission in Transition Metal Oxides Predicted at 2 p Threshold
journal, July 1994

  • Tanaka, Arata; Jo, Takeo
  • Journal of the Physical Society of Japan, Vol. 63, Issue 7
  • DOI: 10.1143/jpsj.63.2788

Restricted Open-Shell Configuration Interaction Cluster Calculations of the L-Edge X-ray Absorption Study of TiO 2 and CaF 2 Solids
journal, May 2014

  • Maganas, Dimitrios; DeBeer, Serena; Neese, Frank
  • Inorganic Chemistry, Vol. 53, Issue 13
  • DOI: 10.1021/ic500197v

A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface
journal, January 2004


Comparison of x-ray absorption with x-ray photoemission of nickel dihalides and NiO
journal, March 1986


Probing ferroelectricity in PbZr 0.2 Ti 0.8 O 3 with polarized soft x rays
journal, October 2010


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


Structural effects on the spin-state transition in epitaxially strained LaCoO 3 films
journal, February 2009


Spectroscopic mapping of local structural distortions in ferroelectric PbTiO 3 /SrTiO 3 superlattices at the unit-cell scale
journal, December 2011


Physics of thin-film ferroelectric oxides
journal, October 2005


Superconducting Interfaces Between Insulating Oxides
journal, August 2007


Switchable Ferroelectric Diode and Photovoltaic Effect in BiFeO 3
journal, February 2009


Split-Off State Formation in the Final State of Photoemission in Ti Compounds
journal, August 1994

  • Okada, Kozo; Uozumi, Takayuki; Kotani, Akio
  • Journal of the Physical Society of Japan, Vol. 63, Issue 8
  • DOI: 10.1143/jpsj.63.3176

Multiplet calculations of L 2,3 x-ray absorption near-edge structures for 3d transition-metal compounds
journal, February 2009


Asymmetric Orbital-Lattice Interactions in Ultrathin Correlated Oxide Films
journal, September 2011


Final-State Projection Method in Charge-Transfer Multiplet Calculations: An Analysis of Ti L-Edge Absorption Spectra
journal, April 2015

  • Kroll, Thomas; Solomon, Edward I.; de Groot, Frank M. F.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 43
  • DOI: 10.1021/acs.jpcb.5b04133

Band alignment of epitaxial SrTiO3 thin films with (LaAlO3)0.3-(Sr2AlTaO6)0.7 (001)
journal, September 2015

  • Comes, Ryan B.; Xu, Peng; Jalan, Bharat
  • Applied Physics Letters, Vol. 107, Issue 13
  • DOI: 10.1063/1.4932063

Strain and composition dependence of orbital polarization in nickel oxide superlattices
journal, September 2013


L 2,3 edge photoabsorption spectra of bulk V 2 O 5 : A two components relativistic time dependent density functional theory description with finite cluster model
journal, December 2012

  • Fronzoni, Giovanna; De Francesco, Renato; Stener, Mauro
  • The Journal of Chemical Physics, Vol. 137, Issue 22
  • DOI: 10.1063/1.4769789

Investigation of the multiplet structures and crystal field effects of a TiO 6 3 d 1 cluster based on configuration interaction calculations
journal, March 2017

  • Wu, Meng; Zheng, Jin-Cheng; Wang, Hui-Qiong
  • Journal of Applied Crystallography, Vol. 50, Issue 2
  • DOI: 10.1107/s160057671700334x

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


Strain Tuning of Ferroelectric Thin Films
journal, August 2007


Probing ferroelectricity in PbZr 0.2 Ti 0.8 O 3 with polarized soft x rays
journal, October 2010


Electronic structure of early 3 d -transition-metal oxides by analysis of the 2 p core-level photoemission spectra
journal, January 1996


Time-dependent density functional theory applied to x-ray absorption spectroscopy
journal, April 2012


Asymmetric Orbital-Lattice Interactions in Ultrathin Correlated Oxide Films
journal, September 2011


Physics of thin-film ferroelectric oxides
journal, October 2005


L 2 , 3 x-ray-absorption edges of d 0 compounds: K + , Ca 2 + , Sc 3 + , and Ti 4 + in O h (octahedral) symmetry
journal, January 1990


Multiplet ligand-field theory using Wannier orbitals
journal, April 2012


Satellite structure in photoelectron and Auger spectra of copper dihalides
journal, May 1981


Comparison of x-ray absorption with x-ray photoemission of nickel dihalides and NiO
journal, March 1986


Understanding the L 2 , 3 x-ray absorption spectra of early 3 d transition elements
journal, November 2010


Split-Off State Formation in the Final State of Photoemission in Ti Compounds
journal, August 1994

  • Okada, Kozo; Uozumi, Takayuki; Kotani, Akio
  • Journal of the Physical Society of Japan, Vol. 63, Issue 8
  • DOI: 10.1143/JPSJ.63.3176

A non-empirical calculation of 2p core-electron excitation in compounds with 3d transition metal ions using ligand-field and density functional theory (LFDFT)
journal, January 2017

  • Ramanantoanina, Harry; Daul, Claude
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 31
  • DOI: 10.1039/C7CP03140H

Structural effects on the spin-state transition in epitaxially strained LaCoO 3 films
journal, February 2009


Simplified LCAO Method for the Periodic Potential Problem
journal, June 1954


Resonant 3 d , 3 p and 3 s Photoemission in Transition Metal Oxides Predicted at 2 p Threshold
journal, July 1994

  • Tanaka, Arata; Jo, Takeo
  • Journal of the Physical Society of Japan, Vol. 63, Issue 7
  • DOI: 10.1143/JPSJ.63.2788

Spectroscopic mapping of local structural distortions in ferroelectric PbTiO 3 /SrTiO 3 superlattices at the unit-cell scale
journal, December 2011


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


Strain and composition dependence of orbital polarization in nickel oxide superlattices
journal, September 2013


Investigation of the multiplet structures and crystal field effects of a TiO 6 3 d 1 cluster based on configuration interaction calculations
journal, March 2017

  • Wu, Meng; Zheng, Jin-Cheng; Wang, Hui-Qiong
  • Journal of Applied Crystallography, Vol. 50, Issue 2
  • DOI: 10.1107/S160057671700334X

Structural, electronic, and magnetic properties of Sr Ru O 3 under epitaxial strain
journal, September 2006


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.