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

Title: Demonstration of resonant inelastic x-ray scattering as a probe of exciton-phonon coupling

Abstract

Resonant inelastic x-ray scattering (RIXS) is a promising technique for obtaining electron-phonon coupling constants. However, the ability to extract these coupling constants throughout the Brillouin zone for crystalline materials remains limited. To address this need, we developed a Green's function formalism to capture electron-phonon contributions to core-level spectroscopies without explicitly solving the full vibronic problem. Our approach is based on the cumulant expansion of the Green's function combined with many-body theory calculated vibrational coupling constants. The methodology is applied to x-ray photoemission spectroscopy, x-ray absorption spectroscopy (XAS), and RIXS. In the case of the XAS and RIXS, we use a two-particle exciton Green's function, which accounts implicitly for particle-hole interference effects that have previously proved difficult. To demonstrate the methodology and gain a deeper understanding of the experimental technique, we apply our formalism to small molecules, for which unambiguous experimental data exist. This comparison reveals that the vibronic coupling constant probed by RIXS is in fact related to exciton-phonon coupling rather than electron-phonon coupling, challenging the conventional interpretation of the experiment.

Authors:
 [1]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
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:
1637655
Report Number(s):
BNL-216122-2020-JAAM
Journal ID: ISSN 2469-9950;2469-9969
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 98; Journal Issue: 21; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Electron-phonon coupling; First-principles calculations; Bethe-Salpeter equation; Diagrammatic methods; Resonant inelastic x-ray scattering; X-ray absorption near-edge spectroscopy

Citation Formats

Geondzhian, Andrey, and Gilmore, Keith. Demonstration of resonant inelastic x-ray scattering as a probe of exciton-phonon coupling. United States: N. p., 2018. Web. doi:10.1103/physrevb.98.214305.
Geondzhian, Andrey, & Gilmore, Keith. Demonstration of resonant inelastic x-ray scattering as a probe of exciton-phonon coupling. United States. doi:10.1103/physrevb.98.214305.
Geondzhian, Andrey, and Gilmore, Keith. Mon . "Demonstration of resonant inelastic x-ray scattering as a probe of exciton-phonon coupling". United States. doi:10.1103/physrevb.98.214305. https://www.osti.gov/servlets/purl/1637655.
@article{osti_1637655,
title = {Demonstration of resonant inelastic x-ray scattering as a probe of exciton-phonon coupling},
author = {Geondzhian, Andrey and Gilmore, Keith},
abstractNote = {Resonant inelastic x-ray scattering (RIXS) is a promising technique for obtaining electron-phonon coupling constants. However, the ability to extract these coupling constants throughout the Brillouin zone for crystalline materials remains limited. To address this need, we developed a Green's function formalism to capture electron-phonon contributions to core-level spectroscopies without explicitly solving the full vibronic problem. Our approach is based on the cumulant expansion of the Green's function combined with many-body theory calculated vibrational coupling constants. The methodology is applied to x-ray photoemission spectroscopy, x-ray absorption spectroscopy (XAS), and RIXS. In the case of the XAS and RIXS, we use a two-particle exciton Green's function, which accounts implicitly for particle-hole interference effects that have previously proved difficult. To demonstrate the methodology and gain a deeper understanding of the experimental technique, we apply our formalism to small molecules, for which unambiguous experimental data exist. This comparison reveals that the vibronic coupling constant probed by RIXS is in fact related to exciton-phonon coupling rather than electron-phonon coupling, challenging the conventional interpretation of the experiment.},
doi = {10.1103/physrevb.98.214305},
journal = {Physical Review B},
issn = {2469-9950},
number = 21,
volume = 98,
place = {United States},
year = {2018},
month = {12}
}

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

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Dynamic Jahn-Teller Effect and Colossal Magnetoresistance in La 1 x Sr x MnO 3
journal, July 1996


Spin-Hall Conductivity in Electron-Phonon Coupled Systems
journal, August 2006


Thermal conductivity and phonon transport properties of silicon using perturbation theory and the environment-dependent interatomic potential
journal, September 2009

  • Pascual-Gutiérrez, José A.; Murthy, Jayathi Y.; Viskanta, Raymond
  • Journal of Applied Physics, Vol. 106, Issue 6
  • DOI: 10.1063/1.3195080

Electron-phonon interactions from first principles
journal, February 2017


Theory of Superconductivity
journal, December 1957


Photoemission Study of a Strongly Coupled Electron-Phonon System
journal, July 1999


Electron-Phonon Renormalization of the Direct Band Gap of Diamond
journal, December 2010


Effect of Exciton-Phonon Coupling in the Calculated Optical Absorption of Carbon Nanotubes
journal, January 2005


Electron-phonon coupling effects explored by inelastic neutron scattering
journal, January 2005


Electron-Phonon Interaction in N-Doped Cuprates: an Inelastic X-Ray Scattering Study
journal, March 2003

  • D'Astuto, M.; Mang, P. K.; Giura, P.
  • International Journal of Modern Physics B, Vol. 17, Issue 04n06
  • DOI: 10.1142/S0217979203016133

Phonon spectra in pure and carbon doped MgB2 by inelastic X-ray scattering
journal, June 2007

  • Baron, Alfred Q. R.; Uchiyama, Hiroshi; Tsutsui, Satoshi
  • Physica C: Superconductivity, Vol. 456, Issue 1-2
  • DOI: 10.1016/j.physc.2007.01.028

Scanning tunneling spectroscopy of high-temperature superconductors
journal, March 2007

  • Fischer, Øystein; Kugler, Martin; Maggio-Aprile, Ivan
  • Reviews of Modern Physics, Vol. 79, Issue 1
  • DOI: 10.1103/RevModPhys.79.353

Effective Tunneling Density of States in Superconductors
journal, April 1963


Direct observation of the electron-phonon coupling between empty states in graphite via high-resolution electron energy-loss spectroscopy
journal, April 2017


Photoemission and inverse-photoemission study of superconducting YNi 2 B 2 C: Effects of electron-electron and electron-phonon interactions
journal, October 1994


Ubiquitous strong electron–phonon coupling at the interface of FeSe/SrTiO3
journal, February 2017

  • Zhang, Chaofan; Liu, Zhongkai; Chen, Zhuoyu
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14468

Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects
journal, July 2007


Resonant inelastic x-ray scattering studies of elementary excitations
journal, June 2011

  • Ament, Luuk J. P.; van Veenendaal, Michel; Devereaux, Thomas P.
  • Reviews of Modern Physics, Vol. 83, Issue 2
  • DOI: 10.1103/RevModPhys.83.705

Directly Characterizing the Relative Strength and Momentum Dependence of Electron-Phonon Coupling Using Resonant Inelastic X-Ray Scattering
journal, October 2016


Determining the electron-phonon coupling strength from Resonant Inelastic X-ray Scattering at transition metal L-edges
journal, July 2011

  • Ament, L. J. P.; van Veenendaal, M.; van den Brink, J.
  • EPL (Europhysics Letters), Vol. 95, Issue 2
  • DOI: 10.1209/0295-5075/95/27008

Inelastic X-ray scattering in YBa2Cu3O6.6 reveals giant phonon anomalies and elastic central peak due to charge-density-wave formation
journal, November 2013

  • Le Tacon, M.; Bosak, A.; Souliou, S. M.
  • Nature Physics, Vol. 10, Issue 1
  • DOI: 10.1038/nphys2805

Ground state potential energy surfaces around selected atoms from resonant inelastic x-ray scattering
journal, January 2016

  • Schreck, Simon; Pietzsch, Annette; Kennedy, Brian
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep20054

Raman Scattering, Luminescence, and Exciton-Phonon Coupling in Cu 2 O
journal, December 1972


On the use of Raman scattering to probe exciton–phonon coupling in molecular crystals
journal, February 1975

  • Sceats, M. G.; Rice, Stuart A.
  • The Journal of Chemical Physics, Vol. 62, Issue 3
  • DOI: 10.1063/1.430552

One-phonon resonant Raman scattering: Fröhlich exciton-phonon interaction
journal, August 1989


Ab Initio Approach to Second-order Resonant Raman Scattering Including Exciton-Phonon Interaction
journal, August 2017


Selective gating to vibrational modes through resonant X-ray scattering
journal, January 2017

  • Couto, Rafael C.; Cruz, Vinícius V.; Ertan, Emelie
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14165

Electron-lattice interactions strongly renormalize the charge-transfer energy in the spin-chain cuprate Li2CuO2
journal, February 2016

  • Johnston, Steve; Monney, Claude; Bisogni, Valentina
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10563

Cumulant expansion for phonon contributions to the electron spectral function
journal, November 2014


Über die Streuung von Strahlung durch Atome
journal, February 1925

  • Kramers, H. A.; Heisenberg, W.
  • Zeitschrift für Physik, Vol. 31, Issue 1
  • DOI: 10.1007/BF02980624

A new formula to calculate Franck–Condon factors for displaced and distorted harmonic oscillators
journal, July 2005


Role of Lattice Coupling in Establishing Electronic and Magnetic Properties in Quasi-One-Dimensional Cuprates
journal, June 2013


Electron-Phonon Coupling in the Bulk of Anatase TiO 2 Measured by Resonant Inelastic X-Ray Spectroscopy
journal, August 2015


Hybridization and electron-phonon coupling in ferroelectric BaTiO 3 probed by resonant inelastic x-ray scattering
journal, November 2016


Observation of phonons with resonant inelastic x-ray scattering
journal, November 2010


Exciton–Phonon Interactions in Molecular Crystals
journal, February 1970

  • Grover, M. K.; Silbey, R.
  • The Journal of Chemical Physics, Vol. 52, Issue 4
  • DOI: 10.1063/1.1673263

Dynamical properties of X-ray Raman scattering
journal, January 2003

  • Sałek, P.; Baev, A.; Gel'mukhanov, F.
  • Phys. Chem. Chem. Phys., Vol. 5, Issue 1
  • DOI: 10.1039/B209717F

Intramolecular soft modes and intermolecular interactions in liquid acetone
journal, October 2011


Theoretical simulations of oxygen K -edge resonant inelastic x-ray scattering of kaolinite
journal, April 2017


A study of the water molecule using frequency control over nuclear dynamics in resonant X-ray scattering
journal, January 2017

  • Vaz da Cruz, Vinícius; Ertan, Emelie; Couto, Rafael C.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 30
  • DOI: 10.1039/C7CP01215B

Many-body correlations and excitonic effects in semiconductor spectroscopy
journal, January 2006


Optical absorption spectra of the Holstein molecular crystal for weak and intermediate electronic coupling
journal, July 2002


Raman-scattering study of exciton-phonon coupling in PbS nanocrystals
journal, April 1997


Comments on exciton phonon coupling: Temperature dependence
journal, August 1976

  • Yarkony, David; Silbey, Robert
  • The Journal of Chemical Physics, Vol. 65, Issue 3
  • DOI: 10.1063/1.433182

Exciton-phonon interaction in CdSe and CuCl polar semiconductor nanospheres
journal, November 1994


Ab Initio Finite-Temperature Excitons
journal, September 2008


Valence Electron Photoemission Spectrum of Semiconductors: Ab Initio Description of Multiple Satellites
journal, October 2011


Physical Origin of Satellites in Photoemission of Doped Graphene: An Ab Initio G W Plus Cumulant Study
journal, April 2013


Singularities in the X-Ray Spectra of Metals
journal, January 1970


Threshold singularities of the x-ray Raman scattering in metals
journal, October 1974


Effects of Recoil on Shake-Up Spectra in Metals
journal, January 1980


Corrections to Migdal’s theorem for spectral functions: A cumulant treatment of the time-dependent Green’s function
journal, October 1994


Multiple Plasmon Satellites in Na and Al Spectral Functions from Ab Initio Cumulant Expansion
journal, September 1996


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


Cumulant expansion of the retarded one-electron Green function
journal, August 2014


Dynamical effects in electron spectroscopy
journal, November 2015

  • Zhou, Jianqiang Sky; Kas, J. J.; Sponza, Lorenzo
  • The Journal of Chemical Physics, Vol. 143, Issue 18
  • DOI: 10.1063/1.4934965

The GW plus cumulant method and plasmonic polarons: application to the homogeneous electron gas*
journal, November 2016


Revisiting the origin of satellites in core-level photoemission of transparent conducting oxides: The case of n -doped SnO 2
journal, April 2018


Band Structures of Plasmonic Polarons
journal, April 2015


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


Dynamical screening in correlated metals: Spectral properties of SrVO 3 in the G W approximation and beyond
journal, April 2013


Ab initio G W plus cumulant calculation for isolated band systems: Application to organic conductor ( TMTSF ) 2 PF 6 and transition-metal oxide SrVO 3
journal, February 2016


Real-time cumulant approach for charge-transfer satellites in x-ray photoemission spectra
journal, March 2015


Particle-hole cumulant approach for inelastic losses in x-ray spectra
journal, July 2016


Electron–vibration coupling induced renormalization in the photoemission spectrum of diamondoids
journal, April 2016

  • Gali, Adam; Demján, Tamás; Vörös, Márton
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11327

Electron–Phonon Interactions in an Insulator
journal, February 1975

  • Dunn, Dennis
  • Canadian Journal of Physics, Vol. 53, Issue 4
  • DOI: 10.1139/p75-042

Anomalous Natural Linewidth in the 2 p Photoelectron Spectrum of S i F 4
journal, November 2002


Influence of core hole screening on molecular Auger rates and inner-shell lifetimes
journal, March 1994


Vibrationally resolved O 1s photoelectron spectrum of water
journal, October 2003


A Relativistic Equation for Bound-State Problems
journal, December 1951


Excitonic Effects and the Optical Absorption Spectrum of Hydrogenated Si Clusters
journal, April 1998


Electron-Hole Excitations in Semiconductors and Insulators
journal, September 1998


Ab Initio Calculation of Excitonic Effects in the Optical Spectra of Semiconductors
journal, May 1998


Vibrational effects on SrTiO 3 Ti 1s absorption spectra studied using first-principles methods
journal, August 2008


Numerical quantification of the vibronic broadening of the SrTiO 3 Ti L-edge spectrum
journal, July 2010


Vibrationally resolved O 1 s core-excitation spectra of CO and NO
journal, May 1999


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


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


K -shell photoabsorption of the N 2 molecule
journal, December 1989


Evidence for ubiquitous strong electron–phonon coupling in high-temperature superconductors
journal, August 2001

  • Lanzara, A.; Bogdanov, P. V.; Zhou, X. J.
  • Nature, Vol. 412, Issue 6846
  • DOI: 10.1038/35087518

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

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


First-principles calculations of x-ray absorption in a scheme based on ultrasoft pseudopotentials: From α -quartz to high- T c compounds
journal, August 2009