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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 Laboratory (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; TRN: US2201658
Grant/Contract Number:  
SC0012704
Resource Type:
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

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. https://doi.org/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. https://doi.org/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},
number = 21,
volume = 98,
place = {United States},
year = {Mon Dec 10 00:00:00 EST 2018},
month = {Mon Dec 10 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 15 works
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Figures / Tables:

FIG. 1 FIG. 1: RIXS loss profile for two equally coupled modes. The contribution from the two mode model that includes mixing of the modes (black curve an grey shading) is compared to the independent mode approximation (red curve). In the latter case, the individual contributions from the two modes are givenmore » by the dashed blue and dotted green curves. In each panel, the energies of the two modes are ω1 = 30 meV and ω2 = 75 meV, the core-hole lifetime is γ/2 = 200 meV and the excitation was tuned to the resonance. The dimensionful coupling strength of the two modes are set equal in each panel and are 50 meV (2M/γ = 0.25) (a), 100 meV (2M/γ = 0.5) (b), and 200 meV (2M/γ = 1) (c). The elastic lines are not shown.« less

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Works referenced in this record:

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


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


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


Effective Tunneling Density of States in Superconductors
journal, April 1963


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

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


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


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

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


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

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

Band Structures of Plasmonic Polarons
journal, April 2015


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

Ab Initio Finite-Temperature Excitons
journal, September 2008


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


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


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


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


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

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


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


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


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


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


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


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

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


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

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

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

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


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

Electron-phonon interactions from first principles
journal, February 2017


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


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


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


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


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


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


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


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

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


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


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


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


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


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


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


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

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


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


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


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


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


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


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


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

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


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


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


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


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

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

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


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


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


Electron–Phonon Interactions in an Insulator
journal, February 1975

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

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


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


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

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


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


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

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


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


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


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

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


Works referencing / citing this record:

Experimental Determination of Momentum-Resolved Electron-Phonon Coupling
journal, July 2019


High-resolution resonant inelastic x-ray scattering study of the electron-phonon coupling in honeycomb α Li 2 IrO 3
journal, December 2019


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