Polaron-induced phonon localization and stiffening in rutile $\mathrm{TiO_2}$

doi:10.1103/PhysRevB.96.195165

Title: Polaron-induced phonon localization and stiffening in rutile $$\mathrm{TiO_2}$$

Abstract

Small polaron formation in transition metal oxides, like the prototypical material rutile $$\mathrm{TiO_2}$$, remains a puzzle and a challenge to simple theoretical treatment. In our combined experimental and theoretical study, we examine this problem using Raman spectroscopy of photoexcited samples and real-time time-dependent density functional theory (RT-TDDFT), which employs Ehrenfest dynamics to couple the electronic and ionic subsystems. We observe experimentally the unexpected stiffening of the $$A_{1g}$$ phonon mode under UV illumination and provide a theoretical explanation for this effect. Our analysis also reveals a possible reason for the observed anomalous temperature dependence of the Hall mobility. Finally, small polaron formation in rutile $$\mathrm{TiO_2}$$ is a strongly nonadiabatic process and is adequately described by Ehrenfest dynamics at time scales of polaron formation.

Authors:

Kolesov, Grigory ^[1]; Kolesov, Boris A. ^[2]; Kaxiras, Efthimios ^[1]

Harvard Univ., Cambridge, MA (United States)
Russia and Novosibirsk States Univ. (Russia)

Publication Date:: 2017-11-29

Research Org.:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1523842

Resource Type:: Accepted Manuscript

Journal Name:: Physical Review B

Additional Journal Information:: Journal Volume: 96; Journal Issue: 19; 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


                    Kolesov, Grigory, Kolesov, Boris A., and Kaxiras, Efthimios. Polaron-induced phonon localization and stiffening in rutile $\mathrm{TiO_2}$.  United States: N. p., 2017. 
        Web.  doi:10.1103/PhysRevB.96.195165.

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                    Kolesov, Grigory, Kolesov, Boris A., & Kaxiras, Efthimios. Polaron-induced phonon localization and stiffening in rutile $\mathrm{TiO_2}$.  United States.  doi:10.1103/PhysRevB.96.195165.

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                    Kolesov, Grigory, Kolesov, Boris A., and Kaxiras, Efthimios. Wed .  
        "Polaron-induced phonon localization and stiffening in rutile $\mathrm{TiO_2}$".  United States.  doi:10.1103/PhysRevB.96.195165.  https://www.osti.gov/servlets/purl/1523842.

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@article{osti_1523842,

  title        = {Polaron-induced phonon localization and stiffening in rutile $\mathrm{TiO_2}$},

  author       = {Kolesov, Grigory and Kolesov, Boris A. and Kaxiras, Efthimios},

  abstractNote = {Small polaron formation in transition metal oxides, like the prototypical material rutile $\mathrm{TiO_2}$, remains a puzzle and a challenge to simple theoretical treatment. In our combined experimental and theoretical study, we examine this problem using Raman spectroscopy of photoexcited samples and real-time time-dependent density functional theory (RT-TDDFT), which employs Ehrenfest dynamics to couple the electronic and ionic subsystems. We observe experimentally the unexpected stiffening of the $A_{1g}$ phonon mode under UV illumination and provide a theoretical explanation for this effect. Our analysis also reveals a possible reason for the observed anomalous temperature dependence of the Hall mobility. Finally, small polaron formation in rutile $\mathrm{TiO_2}$ is a strongly nonadiabatic process and is adequately described by Ehrenfest dynamics at time scales of polaron formation.},

  doi          = {10.1103/PhysRevB.96.195165},

  journal      = {Physical Review B},

  number       = 19,

  volume       = 96,

  place        = {United States},

  year         = {2017},

  month        = {11}

}

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Works referenced in this record:

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Similar Records

Title: Polaron-induced phonon localization and stiffening in rutile $$\mathrm{TiO_2}$$

Abstract

Citation Formats

Raman Spectra of Ti O 2 , Mg F 2 , Zn F 2 , Fe F 2 , and Mn F 2 journal, February 1967

The nature of excess electrons in anatase and rutile from hybrid DFT and RPA journal, January 2014

Phonons in a strongly coupled electron-phonon system journal, January 1991

Localized Electronic States from Surface Hydroxyls and Polarons in TiO 2 (110) journal, July 2009

A surface science perspective on TiO2 photocatalysis journal, June 2011

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Chemical bonding in rutile-type compounds journal, February 1992

Charge density and chemical bonding in rutile, TiO 2 journal, June 2003

Quasiparticle and optical properties of rutile and anatase TiO 2 journal, August 2010

Distinction of electron pathways at titanium oxide/liquid interfaces in photocatalytic processes and co-catalyst effects journal, January 2016

Dual behavior of excess electrons in rutile TiO 2 journal, January 2013

On the calculation of multiplet energies by the hartree-fock-slater method journal, January 1977

Studies of polaron motion journal, November 1959

The SIESTA method for ab initio order- N materials simulation journal, March 2002

Spin bags, polarons, and impurity potentials in La 2 − x Sr x CuO 4 from first principles journal, January 1992

Self-Consistent Optimization of Excited States within Density-Functional Tight-Binding journal, December 2015

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

Electronic conduction above 4 K of slightly reduced oxygen-deficient rutile TiO 2 − x journal, September 1996

Polarons in crystalline and non-crystalline materials journal, January 1969

Phonon anharmonicity of rutile TiO 2 studied by Raman spectrometry and molecular dynamics simulations journal, March 2012

Optical Absorption by Polarons in Rutile (TiO2) Single Crystals journal, January 1968

XSEDE: Accelerating Scientific Discovery journal, September 2014

Direct View at Excess Electrons in TiO 2 Rutile and Anatase journal, August 2014

Studies of polaron motion journal, November 1959

Dynamics of the Photogenerated Hole at the Rutile TiO 2 (110)/Water Interface: A Nonadiabatic Simulation Study journal, November 2014

Anatomy of the Photochemical Reaction: Excited-State Dynamics Reveals the C–H Acidity Mechanism of Methoxy Photo-oxidation on Titania journal, April 2015

Electron transport in TiO 2 probed by THz time-domain spectroscopy journal, February 2004

Hall mobility of reduced rutile in the temperature range 300–1250°K journal, January 1969

From electron to small polaron: An exact cluster solution journal, April 1994

Real-Time TD-DFT with Classical Ion Dynamics: Methodology and Applications journal, December 2015

Raman Spectra of Ti $O_{2}$ , Mg $F_{2}$ , Zn $F_{2}$ , Fe $F_{2}$ , and Mn $F_{2}$
journal, February 1967

The nature of excess electrons in anatase and rutile from hybrid DFT and RPA
journal, January 2014

Phonons in a strongly coupled electron-phonon system
journal, January 1991

Localized Electronic States from Surface Hydroxyls and Polarons in TiO ₂ (110)
journal, July 2009

A surface science perspective on TiO2 photocatalysis
journal, June 2011

Computational modeling of self-trapped electrons in rutile TiO ₂
journal, January 2015

Chemical bonding in rutile-type compounds
journal, February 1992

Charge density and chemical bonding in rutile, TiO ₂
journal, June 2003

Quasiparticle and optical properties of rutile and anatase ${TiO}_{2}$
journal, August 2010

Distinction of electron pathways at titanium oxide/liquid interfaces in photocatalytic processes and co-catalyst effects
journal, January 2016

Dual behavior of excess electrons in rutile TiO ₂
journal, January 2013

On the calculation of multiplet energies by the hartree-fock-slater method
journal, January 1977

Studies of polaron motion
journal, November 1959

The SIESTA method for ab initio order- N materials simulation
journal, March 2002

Spin bags, polarons, and impurity potentials in ${La}_{2 - x}$ ${Sr}_{x}$ ${CuO}_{4}$ from first principles
journal, January 1992

Self-Consistent Optimization of Excited States within Density-Functional Tight-Binding
journal, December 2015

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

Electronic conduction above 4 K of slightly reduced oxygen-deficient rutile ${TiO}_{2 - x}$
journal, September 1996

Polarons in crystalline and non-crystalline materials
journal, January 1969

Phonon anharmonicity of rutile TiO $_{2}$ studied by Raman spectrometry and molecular dynamics simulations
journal, March 2012

Optical Absorption by Polarons in Rutile (TiO2) Single Crystals
journal, January 1968

XSEDE: Accelerating Scientific Discovery
journal, September 2014

Direct View at Excess Electrons in ${TiO}_{2}$ Rutile and Anatase
journal, August 2014

Studies of polaron motion
journal, November 1959

Dynamics of the Photogenerated Hole at the Rutile TiO ₂ (110)/Water Interface: A Nonadiabatic Simulation Study
journal, November 2014

Anatomy of the Photochemical Reaction: Excited-State Dynamics Reveals the C–H Acidity Mechanism of Methoxy Photo-oxidation on Titania
journal, April 2015

Electron transport in ${TiO}_{2}$ probed by THz time-domain spectroscopy
journal, February 2004

Hall mobility of reduced rutile in the temperature range 300–1250°K
journal, January 1969

From electron to small polaron: An exact cluster solution
journal, April 1994

Real-Time TD-DFT with Classical Ion Dynamics: Methodology and Applications
journal, December 2015