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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:
 [1];  [2];  [1]
  1. Harvard Univ., Cambridge, MA (United States)
  2. Russia and Novosibirsk States Univ. (Russia)
Publication Date:
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.
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.
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.
@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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