Quasiparticle and Optical Properties of Rutile and Anatase TiO${}_2$

Abstract

Quasiparticle excitation energies and optical properties of TiO${}_2$ in the rutile and anatase structures are calculated using many-body perturbation theory methods. Calculations are performed for a frozen crystal lattice; electron-phonon coupling is not explicitly considered. In the GW method, several approximations are compared and it is found that inclusion of the full frequency dependence as well as explicit treatment of the Ti semicore states are essential for accurate calculation of the quasiparticle energy band gap. The calculated quasiparticle energies are in good agreement with available photoemission and inverse photoemission experiments. The results of the GW calculations, together with the calculated static screened Coulomb interaction, are utilized in the Bethe-Salpeter equation to calculate the dielectric function ${\epsilon }_2(\omega )$ for both the rutile and anatase structures. The results are in good agreement with experimental observations, particularly the onset of the main absorption features around 4 eV. For comparison to low temperature optical absorption measurements that resolve individual excitonic transitions in rutile, the low-lying discrete excitonic energy levels are calculated with electronic screening only. The lowest energy exciton found in the energy gap of rutile has a binding energy of 0.13 eV. In agreement with experiment, it is not dipole allowed, but the calculated exciton energy exceeds that measured in absorption experiments by about 0.22 eV and the scale of the exciton binding energy is also too large. The quasiparticle energy alignment of rutile is calculated for non-polar (110) surfaces. In the GW approximation, the valence band maximum is 7.8 eV below the vacuum level, showing a small shift from density functional theory results.

arXiv commentSubmitted to Physical Review B

References in corpus (20)

• The GW method
• Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density-functional theory
• Yambo: an \textit{ab initio} tool for excited state calculations
• Quasiparticle Self-Consistent GW Theory
• All-electron self-consistent GW approximation: Application to Si, MnO, and NiO
• Quasiparticle self-consistent $GW$ method; a basis for the independent-particle approximation
• Self-Energy and Excitonic Effects in the Electronic and Optical Properties of TiO2 Crystalline Phases
• Implementation of an all-electron GW approximation based on the PAW method without plasmon pole approximation: application to Si, SiC, AlAs, InAs, NaH and KH
• {\it Ab--initio} finite temperature excitons
• The Band-Gap Problem in Semiconductors Revisited: Effects of Core States and Many-Body Self-Consistency
• The GW space-time method for the self-energy of large systems
• Band Offsets at the Si/SiO${}_2$ Interface from Many-Body Perturbation Theory
• Quasiparticle Electronic structure of Copper in the GW approximation
• Exciton-plasmon states in nanoscale materials: breakdown of the Tamm-Dancoff approximation
• Stability and Electronic Properties of TiO2 Nanostructures With and Without B and N Doping
• Dynamical excitonic effects in metals and semiconductors
• Effects of polarization on the band-structure of delafossite transparent conductive oxides
• Optical to UV spectra and birefringence of SiO${}_2$ and TiO${}_2$: First-principles calculations with excitonic effects
• Quasiparticle bandstructure effects on the {\it d} hole lifetimes of copper within the GW approximation
• Large crystal local-field effects in the dynamical structure factor of rutile TiO2

Cited by in corpus (47)

• Many-body perturbation theory calculations using the yambo code
• The stability, electronic structure, and optical property of TiO2 polymorphs
• Quasiparticle GW calculations for solids, molecules and 2D materials
• Strongly bound excitons in anatase TiO2 single crystals and nanoparticles
• Bootstrap approximation for the exchange-correlation kernel of time-dependent density functional theory
• Electronic structure and phase stability of oxide semiconductors: Performance of dielectric-dependent hybrid functional DFT, benchmarked against $GW$ band structure calculations and experiments
• Quasiparticle band-edge energy and band offsets of monolayer of molybdenum and tungsten chalcogenide
• Band Gap and Edge Engineering via Ferroic Distortion and Anisotropic Strain: The Case of SrTiO${}_3$
• Defect calculations in semiconductors through a dielectric-dependent hybrid DFT functional: the case of oxygen vacancies in metal oxides
• GW quasiparticle bandgaps of anatase TiO2 starting from DFT+U
• Quasiparticle level alignment for photocatalytic interfaces
• Reproducibility in $G_0{W}_0$ Calculations for Solids
• Strong renormalization of the electronic band gap due to lattice polarization in the GW formalism
• Quantitative Molecular Orbital Energies within a $G_0{W}_0$ Approximation
• First-principles Hubbard U and Hund's J corrected approximate density-functional theory predicts an accurate fundamental gap in rutile and anatase TiO2
• Addressing electron-hole correlation in core excitations of solids: An all-electron many-body approach from first principles
• Converged GW quasiparticle energies for transition metal oxide perovskites
• Comparing quasiparticle H${}_2$O level alignment on anatase and rutile TiO${}_2$
• Optical Absorption Induced by Small Polaron Formation in Transition Metal Oxides -- The Case of Co${}_3$O${}_4$
• Self energy and excitonic effect in (un)doped TiO${}_2$ anatase : A comparative study of hybrid DFT, GW and BSE to explore optical properties
• X-ray Absorption Linear Dichroism at the Ti K-edge of TiO2 anatase single crystals
• Electron-plasmon and electron-phonon satellites in the angle-resolved photoelectron spectra of n-doped anatase TiO2
• Exploring the Statically Screened $G3W2$ Correction to the $GW$ Self-Energy: Charged Excitations and Total Energies of Finite Systems
• DFT+U+J with linear response parameters predicts non-magnetic oxide band gaps with hybrid-functional accuracy
• Electronic and optical properties of doped TiO2 by many-body perturbation theory
• Disorder-induced electron and hole trapping in amorphous TiO2
• Electronic Band Structure of Cuprous and Silver Halides: a Numerically Accurate All-Electron $GW$ Study
• Two-component $GW$ calculations: Cubic scaling implementation and comparison of vertex corrected and partially self-consistent $GW$ variants
• Optical absorption spectra of metal oxides from time-dependent density functional theory and many-body perturbation theory based on optimally-tuned hybrid functionals
• Hubbard-$U$ corrected Hamiltonians for non-self-consistent random-phase approximation total-energy calculations: A study of ZnS, TiO${}_2$, and NiO
• First-principles thermodynamic screening approach to photo-catalytic water splitting with co-catalysts
• Insulating titanium oxynitride for visible light photocatalysis
• Insights and challenges of applying the $GW$ method to transition metal oxides
• Effects of quantum confinement on excited state properties of SrTiO${}_3$ from ab initio many-body perturbation theory
• Polaron-induced phonon localization and stiffening in rutile TiO${}_2$
• Emerging giant resonant exciton induced by Ta-substitution in anatase TiO${}_2$: a tunable correlation effect
• Density fitting in periodic systems: application to TDHF in diamond and oxides
• Electronic structures and optical spectra of thin anatase TiO2 nanowires through hybrid density functional and quasiparticle calculations
• Coverage Dependence of the Level Alignment for Methanol on TiO${}_2$(110)
• DFT study of noble metal impurities on TiO_2(110)
• Anomalous Anisotropic Exciton Temperature Dependence in Rutile TiO2
• First-principles study of excitons in the optical spectra of silver chloride
• Reformulation of DFT+U as a pseudo-hybrid Hubbard density functional
• Band Alignment in Quantum Wells from Automatically Tuned DFT+$U$
• Absorption mechanism of dopamine/DOPAC modified TiO 2 nanoparticles by time-dependent density functional theory calculations
• First-principles approach to ultrafast pump-probe spectroscopy in solids
• Predicting the suitability of photocatalysts for water splitting using Koopmans spectral functionals: The case of TiO${}_2$ polymorphs