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Title: First-principles real-space study of electronic and optical excitations in rutile TiO 2 nanocrystals

Abstract

We model rutile titanium dioxide nanocrystals (NCs) up to ~1.5 nm in size to study the effects of quantum confinement on their electronic and optical properties. Ionization potentials (IPs) and electron affinities (EAs) are obtained via the perturbative GW approximation (G0W0) and ΔSCF method for NCs up to 24 and 64 TiO2 formula units, respectively. These demanding GW computations are made feasible by using a real-space framework that exploits quantum confinement to reduce the number of empty states needed in GW summations. Time-dependent density functional theory (TDDFT) is used to predict the optical properties of NCs up to 64 TiO2 units. For a NC containing only 2 TiO2 units, the offsets of the IP and the EA from the corresponding bulk limits are of similar magnitude. However, as NC size increases, the EA is found to converge more slowly to the bulk limit than the IP. The EA values computed at the G0W0 and ΔSCF levels of theory are found to agree fairly well with each other, while the IPs computed with ΔSCF are consistently smaller than those computed with G0W0 by a roughly constant amount. TDDFT optical gaps exhibit weaker size dependence than GW quasiparticle gaps, and result inmore » exciton binding energies on the order of eV. Finally, altering the dimensions of a fixed-size NC can change electronic and optical excitations up to several tenths of an eV. The largest NCs modeled are still quantum confined and do not yet have quasiparticle levels or optical gaps at bulk values. Nevertheless, we find that classical Mie-Gans theory can quite accurately reproduce the line shape of TDDFT absorption spectra, even for (anisotropic) TiO2 NCs of subnanometer size.« less

Authors:
ORCiD logo [1];  [1];  [1]
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  1. Univ. of Illinois, Chicago, IL (United States)
Publication Date:
Research Org.:
Univ. of Illinois, Chicago, IL (United States); Univ. of Illinois, Chicago, IL (United States). Dept. of Physics
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1351313
Alternate Identifier(s):
OSTI ID: 1180582; OSTI ID: 1351312
Grant/Contract Number:  
SC0001853; AC02-05CH11231; FG02-09ER16072
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. B, Condensed Matter and Materials Physics
Additional Journal Information:
Journal Volume: 90; Journal Issue: 16; Journal ID: ISSN 1098-0121
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Hung, Linda, Baishya, Kopinjol, and Öğüt, Serdar. First-principles real-space study of electronic and optical excitations in rutile TiO2 nanocrystals. United States: N. p., 2014. Web. doi:10.1103/PhysRevB.90.165424.
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Hung, Linda, Baishya, Kopinjol, & Öğüt, Serdar. First-principles real-space study of electronic and optical excitations in rutile TiO2 nanocrystals. United States. https://doi.org/10.1103/PhysRevB.90.165424
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Hung, Linda, Baishya, Kopinjol, and Öğüt, Serdar. Fri . "First-principles real-space study of electronic and optical excitations in rutile TiO2 nanocrystals". United States. https://doi.org/10.1103/PhysRevB.90.165424. https://www.osti.gov/servlets/purl/1351313.
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@article{osti_1351313,
title = {First-principles real-space study of electronic and optical excitations in rutile TiO2 nanocrystals},
author = {Hung, Linda and Baishya, Kopinjol and Öğüt, Serdar},
abstractNote = {We model rutile titanium dioxide nanocrystals (NCs) up to ~1.5 nm in size to study the effects of quantum confinement on their electronic and optical properties. Ionization potentials (IPs) and electron affinities (EAs) are obtained via the perturbative GW approximation (G0W0) and ΔSCF method for NCs up to 24 and 64 TiO2 formula units, respectively. These demanding GW computations are made feasible by using a real-space framework that exploits quantum confinement to reduce the number of empty states needed in GW summations. Time-dependent density functional theory (TDDFT) is used to predict the optical properties of NCs up to 64 TiO2 units. For a NC containing only 2 TiO2 units, the offsets of the IP and the EA from the corresponding bulk limits are of similar magnitude. However, as NC size increases, the EA is found to converge more slowly to the bulk limit than the IP. The EA values computed at the G0W0 and ΔSCF levels of theory are found to agree fairly well with each other, while the IPs computed with ΔSCF are consistently smaller than those computed with G0W0 by a roughly constant amount. TDDFT optical gaps exhibit weaker size dependence than GW quasiparticle gaps, and result in exciton binding energies on the order of eV. Finally, altering the dimensions of a fixed-size NC can change electronic and optical excitations up to several tenths of an eV. The largest NCs modeled are still quantum confined and do not yet have quasiparticle levels or optical gaps at bulk values. Nevertheless, we find that classical Mie-Gans theory can quite accurately reproduce the line shape of TDDFT absorption spectra, even for (anisotropic) TiO2 NCs of subnanometer size.},
doi = {10.1103/PhysRevB.90.165424},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 16,
volume = 90,
place = {United States},
year = {Fri Oct 17 00:00:00 EDT 2014},
month = {Fri Oct 17 00:00:00 EDT 2014}
}
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https://doi.org/10.1103/PhysRevB.90.165424
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    Modeling Excited States of Confined Systems
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