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Title: Benchmarking the Fundamental Electronic Properties of small TiO2 Nanoclusters by GW and Coupled Cluster Theory Calculations

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [3];  [3];  [4]; ORCiD logo [5]; ORCiD logo [6]
  1. Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, United Kingdom, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom
  2. Institute of Nanotechnology, Karlsruhe Institute of Technology, Campus North, D-76344 Karlsruhe, Germany
  3. Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, Louisiana 70803, United States
  4. Nanoscopic Physics, Institute of Condensed Matter and Nanosciences, Université Catholique de Louvain, 1348 Louvain-la-Neuve, Belgium
  5. William R. Wiley Environmental Molecular Science Laboratory, Battelle, Pacific Northwest National Laboratory, K8-91, P. O. Box 999, Richland, Washington 99352, United States
  6. Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom
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We study the vertical and adiabatic ionization potentials and electron affinities of bare and hydroxylated TiO2 nanoclusters, as well as their fundamental gap and exciton binding energy values, to understand how the clusters’ electronic properties change as a function of size and hydroxylation. In addition, we have employed a range of many-body methods; including G0W0, qsGW, EA/IP-EOM-CCSD, and DFT (B3LYP, PBE), to compare the performance and predictions of the different classes of methods. We demonstrate that, for bare clusters, all many-body methods predict the same trend with cluster size. The highest occupied and lowest unoccupied DFT orbitals follow the same trends as the electron affinity and ionization potentials predicted by the many-body methods, but are generally far too shallow and deep respectively in absolute terms. In contrast, the ΔDFT method is found to yield values in the correct energy window. However, its predictions depend upon the functional used and do not necessarily follow trends based on the many-body methods. Adiabatic potentials are predicted to be similar to their vertical counterparts and holes found to be trapped more strongly than excess electrons. The effect of hydroxylation on the clusters is to open up both the optical and fundamental gap. Finally, a simple microscopic explanation for the observed trends with cluster size and upon hydroxylation is proposed in terms of the onsite electrostatic potential.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Louisiana State Univ., Baton Rouge, LA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC06-76RL01830; SC0012432; AC05-76RL01830
OSTI ID:
1371788
Alternate ID(s):
OSTI ID: 1390409; OSTI ID: 1508246; OSTI ID: 1508249
Report Number(s):
PNNL-SA-125647
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

References (104)

Resolved Quadrupolar Transition in Ti O 2 journal December 1977
Probing the Electronic Structure and Band Gap Evolution of Titanium Oxide Clusters (TiO 2 ) n - ( n = 1−10) Using Photoelectron Spectroscopy journal March 2007
Effect of TiO2 Crystallite Diameter on Photocatalytic Water Splitting Rate journal January 2014
Bulk and Surface Polarons in Photoexcited Anatase TiO 2 journal August 2011
Photodecomposition of water over Pt/TiO2 catalysts journal May 1980
Off-Diagonal Self-Energy Terms and Partially Self-Consistency in GW Calculations for Single Molecules: Efficient Implementation and Quantitative Effects on Ionization Potentials journal October 2015
Structure and Stability of Small TiO 2 Nanoparticles journal August 2005
Quasiparticle and optical properties of rutile and anatase TiO 2 journal August 2010
Modeling the Water Splitting Activity of a TiO 2 Rutile Nanoparticle journal June 2015
Molecular Structures and Energetics of the (TiO 2 ) n ( n = 1−4) Clusters and Their Anions journal July 2008
Formation and fragmentation of gas-phase titanium/oxygen cluster positive ions journal September 1990
Theoretical Investigation of the Hydrogenation of (TiO 2 ) N Clusters ( N = 1–10) journal July 2011
Second order many‐body perturbation approximations to the coupled cluster Green’s function journal January 1995
Electron propagator theory with the ground state correlated by the coupled-cluster method journal March 1993
Studies of reactions of small titanium oxide cluster cations toward oxygen at thermal energies journal September 1992
Coupled-cluster representation of Green function employing modified spectral resolutions of similarity transformed Hamiltonians journal September 2014
Electronic structure calculations on workstation computers: The program system turbomole journal October 1989
The density functional formalism, its applications and prospects journal July 1989
Disinfection of spring water and secondary treated municipal wastewater by TiO2 photocatalysis journal January 2010
Mechanism of Photocatalytic Water Splitting in TiO 2 . Reaction of Water with Photoholes, Importance of Charge Carrier Dynamics, and Evidence for Four-Hole Chemistry journal October 2008
Probing the Optical Property and Electronic Structure of TiO 2 Nanomaterials for Renewable Energy Applications journal May 2014
Nobel Lecture: Electronic structure of matter—wave functions and density functionals journal October 1999
Quasi-Particle Self-Consistent GW for Molecules journal May 2016
Electronic excitations in single-walled GaN nanotubes from first principles: Dark excitons and unconventional diameter dependences journal January 2008
Vibronic coupling effects on the structure and spectroscopy of neutral and charged TiO2 clusters journal October 2012
Electronic structure of titanium oxide clusters: TiOy (y = 1−3) and (TiO2)n (n = 1−4) journal November 1997
Reactivity of (TiO 2 ) N Clusters ( N = 1−10): Probing Gas-Phase Acidity and Basicity Properties journal September 2008
Long range coupling between defect centres in inorganic nanostructures: Valence alternation pairs in nanoscale silica journal October 2012
Size and Shape Dependence of the Electronic and Spectral Properties in TiO 2 Nanoparticles journal April 2011
Calculations of the low-lying excited states of the TiO 2 molecule journal November 2010
Optical excitations in stoichiometric uncapped ZnS nanostructures journal January 2011
Determination of the Exciton Binding Energy in CdSe Quantum Dots journal January 2009
On correlation effects in electron spectroscopies and the GW approximation journal October 1999
The nature of excess electrons in anatase and rutile from hybrid DFT and RPA journal January 2014
Size Effects in the Interface Level Alignment of Dye-Sensitized TiO 2 Clusters journal June 2014
Diagrammatic analysis and application of the coupled cluster response approach to ground-state expectation values journal July 1993
The Kohn–Sham gap, the fundamental gap and the optical gap: the physical meaning of occupied and virtual Kohn–Sham orbital energies journal January 2013
Turbomole
  • Furche, Filipp; Ahlrichs, Reinhart; Hättig, Christof
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 2 https://doi.org/10.1002/wcms.1162
journal July 2013
Theoretical Study of the Electronic Structure and Stability of Titanium Dioxide Clusters (TiO 2 ) n with n = 1−9 journal May 2006
Realistic Cluster Modeling of Electron Transport and Trapping in Solvated TiO 2 Nanoparticles journal July 2012
New Method for Calculating the One-Particle Green's Function with Application to the Electron-Gas Problem journal August 1965
Benchmark Calculations of Energetic Properties of Groups 4 and 6 Transition Metal Oxide Nanoclusters Including Comparison to Density Functional Theory journal July 2016
Computational Study of H 2 and O 2 Production from Water Splitting by Small (MO 2 ) n Clusters (M = Ti, Zr, Hf) journal April 2013
Quasiparticle Self-Consistent G W Theory journal June 2006
Electron Counting in Solids: Oxidation States, Partial Charges, and Ionicity journal April 2017
Coupled cluster Green function: Model involving single and double excitations journal April 2016
The equation-of-motion coupled-cluster method: Excitation energies of Be and CO journal December 1989
Coupled cluster calculations on TiO 2 nanoclusters journal August 2013
Effect of Dot Size on Exciton Binding Energy and Electron–Hole Recombination Probability in CdSe Quantum Dots journal September 2013
Photocatalytic properties of rutile TiO 2 powder for overall water splitting journal January 2014
Visible-Light-Driven N−F−Codoped TiO 2 Photocatalysts. 2. Optical Characterization, Photocatalysis, and Potential Application to Air Purification journal May 2005
Polymorph Engineering of TiO 2 : Demonstrating How Absolute Reference Potentials Are Determined by Local Coordination journal May 2015
Structure, electronic, and optical properties of TiO 2 atomic clusters: An ab initio study journal December 2011
Electronic and Optical Properties of Doped and Undoped (TiO 2 ) n Nanoparticles journal September 2010
Mechanism of photocatalytic water oxidation on small TiO 2 nanoparticles journal January 2017
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields journal November 1994
Mechanism of Photoinduced Superhydrophilicity on the TiO 2 Photocatalyst Surface journal August 2005
Effect of Size and Structure on the Ground-State and Excited-State Electronic Structure of TiO 2 Nanoparticles journal July 2016
Highly efficient dye-sensitized solar cells: progress and future challenges journal January 2013
Mind the gap! journal January 2014
Band alignment of rutile and anatase TiO2 journal July 2013
Describing Excited State Relaxation and Localization in TiO 2 Nanoparticles Using TD-DFT journal November 2014
The GW -Method for Quantum Chemistry Applications: Theory and Implementation journal December 2012
Photoactivity of Molecule–TiO 2 Clusters with Time-Dependent Density-Functional Theory journal February 2016
Computational Study of the Hydrolysis Reactions of the Ground and First Excited Triplet States of Small TiO 2 Nanoclusters journal April 2011
Electronic structure of dye-sensitized TiO 2 clusters from many-body perturbation theory journal December 2011
Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism journal May 1976
Covalent O–H Bonds as Electron Traps in Proton-Rich Rutile TiO 2 Nanoparticles journal March 2014
Self-cleaning coatings journal January 2005
Quantum Chemical Investigation of Cluster Models for TiO 2 Nanoparticles with Water-Derived Ligand Passivation: Studies of Excess Electron States and Implications for Charge Transport in the Gratzel Cell journal October 2009
Light-induced water splitting by titanium-tetrahydroxide: a computational study journal January 2015
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Dependence of Activity of Rutile Titanium(IV) Oxide Powder for Photocatalytic Overall Water Splitting on Structural Properties journal April 2014
Structure Selection Based on High Vertical Electron Affinity for TiO 2 Clusters journal March 2012
Equation of motion coupled cluster methods for electron attachment and ionization potential in fullerenes C 60 and C 70 journal August 2014
Structural and Electronic Properties of Photoexcited TiO 2 Nanoparticles from First Principles journal January 2015
The equation of motion coupled‐cluster method. A systematic biorthogonal approach to molecular excitation energies, transition probabilities, and excited state properties journal May 1993
Photocatalytic Activity of Rutile Titania for Hydrogen Evolution journal April 2014
Electronic excitations: density-functional versus many-body Green’s-function approaches journal June 2002
Tree Growth—Hybrid Genetic Algorithm for Predicting the Structure of Small (TiO 2 ) n , n = 2–13, Nanoclusters journal June 2013
Fully optimized contracted Gaussian basis sets for atoms Li to Kr journal August 1992
All-Electron Self-Consistent G W Approximation: Application to Si, MnO, and NiO journal September 2004
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
Coupled-cluster theory in quantum chemistry journal February 2007
Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc–Zn journal August 2005
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Self-energy and excitonic effects in the electronic and optical properties of TiO 2 crystalline phases journal July 2010
Modeling Excited States in TiO 2 Nanoparticles: On the Accuracy of a TD-DFT Based Description journal February 2014
T i O 2 -Based Photocatalytic Process for Purification of Polluted Water: Bridging Fundamentals to Applications journal January 2013
Coupled cluster approach to the single-particle Green's function journal March 1992
GW 100: Benchmarking G 0 W 0 for Molecular Systems journal November 2015
Is There a Nanosize for the Activity of TiO 2 Compounds? journal June 2009
Photocatalytic degradation for environmental applications - a review
  • Bhatkhande, Dhananjay S.; Pangarkar, Vishwas G.; Beenackers, Anthony A?C?M
  • Journal of Chemical Technology & Biotechnology, Vol. 77, Issue 1 https://doi.org/10.1002/jctb.532
journal January 2001
Understanding TiO 2 Photocatalysis: Mechanisms and Materials journal May 2014
Stability and Electronic Properties of TiO 2 Nanostructures With and Without B and N Doping journal June 2009
Computational design of nanoclusters by property-based genetic algorithms: Tuning the electronic properties of ( TiO 2 ) n clusters journal June 2015
Excitonic Effects and the Optical Absorption Spectrum of Hydrogenated Si Clusters journal April 1998
The equation-of-motion coupled-cluster method. Applications to open- and closed-shell reference states journal May 1993
First-principles real-space study of electronic and optical excitations in rutile TiO 2 nanocrystals journal October 2014
Coupled cluster Green's function method: Working equations and applications journal October 1993
Solar Energy Conversion by Dye-Sensitized Photovoltaic Cells journal October 2005
Direct splitting of pure water into hydrogen and oxygen using rutile titania powder as a photocatalyst journal January 2013
Visible Light Absorption of N-Doped TiO 2 Rutile Using (LR/RT)-TDDFT and Active Space EOMCCSD Calculations journal October 2011

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