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Title: Modeling Excited States in TiO2 Nanoparticles: On the Accuracy of a TD-DFT Based Description

Journal Article · · Journal of Chemical Theory and Computation, 10(3):1189-1199
DOI:https://doi.org/10.1021/ct4010273· OSTI ID:1129283
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We have investigated the suitability of Time-Dependent Density Functional Theory (TD-DFT) to describe vertical low-energy excitations in naked and hydrated titanium dioxide nanoparticles through a comparison with results from Equation-of-Motion Coupled Cluster (EOM-CC) quantum chemistry methods. We demonstrate that for most TiO2 nanoparticles TD-DFT calculations with commonly used exchange-correlation (XC-)potentials (e.g. B3LYP) and EOM-CC methods give qualitatively similar results. Importantly, however, we also show that for an important subset of structures, TD-DFT gives qualitatively different results depending upon the XC-potential used and that in this case only TD-CAM-B3LYP and TD-BHLYP calculations yield results that are consistent with those obtained using EOM-CC theory. Moreover, we demonstrate that the discrepancies for such structures arise from a particular combination of defects, excitations involving which are charge-transfer excitations and hence are poorly described by XC-potentials that contain no or low fractions of Hartree-Fock like exchange. Finally, we discuss that such defects are readily healed in the presence of ubiquitously present water and that as a result the description of vertical low-energy excitations for hydrated TiO2 nanoparticles is hence non-problematic.

Research Organization:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1129283
Report Number(s):
PNNL-SA-99856; 47720; KP1704020
Journal Information:
Journal of Chemical Theory and Computation, 10(3):1189-1199, Journal Name: Journal of Chemical Theory and Computation, 10(3):1189-1199
Country of Publication:
United States
Language:
English

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Related Subjects

TiO2
nanoparticles
TD-DFT
Equation-of-Motion Coupled Cluster
quantum
chemistry
calculations
time-dependent density funcational theory
Environmental Molecular Sciences Laboratory