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Describing excited state relaxation and localization in TiO2 nanoparticles using TD-DFT

Journal Article · · Journal of Chemical Theory and Computation
DOI:https://doi.org/10.1021/ct4010273· OSTI ID:1167290
 [1];  [2];  [2];  [1];  [1];  [2];  [1]
  1. Univ. College London, London (United Kingdom)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
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We have investigated the description of excited state relaxation in naked and hydrated TiO2 nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials; B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to be the inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree-Fock Like Exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT-problems for certain particles. We hypothesize that the spurious stabilization of CT-states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries than those obtained using TD-CAM-B3LYP or TD-BHLYP. In conclusion, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in naked and hydrated TiO2 nanoparticles is predicted to be associated with a large Stokes’ shift.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1167290
Alternate ID(s):
OSTI ID: 1129283
Report Number(s):
PNNL-SA--105025; 48197; KP1704020
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 3 Vol. 10; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Time-dependent DFT and experimental study on visible light photocatalysis by metal oxides of Ti, V and Zn after complexing with a conjugated polymer journal January 2019
Investigating the character of excited states in TiO 2 nanoparticles from topological descriptors: implications for photocatalysis journal January 2020
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Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
Environmental Molecular Sciences Laboratory
TD-DFT
Time-Dependent Density Functional Theory
localization
nanoparticles