Berardo, E;
Hu, H-S;
van Dam, HJJ;
Shevlin, SA;
Woodley, SM;
Kowalski, K;
Zwijnenburg, MA;
(2014)
Describing Excited State Relaxation and Localization in TiO2 Nanoparticles Using TD-DFT.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
, 10
(12)
5538 - 5548.
10.1021/ct500787x.
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Abstract
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 during excited state relaxation 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 from those obtained using TD-CAM-B3LYP or TD-BHLYP. Finally, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in small naked and hydrated TiO2 nanoparticles is predicted to be associated with a large Stokes’ shift.
| Type: | Article |
|---|---|
| Title: | Describing Excited State Relaxation and Localization in TiO2 Nanoparticles Using TD-DFT |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/ct500787x |
| Publisher version: | http://dx.doi.org/10.1021/ct500787x |
| Language: | English |
| Additional information: | ACS AuthorChoice - This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/1462274 |
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