Please use this identifier to cite or link to this item:
http://hdl.handle.net/2445/114921
Title: | Effect of size and structure on the ground-state and excited-state electronic structure of TiO2 nanoparticles |
Author: | Cho, Daeheum Ko, Kyoung Chul Lamiel Garcia, Josep Oriol Bromley, Stefan Thomas Lee, Jin Yong Illas i Riera, Francesc |
Keywords: | Diòxid de titani Nanopartícules Teoria del funcional de densitat Titanium dioxide Nanoparticles Density functionals |
Issue Date: | 1-Aug-2016 |
Publisher: | American Chemical Society |
Abstract: | We investigated the influence of size and structure on the electronic structure of TiO2 nanoparticles 0.5-3.2 nm in diameter, in both vacuum and water, using density functional theory (DFT) calculations. Specifically, we tracked the optical and electronic energy gap of a set of (TiO2)(n) nanoparticles ranging from small non-bulklike clusters with n = 4, 8, and 16, to larger nanoparticles derived from the anatase bulk crystal with n = 35 and 84. As the difference between these two energy gaps (the exciton binding energy) becomes negligible in the bulk, this magnitude provides an indicator of the bulklike character of the electronic structure of the nanoparticles under study. Extrapolating our results to larger sizes, we obtain a rough estimate of the nanoparticle size at which the electronic structure will begin to be effectively bulklike. Our results generally confirmed that the electronic structure of the nanoparticle ground state and excited state has a more pronounced structure dependency than size dependency within a size range of 0.5-1.5 nm. We also showed that the thermodynamic preference for the photocatalytic species is the first S-1 exciton. This S-1 exciton is stable under vacuum but may evolve to free charge carriers upon structural relaxation in an aqueous environment for particles 0.5-1.5 nm in size studied in the present article. An analysis of ionization potentials and electron affinities, relative to the standard reduction potential for the water splitting half-reactions, revealed the importance of considering the structural relaxation in the excited states and the presence of water for assessing the thermodynamic conditions for photocatalytic water splitting. |
Note: | Versió postprint del document publicat a: https://doi.org/10.1021/acs.jctc.6b00519 |
It is part of: | Journal of Chemical Theory and Computation, 2016, vol. 12, num. 8, p. 3751-3763 |
URI: | http://hdl.handle.net/2445/114921 |
Related resource: | https://doi.org/10.1021/acs.jctc.6b00519 |
ISSN: | 1549-9618 |
Appears in Collections: | Articles publicats en revistes (Ciència dels Materials i Química Física) |
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667510.pdf | 1.64 MB | Adobe PDF | View/Open |
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