Dimensionality of nanoscale TiO2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle
Abstract
Assumptions about electron transfer (ET) mechanisms guide design of catalytic, photovoltaic, and electronic systems. We demonstrate that the mechanism of ET from a CdSe quantum dot (QD) into nanoscale TiO2 depends on TiO2 dimensionality. The injection into a TiO2 QD is adiabatic due to strong donor–acceptor coupling, arising from unsaturated chemical bonds on the QD surface, and low density of acceptor states. In contrast, the injection into a TiO2 nanobelt (NB) is nonadiabatic, because the state density is high, the donor–acceptor coupling is weak, and multiple phonons accommodate changes in the electronic energy. The CdSe adsorbant breaks symmetry of delocalized TiO2 NB states, relaxing coupling selection rules, and generating more ET channels. Both mechanisms can give efficient ultrafast injection. Furthermore, the dependence on system properties is very different for the two mechanisms, demonstrating that the fundamental principles leading to efficient charge separation depend strongly on the type of nanoscale material.
- Authors:
-
- National Energy Technology Lab. (NETL), Albany, OR (United States); URS Corp., Albany, OR (United States)
- Univ. College Dublin, Dublin (Ireland)
- Univ. of Rochester, Rochester, NY (United States)
- Publication Date:
- Research Org.:
- National Energy Technology Lab. (NETL), Albany, OR (United States)
- Sponsoring Org.:
- USDOE Office of Fossil Energy (FE)
- OSTI Identifier:
- 1165415
- Report Number(s):
- CONTR-PUB-044
Journal ID: ISSN 1530-6984
- Grant/Contract Number:
- FE0004000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 14; Journal Issue: 4; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; nonadiabatic molecular dynamics; time-domain density functional theory; semiconductor quantum dots; electron-vibrational interaction; adiabatic electron transfer
Citation Formats
Tafen, De Nyago, Long, Run, and Prezhdo, Oleg V. Dimensionality of nanoscale TiO2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle. United States: N. p., 2014.
Web. doi:10.1021/nl404352a.
Tafen, De Nyago, Long, Run, & Prezhdo, Oleg V. Dimensionality of nanoscale TiO2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle. United States. https://doi.org/10.1021/nl404352a
Tafen, De Nyago, Long, Run, and Prezhdo, Oleg V. Mon .
"Dimensionality of nanoscale TiO2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle". United States. https://doi.org/10.1021/nl404352a. https://www.osti.gov/servlets/purl/1165415.
@article{osti_1165415,
title = {Dimensionality of nanoscale TiO2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle},
author = {Tafen, De Nyago and Long, Run and Prezhdo, Oleg V.},
abstractNote = {Assumptions about electron transfer (ET) mechanisms guide design of catalytic, photovoltaic, and electronic systems. We demonstrate that the mechanism of ET from a CdSe quantum dot (QD) into nanoscale TiO2 depends on TiO2 dimensionality. The injection into a TiO2 QD is adiabatic due to strong donor–acceptor coupling, arising from unsaturated chemical bonds on the QD surface, and low density of acceptor states. In contrast, the injection into a TiO2 nanobelt (NB) is nonadiabatic, because the state density is high, the donor–acceptor coupling is weak, and multiple phonons accommodate changes in the electronic energy. The CdSe adsorbant breaks symmetry of delocalized TiO2 NB states, relaxing coupling selection rules, and generating more ET channels. Both mechanisms can give efficient ultrafast injection. Furthermore, the dependence on system properties is very different for the two mechanisms, demonstrating that the fundamental principles leading to efficient charge separation depend strongly on the type of nanoscale material.},
doi = {10.1021/nl404352a},
journal = {Nano Letters},
number = 4,
volume = 14,
place = {United States},
year = {Mon Mar 10 00:00:00 EDT 2014},
month = {Mon Mar 10 00:00:00 EDT 2014}
}
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