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Title: Crucial role of nuclear dynamics for electron injection in a dye–semiconductor complex

Abstract

In this study, we investigate the electron injection from a terrylene-based chromophore to the TiO2 semiconductor bridged by a recently proposed phenyl-amide-phenyl molecular rectifier. The mechanism of electron transfer is studied by means of quantum dynamics simulations using an extended Hückel Hamiltonian. It is found that the inclusion of the nuclear motion is necessary to observe the photoinduced electron transfer. In particular, the fluctuations of the dihedral angle between the terrylene and the phenyl ring modulate the localization and thus the electronic coupling between the donor and acceptor states involved in the injection process. The electron propagation shows characteristic oscillatory features that correlate with interatomic distance fluctuations in the bridge, which are associated with the vibrational modes driving the process. The understanding of such effects is important for the design of functional dyes with optimal injection and rectification properties.

Authors:
 [1];  [2];  [3];  [4];  [1];  [1]
+ Show Author Affiliations
  1. Leiden Univ., Leiden (Netherlands)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Yale Univ., New Haven, CT (United States)
  4. Univ. Federal de Santa Catarina, Santa Catarina (Brazil)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1239325
Report Number(s):
LA-UR-15-22078
Journal ID: ISSN 1948-7185
Grant/Contract Number:  
AC52-06NA25396; SC0001059
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 6; Journal Issue: 12; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; dye-sensitized solar cells; interfacial electron transfer; tight-binding nonadiabatic dynamics; quantum coherence

Citation Formats

Monti, Adriano, Negre, Christian F. A., Batista, Victor S., Rego, Luis G. C., de Groot, Huub J. M., and Buda, Francesco. Crucial role of nuclear dynamics for electron injection in a dye–semiconductor complex. United States: N. p., 2015. Web. doi:10.1021/acs.jpclett.5b00876.
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Monti, Adriano, Negre, Christian F. A., Batista, Victor S., Rego, Luis G. C., de Groot, Huub J. M., & Buda, Francesco. Crucial role of nuclear dynamics for electron injection in a dye–semiconductor complex. United States. https://doi.org/10.1021/acs.jpclett.5b00876
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Monti, Adriano, Negre, Christian F. A., Batista, Victor S., Rego, Luis G. C., de Groot, Huub J. M., and Buda, Francesco. Fri . "Crucial role of nuclear dynamics for electron injection in a dye–semiconductor complex". United States. https://doi.org/10.1021/acs.jpclett.5b00876. https://www.osti.gov/servlets/purl/1239325.
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@article{osti_1239325,
title = {Crucial role of nuclear dynamics for electron injection in a dye–semiconductor complex},
author = {Monti, Adriano and Negre, Christian F. A. and Batista, Victor S. and Rego, Luis G. C. and de Groot, Huub J. M. and Buda, Francesco},
abstractNote = {In this study, we investigate the electron injection from a terrylene-based chromophore to the TiO2 semiconductor bridged by a recently proposed phenyl-amide-phenyl molecular rectifier. The mechanism of electron transfer is studied by means of quantum dynamics simulations using an extended Hückel Hamiltonian. It is found that the inclusion of the nuclear motion is necessary to observe the photoinduced electron transfer. In particular, the fluctuations of the dihedral angle between the terrylene and the phenyl ring modulate the localization and thus the electronic coupling between the donor and acceptor states involved in the injection process. The electron propagation shows characteristic oscillatory features that correlate with interatomic distance fluctuations in the bridge, which are associated with the vibrational modes driving the process. The understanding of such effects is important for the design of functional dyes with optimal injection and rectification properties.},
doi = {10.1021/acs.jpclett.5b00876},
journal = {Journal of Physical Chemistry Letters},
number = 12,
volume = 6,
place = {United States},
year = {Fri Jun 05 00:00:00 EDT 2015},
month = {Fri Jun 05 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acs.jpclett.5b00876
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    Works referencing / citing this record:

    Structure–function relationships in single molecule rectification by N-phenylbenzamide derivatives
    journal, January 2016

    • Koenigsmann, Christopher; Ding, Wendu; Koepf, Matthieu
    • New Journal of Chemistry, Vol. 40, Issue 9
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    Photoinduced charge-transfer dynamics simulations in noncovalently bonded molecular aggregates
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    Photoinduced Electron Transfer in Donor–Acceptor Complexes: Isotope Effect and Dynamic Symmetry Breaking
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    • Menzel, Jan Paul; de Groot, Huub J. M.; Buda, Francesco
    • The Journal of Physical Chemistry Letters, Vol. 10, Issue 21
    • DOI: 10.1021/acs.jpclett.9b02408
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