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Title: Dye aggregation identified by vibrational coupling using 2D IR spectroscopy

Abstract

We report that a model dye, Re(CO){sub 3}(bypy)CO{sub 2}H, aggregates into clusters on TiO{sub 2} nanoparticles regardless of our preparation conditions. Using two-dimensional infrared (2D IR) spectroscopy, we have identified characteristic frequencies of monomers, dimers, and trimers. A comparison of 2D IR spectra in solution versus those deposited on TiO{sub 2} shows that the propensity to dimerize in solution leads to higher dimer formation on TiO{sub 2}, but that dimers are formed even if there are only monomers in solution. Aggregates cannot be washed off with standard protocols and are present even at submonolayer coverages. We observe cross peaks between aggregates of different sizes, primarily dimers and trimers, indicating that clusters consist of microdomains in close proximity. 2D IR spectroscopy is used to draw these conclusions from measurements of vibrational couplings, but if molecules are close enough to be vibrationally coupled, then they are also likely to be electronically coupled, which could alter charge transfer.

Authors:
; ;  [1]; ;  [2]
  1. Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States)
  2. Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States)
Publication Date:
OSTI Identifier:
22415915
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 21; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AGGLOMERATION; CARBON MONOXIDE; COMPARATIVE EVALUATIONS; DIMERS; DYES; HYDROCARBONS; INFRARED SPECTRA; MOLECULES; MONOMERS; NANOPARTICLES; ORGANIC OXYGEN COMPOUNDS; TITANIUM OXIDES; TWO-DIMENSIONAL SYSTEMS

Citation Formats

Oudenhoven, Tracey A., Laaser, Jennifer E., Zanni, Martin T., E-mail: zanni@chem.wisc.edu, Joo, Yongho, and Gopalan, Padma. Dye aggregation identified by vibrational coupling using 2D IR spectroscopy. United States: N. p., 2015. Web. doi:10.1063/1.4921649.
Oudenhoven, Tracey A., Laaser, Jennifer E., Zanni, Martin T., E-mail: zanni@chem.wisc.edu, Joo, Yongho, & Gopalan, Padma. Dye aggregation identified by vibrational coupling using 2D IR spectroscopy. United States. doi:10.1063/1.4921649.
Oudenhoven, Tracey A., Laaser, Jennifer E., Zanni, Martin T., E-mail: zanni@chem.wisc.edu, Joo, Yongho, and Gopalan, Padma. 2015. "Dye aggregation identified by vibrational coupling using 2D IR spectroscopy". United States. doi:10.1063/1.4921649.
@article{osti_22415915,
title = {Dye aggregation identified by vibrational coupling using 2D IR spectroscopy},
author = {Oudenhoven, Tracey A. and Laaser, Jennifer E. and Zanni, Martin T., E-mail: zanni@chem.wisc.edu and Joo, Yongho and Gopalan, Padma},
abstractNote = {We report that a model dye, Re(CO){sub 3}(bypy)CO{sub 2}H, aggregates into clusters on TiO{sub 2} nanoparticles regardless of our preparation conditions. Using two-dimensional infrared (2D IR) spectroscopy, we have identified characteristic frequencies of monomers, dimers, and trimers. A comparison of 2D IR spectra in solution versus those deposited on TiO{sub 2} shows that the propensity to dimerize in solution leads to higher dimer formation on TiO{sub 2}, but that dimers are formed even if there are only monomers in solution. Aggregates cannot be washed off with standard protocols and are present even at submonolayer coverages. We observe cross peaks between aggregates of different sizes, primarily dimers and trimers, indicating that clusters consist of microdomains in close proximity. 2D IR spectroscopy is used to draw these conclusions from measurements of vibrational couplings, but if molecules are close enough to be vibrationally coupled, then they are also likely to be electronically coupled, which could alter charge transfer.},
doi = {10.1063/1.4921649},
journal = {Journal of Chemical Physics},
number = 21,
volume = 142,
place = {United States},
year = 2015,
month = 6
}
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