Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells

Thomas P. Brennan; Jukka T. Tanskanen; Jonathan R. Bakke; William H. Nguyen; Dennis Nordlund; Michael F. Toney; Michael D. McGehee; Alan Sellinger; Stacey F. Bent

doi:10.1021/cm402609k

Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells

Thomas P. Brennan, Jukka T. Tanskanen, Jonathan R. Bakke, William H. Nguyen, Dennis Nordlund, Michael F. Toney, Michael D. McGehee, Alan Sellinger, Stacey F. Bent

Research output: Contribution to journal › Article › peer-review

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Abstract

A dual experimental-computational approach utilizing near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory-molecular dynamics (DFT-MD) is presented for determining the orientation of a large adsorbate on an oxide substrate. A system of interest in the field of dye-sensitized solar cells is studied: an organic cyanoacrylic acid-based donor-π-acceptor dye (WN1) bound to anatase TiO2. Assessment of nitrogen K-edge NEXAFS spectra is supported by calculations of the electronic structure that indicate energetically discrete transitions associated with the two π systems of the C-N triple bond in the cyanoacrylic acid portion of the dye. Angle-resolved NEXAFS spectra are fitted to determine the orientation of these two orbital systems, and the results indicate an upright orientation of the adsorbed dye, 63 from the TiO2 surface plane. These experimental results are then compared to computational studies of the WN1 dye on an anatase (101) TiO2 slab. The ground state structure obtained from standard DFT optimization is less upright (45 from the surface) than the NEXAFS results. However, DFT-MD simulations, which provide a more realistic depiction of the dye at room temperature, exhibit excellent agreement - within 2 on average - with the angles determined via NEXAFS, demonstrating the importance of accounting for the dynamic nature of adsorbate-substrate interactions and DFT-MD's powerful predictive abilities. © 2013 American Chemical Society.

Original language	English (US)
Pages (from-to)	4354-4363
Number of pages	10
Journal	Chemistry of Materials
Volume	25
Issue number	21
DOIs	https://doi.org/10.1021/cm402609k
State	Published - Nov 4 2013
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KUS-C1-015-21
Acknowledgements: This publication was based on work supported by the Center for Advanced Molecular Photovoltaics (CAMP) (Award No. KUS-C1-015-21), made by King Abdullah University of Science and Technology (KAUST). Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Stanford University under SSRL proposal #3338. T.P.B. would like to thank the Albion Walter Hewlett Fellowship for financial support. J.T.T. gratefully acknowledges the Academy of Finland (Grant 256800/2012) and the Finnish Cultural Foundation for financial support. J.R.B acknowledges funding from the National Science Foundation (NSF) Graduate Fellowship. We would like to thank Dr. Han Bo-Ram Lee for assistance with the ALD of TiO2.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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@article{1de59a760eea493b8deae6ae0c81f7b1,

title = "Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells",

abstract = "A dual experimental-computational approach utilizing near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory-molecular dynamics (DFT-MD) is presented for determining the orientation of a large adsorbate on an oxide substrate. A system of interest in the field of dye-sensitized solar cells is studied: an organic cyanoacrylic acid-based donor-π-acceptor dye (WN1) bound to anatase TiO2. Assessment of nitrogen K-edge NEXAFS spectra is supported by calculations of the electronic structure that indicate energetically discrete transitions associated with the two π systems of the C-N triple bond in the cyanoacrylic acid portion of the dye. Angle-resolved NEXAFS spectra are fitted to determine the orientation of these two orbital systems, and the results indicate an upright orientation of the adsorbed dye, 63 from the TiO2 surface plane. These experimental results are then compared to computational studies of the WN1 dye on an anatase (101) TiO2 slab. The ground state structure obtained from standard DFT optimization is less upright (45 from the surface) than the NEXAFS results. However, DFT-MD simulations, which provide a more realistic depiction of the dye at room temperature, exhibit excellent agreement - within 2 on average - with the angles determined via NEXAFS, demonstrating the importance of accounting for the dynamic nature of adsorbate-substrate interactions and DFT-MD's powerful predictive abilities. {\textcopyright} 2013 American Chemical Society.",

author = "Brennan, {Thomas P.} and Tanskanen, {Jukka T.} and Bakke, {Jonathan R.} and Nguyen, {William H.} and Dennis Nordlund and Toney, {Michael F.} and McGehee, {Michael D.} and Alan Sellinger and Bent, {Stacey F.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-C1-015-21 Acknowledgements: This publication was based on work supported by the Center for Advanced Molecular Photovoltaics (CAMP) (Award No. KUS-C1-015-21), made by King Abdullah University of Science and Technology (KAUST). Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Stanford University under SSRL proposal #3338. T.P.B. would like to thank the Albion Walter Hewlett Fellowship for financial support. J.T.T. gratefully acknowledges the Academy of Finland (Grant 256800/2012) and the Finnish Cultural Foundation for financial support. J.R.B acknowledges funding from the National Science Foundation (NSF) Graduate Fellowship. We would like to thank Dr. Han Bo-Ram Lee for assistance with the ALD of TiO2. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2013",

month = nov,

day = "4",

doi = "10.1021/cm402609k",

language = "English (US)",

volume = "25",

pages = "4354--4363",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "21",

}

TY - JOUR

T1 - Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells

AU - Brennan, Thomas P.

AU - Tanskanen, Jukka T.

AU - Bakke, Jonathan R.

AU - Nguyen, William H.

AU - Nordlund, Dennis

AU - Toney, Michael F.

AU - McGehee, Michael D.

AU - Sellinger, Alan

AU - Bent, Stacey F.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-C1-015-21 Acknowledgements: This publication was based on work supported by the Center for Advanced Molecular Photovoltaics (CAMP) (Award No. KUS-C1-015-21), made by King Abdullah University of Science and Technology (KAUST). Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Stanford University under SSRL proposal #3338. T.P.B. would like to thank the Albion Walter Hewlett Fellowship for financial support. J.T.T. gratefully acknowledges the Academy of Finland (Grant 256800/2012) and the Finnish Cultural Foundation for financial support. J.R.B acknowledges funding from the National Science Foundation (NSF) Graduate Fellowship. We would like to thank Dr. Han Bo-Ram Lee for assistance with the ALD of TiO2. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2013/11/4

Y1 - 2013/11/4

N2 - A dual experimental-computational approach utilizing near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory-molecular dynamics (DFT-MD) is presented for determining the orientation of a large adsorbate on an oxide substrate. A system of interest in the field of dye-sensitized solar cells is studied: an organic cyanoacrylic acid-based donor-π-acceptor dye (WN1) bound to anatase TiO2. Assessment of nitrogen K-edge NEXAFS spectra is supported by calculations of the electronic structure that indicate energetically discrete transitions associated with the two π systems of the C-N triple bond in the cyanoacrylic acid portion of the dye. Angle-resolved NEXAFS spectra are fitted to determine the orientation of these two orbital systems, and the results indicate an upright orientation of the adsorbed dye, 63 from the TiO2 surface plane. These experimental results are then compared to computational studies of the WN1 dye on an anatase (101) TiO2 slab. The ground state structure obtained from standard DFT optimization is less upright (45 from the surface) than the NEXAFS results. However, DFT-MD simulations, which provide a more realistic depiction of the dye at room temperature, exhibit excellent agreement - within 2 on average - with the angles determined via NEXAFS, demonstrating the importance of accounting for the dynamic nature of adsorbate-substrate interactions and DFT-MD's powerful predictive abilities. © 2013 American Chemical Society.

AB - A dual experimental-computational approach utilizing near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory-molecular dynamics (DFT-MD) is presented for determining the orientation of a large adsorbate on an oxide substrate. A system of interest in the field of dye-sensitized solar cells is studied: an organic cyanoacrylic acid-based donor-π-acceptor dye (WN1) bound to anatase TiO2. Assessment of nitrogen K-edge NEXAFS spectra is supported by calculations of the electronic structure that indicate energetically discrete transitions associated with the two π systems of the C-N triple bond in the cyanoacrylic acid portion of the dye. Angle-resolved NEXAFS spectra are fitted to determine the orientation of these two orbital systems, and the results indicate an upright orientation of the adsorbed dye, 63 from the TiO2 surface plane. These experimental results are then compared to computational studies of the WN1 dye on an anatase (101) TiO2 slab. The ground state structure obtained from standard DFT optimization is less upright (45 from the surface) than the NEXAFS results. However, DFT-MD simulations, which provide a more realistic depiction of the dye at room temperature, exhibit excellent agreement - within 2 on average - with the angles determined via NEXAFS, demonstrating the importance of accounting for the dynamic nature of adsorbate-substrate interactions and DFT-MD's powerful predictive abilities. © 2013 American Chemical Society.

UR - http://hdl.handle.net/10754/598032

UR - https://pubs.acs.org/doi/10.1021/cm402609k

UR - http://www.scopus.com/inward/record.url?scp=84887598091&partnerID=8YFLogxK

U2 - 10.1021/cm402609k

DO - 10.1021/cm402609k

M3 - Article

SN - 0897-4756

VL - 25

SP - 4354

EP - 4363

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 21

ER -

Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells

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