Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations
Abstract
Functionalized self-assembled monolayers (SAMs) are the focus of ongoing investigations because they can be chemically tuned to control their structure and dynamics for a wide variety of applications, including electrochemistry, catalysis, and as models of biological interfaces. Here we combine reflection 2D infrared vibrational echo spectroscopy (R-2D IR) and molecular dynamics simulations to determine the relationship between the structures of functionalized alkanethiol SAMs on gold surfaces and their underlying molecular motions on timescales of tens to hundreds of picoseconds. We find that at higher head group density, the monolayers have more disorder in the alkyl chain packing and faster dynamics. The dynamics of alkanethiol SAMs on gold are much slower than the dynamics of alkylsiloxane SAMs on silica. Using the simulations, we assess how the different molecular motions of the alkyl chain monolayers give rise to the dynamics observed in the experiments.
- Authors:
-
- Department of Chemistry, Stanford University, Stanford, CA 94305
- Publication Date:
- Research Org.:
- Stanford Univ., CA (United States)
- Sponsoring Org.:
- US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1245295
- Alternate Identifier(s):
- OSTI ID: 1469314; OSTI ID: 1526760; OSTI ID: 1804759
- Grant/Contract Number:
- SC0014437; FA9550-16-1-0104; FG02-84ER13251
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 113 Journal Issue: 18; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; self-assembled monolayer; dynamics; 2D IR spectroscopy; MD simulation
Citation Formats
Yan, Chang, Yuan, Rongfeng, Pfalzgraff, William C., Nishida, Jun, Wang, Lu, Markland, Thomas E., and Fayer, Michael D. Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations. United States: N. p., 2016.
Web. doi:10.1073/pnas.1603080113.
Yan, Chang, Yuan, Rongfeng, Pfalzgraff, William C., Nishida, Jun, Wang, Lu, Markland, Thomas E., & Fayer, Michael D. Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations. United States. https://doi.org/10.1073/pnas.1603080113
Yan, Chang, Yuan, Rongfeng, Pfalzgraff, William C., Nishida, Jun, Wang, Lu, Markland, Thomas E., and Fayer, Michael D. Tue .
"Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations". United States. https://doi.org/10.1073/pnas.1603080113.
@article{osti_1245295,
title = {Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations},
author = {Yan, Chang and Yuan, Rongfeng and Pfalzgraff, William C. and Nishida, Jun and Wang, Lu and Markland, Thomas E. and Fayer, Michael D.},
abstractNote = {Functionalized self-assembled monolayers (SAMs) are the focus of ongoing investigations because they can be chemically tuned to control their structure and dynamics for a wide variety of applications, including electrochemistry, catalysis, and as models of biological interfaces. Here we combine reflection 2D infrared vibrational echo spectroscopy (R-2D IR) and molecular dynamics simulations to determine the relationship between the structures of functionalized alkanethiol SAMs on gold surfaces and their underlying molecular motions on timescales of tens to hundreds of picoseconds. We find that at higher head group density, the monolayers have more disorder in the alkyl chain packing and faster dynamics. The dynamics of alkanethiol SAMs on gold are much slower than the dynamics of alkylsiloxane SAMs on silica. Using the simulations, we assess how the different molecular motions of the alkyl chain monolayers give rise to the dynamics observed in the experiments.},
doi = {10.1073/pnas.1603080113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 18,
volume = 113,
place = {United States},
year = {Tue May 03 00:00:00 EDT 2016},
month = {Tue May 03 00:00:00 EDT 2016}
}
https://doi.org/10.1073/pnas.1603080113
Web of Science
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