Malyk, Sergey and Shalhout, Fadel Y. and O'Leary, Leslie E. and Lewis, Nathan S. and Benderskii, Alexander V. (2013) Vibrational Sum Frequency Spectroscopic Investigation of the Azimuthal Anisotropy and Rotational Dynamics of Methyl-Terminated Silicon(111) Surfaces. Journal of Physical Chemistry C, 117 (2). pp. 935-944. ISSN 1932-7447. doi:10.1021/jp3067298. https://resolver.caltech.edu/CaltechAUTHORS:20130225-163026469
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Abstract
Polarization-selected vibrational sum frequency generation spectroscopy (SFG) has been used to investigate the molecular orientation of methyl groups on CH_(3)-terminated Si(111) surfaces. The symmetric and asymmetric C–H stretch modes of the surface-bound methyl group were observed by SFG. Both methyl stretches showed a pronounced azimuthal anisotropy of the 3-fold symmetry in registry with the signal from the Si(111) substrate, indicating that the propeller-like rotation of the methyl groups was hindered at room temperature. The difference in the SFG line widths for the CH_3 asymmetric stretch that was observed for different polarization combinations (SPS and PPP for SFG, visible, and IR) indicated that the rotation proceeded on a 1–2 ps time scale, as compared to the 100 fs rotational dephasing of a free methyl rotor at room temperature.
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| Additional Information: | © 2012 American Chemical Society. Received: July 6, 2012; Revised: November 9, 2012; Published: December 14, 2012. This research was supported by the AFOSR, Grant No. FA9550-09-1-0547 (AVB), and by the NSF, CHE-0911682 (NSL). L.E.O. graciously thanks the financial support of the Link Foundation Energy Fellowship. | |||||||||
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| Issue or Number: | 2 | |||||||||
| DOI: | 10.1021/jp3067298 | |||||||||
| Record Number: | CaltechAUTHORS:20130225-163026469 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20130225-163026469 | |||||||||
| Official Citation: | Vibrational Sum Frequency Spectroscopic Investigation of the Azimuthal Anisotropy and Rotational Dynamics of Methyl-Terminated Silicon(111) Surfaces Sergey Malyk, Fadel Y. Shalhout, Leslie E. O’Leary, Nathan S. Lewis, and Alexander V. Benderskii The Journal of Physical Chemistry C 2013 117 (2), 935-944 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 37124 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Jason Perez | |||||||||
| Deposited On: | 26 Feb 2013 20:01 | |||||||||
| Last Modified: | 09 Nov 2021 23:26 |
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