Vibrational spectroscopy of nitroaromatic self-assembled monolayers under extreme conditions

Yuanxi Fu; Elizabeth A. Friedman; Kathryn E. Brown; Dana D. Dlott

doi:10.1016/j.cplett.2010.12.013

Vibrational spectroscopy of nitroaromatic self-assembled monolayers under extreme conditions

Yuanxi Fu, Elizabeth A. Friedman, Kathryn E. Brown, Dana D. Dlott

Chemistry

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Abstract

Vibrational spectra up to 8 GPa and 600 °C were obtained for self-assembled monolayers (SAMs) on noble metal surfaces of the energetic material simulant 4-nitrobenzenethiol (NBT). The high-pressure measurements used a surface-enhanced Raman sensor. The high-temperature measurements used femtosecond laser flash-heating and nonlinear coherent vibrational spectroscopy. The SAM nitro stretching transition νNO2s is insensitive to flash-heating where there is no time for chemical reactivity or thermal expansion. A large pressure broadening in νNO2s of the SAM but not in solid NBT was associated with surface adlayer rearrangement. The implications for time-resolved measurements of shock-compressed energetic materials are discussed.

Original language	English (US)
Pages (from-to)	369-374
Number of pages	6
Journal	Chemical Physics Letters
Volume	501
Issue number	4-6
DOIs	https://doi.org/10.1016/j.cplett.2010.12.013
State	Published - Jan 7 2011

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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10.1016/j.cplett.2010.12.013

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title = "Vibrational spectroscopy of nitroaromatic self-assembled monolayers under extreme conditions",

abstract = "Vibrational spectra up to 8 GPa and 600 °C were obtained for self-assembled monolayers (SAMs) on noble metal surfaces of the energetic material simulant 4-nitrobenzenethiol (NBT). The high-pressure measurements used a surface-enhanced Raman sensor. The high-temperature measurements used femtosecond laser flash-heating and nonlinear coherent vibrational spectroscopy. The SAM nitro stretching transition νNO2s is insensitive to flash-heating where there is no time for chemical reactivity or thermal expansion. A large pressure broadening in νNO2s of the SAM but not in solid NBT was associated with surface adlayer rearrangement. The implications for time-resolved measurements of shock-compressed energetic materials are discussed.",

author = "Yuanxi Fu and Friedman, {Elizabeth A.} and Brown, {Kathryn E.} and Dlott, {Dana D.}",

note = "Funding Information: This material is based on work supported by the Stewardship Sciences Academic Alliance Program from the Carnegie-DOE Alliance Center under grant number DOE CIW 4-3253-13 , and the US Air Force Office of Scientific Research under award number FAA9550-09-1-0163 . Copyright: Copyright 2011 Elsevier B.V., All rights reserved.",

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doi = "10.1016/j.cplett.2010.12.013",

language = "English (US)",

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AU - Fu, Yuanxi

AU - Friedman, Elizabeth A.

AU - Brown, Kathryn E.

AU - Dlott, Dana D.

N1 - Funding Information: This material is based on work supported by the Stewardship Sciences Academic Alliance Program from the Carnegie-DOE Alliance Center under grant number DOE CIW 4-3253-13 , and the US Air Force Office of Scientific Research under award number FAA9550-09-1-0163 . Copyright: Copyright 2011 Elsevier B.V., All rights reserved.

PY - 2011/1/7

Y1 - 2011/1/7

N2 - Vibrational spectra up to 8 GPa and 600 °C were obtained for self-assembled monolayers (SAMs) on noble metal surfaces of the energetic material simulant 4-nitrobenzenethiol (NBT). The high-pressure measurements used a surface-enhanced Raman sensor. The high-temperature measurements used femtosecond laser flash-heating and nonlinear coherent vibrational spectroscopy. The SAM nitro stretching transition νNO2s is insensitive to flash-heating where there is no time for chemical reactivity or thermal expansion. A large pressure broadening in νNO2s of the SAM but not in solid NBT was associated with surface adlayer rearrangement. The implications for time-resolved measurements of shock-compressed energetic materials are discussed.

AB - Vibrational spectra up to 8 GPa and 600 °C were obtained for self-assembled monolayers (SAMs) on noble metal surfaces of the energetic material simulant 4-nitrobenzenethiol (NBT). The high-pressure measurements used a surface-enhanced Raman sensor. The high-temperature measurements used femtosecond laser flash-heating and nonlinear coherent vibrational spectroscopy. The SAM nitro stretching transition νNO2s is insensitive to flash-heating where there is no time for chemical reactivity or thermal expansion. A large pressure broadening in νNO2s of the SAM but not in solid NBT was associated with surface adlayer rearrangement. The implications for time-resolved measurements of shock-compressed energetic materials are discussed.

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JO - Chemical Physics Letters

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Vibrational spectroscopy of nitroaromatic self-assembled monolayers under extreme conditions

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