Interfacial organization of acetonitrile: Simulation and experiment

Feng Ding; Zhonghan Hu; Qin Zhong; Katherine Manfred; Rafael R. Gattass; Michael R. Brindza; John T. Fourkas; Robert A. Walker; John D. Weeks

doi:10.1021/jp104597z

Interfacial organization of acetonitrile: Simulation and experiment

Feng Ding, Zhonghan Hu, Qin Zhong, Katherine Manfred, Rafael R. Gattass, Michael R. Brindza, John T. Fourkas, Robert A. Walker, John D. Weeks

Chemistry

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Abstract

Molecular dynamics simulations and vibrational sum frequency generation (VSFG) experiments in the methyl-stretching spectral region have been used to study acetonitrile at the silica/liquid, silica/vapor, and liquid/vapor interfaces. Our simulations show that, at the silica/liquid interface, acetonitrile takes on a considerably different structure than in the bulk liquid. The interfacial structure is reminiscent of a lipid bilayer, and this type of ordering persists for tens of Ångstroms into the bulk liquid. This result has important implications for processes involving solid/acetonitrile interfaces, such as heterogeneous catalysis and chromatographic separations. Fitting of VSFG data that have an extremely low nonresonant background contribution provides strong evidence for interfacial populations pointing in opposite directions at these interfaces, in agreement with our simulations. The picture developed from our simulations and experiments reconciles conflicting interpretations of data from previous experimental studies of interfacial acetonitrile.

Original language	English
Pages (from-to)	17651-17659
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	114
Issue number	41
DOIs	https://doi.org/10.1021/jp104597z
Publication status	Published - 21 Oct 2010

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title = "Interfacial organization of acetonitrile: Simulation and experiment",

abstract = "Molecular dynamics simulations and vibrational sum frequency generation (VSFG) experiments in the methyl-stretching spectral region have been used to study acetonitrile at the silica/liquid, silica/vapor, and liquid/vapor interfaces. Our simulations show that, at the silica/liquid interface, acetonitrile takes on a considerably different structure than in the bulk liquid. The interfacial structure is reminiscent of a lipid bilayer, and this type of ordering persists for tens of {\AA}ngstroms into the bulk liquid. This result has important implications for processes involving solid/acetonitrile interfaces, such as heterogeneous catalysis and chromatographic separations. Fitting of VSFG data that have an extremely low nonresonant background contribution provides strong evidence for interfacial populations pointing in opposite directions at these interfaces, in agreement with our simulations. The picture developed from our simulations and experiments reconciles conflicting interpretations of data from previous experimental studies of interfacial acetonitrile.",

author = "Feng Ding and Zhonghan Hu and Qin Zhong and Katherine Manfred and Gattass, {Rafael R.} and Brindza, {Michael R.} and Fourkas, {John T.} and Walker, {Robert A.} and Weeks, {John D.}",

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TY - JOUR

T1 - Interfacial organization of acetonitrile

T2 - Simulation and experiment

AU - Ding, Feng

AU - Hu, Zhonghan

AU - Zhong, Qin

AU - Manfred, Katherine

AU - Gattass, Rafael R.

AU - Brindza, Michael R.

AU - Fourkas, John T.

AU - Walker, Robert A.

AU - Weeks, John D.

PY - 2010/10/21

Y1 - 2010/10/21

N2 - Molecular dynamics simulations and vibrational sum frequency generation (VSFG) experiments in the methyl-stretching spectral region have been used to study acetonitrile at the silica/liquid, silica/vapor, and liquid/vapor interfaces. Our simulations show that, at the silica/liquid interface, acetonitrile takes on a considerably different structure than in the bulk liquid. The interfacial structure is reminiscent of a lipid bilayer, and this type of ordering persists for tens of Ångstroms into the bulk liquid. This result has important implications for processes involving solid/acetonitrile interfaces, such as heterogeneous catalysis and chromatographic separations. Fitting of VSFG data that have an extremely low nonresonant background contribution provides strong evidence for interfacial populations pointing in opposite directions at these interfaces, in agreement with our simulations. The picture developed from our simulations and experiments reconciles conflicting interpretations of data from previous experimental studies of interfacial acetonitrile.

AB - Molecular dynamics simulations and vibrational sum frequency generation (VSFG) experiments in the methyl-stretching spectral region have been used to study acetonitrile at the silica/liquid, silica/vapor, and liquid/vapor interfaces. Our simulations show that, at the silica/liquid interface, acetonitrile takes on a considerably different structure than in the bulk liquid. The interfacial structure is reminiscent of a lipid bilayer, and this type of ordering persists for tens of Ångstroms into the bulk liquid. This result has important implications for processes involving solid/acetonitrile interfaces, such as heterogeneous catalysis and chromatographic separations. Fitting of VSFG data that have an extremely low nonresonant background contribution provides strong evidence for interfacial populations pointing in opposite directions at these interfaces, in agreement with our simulations. The picture developed from our simulations and experiments reconciles conflicting interpretations of data from previous experimental studies of interfacial acetonitrile.

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ER -

Interfacial organization of acetonitrile: Simulation and experiment

Abstract

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