Interfacial Organization of Acetonitrile: Simulation and Experiment

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

doi:10.1021/jp104597z

Cited by 79 publications

(234 citation statements)

References 60 publications

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“…Thus, the cancellation for acetonitrile is incomplete due to a spectral shift between the methyl groups in the liquid and the methyl groups of molecules that accept hydrogen bonds from the silica surface. 7 We were therefore able to fit the spectra to the magnitude squared of the sum of two Lorentzian features of opposite sign and with different center frequencies 7…”

Section: Resultsmentioning

confidence: 99%

Structure of Liquid Propionitrile at Interfaces. 2. Experiment

et al. 2012

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Propionitrile has been studied at the liquid/ vapor, silica/vapor, and silica/liquid interfaces using vibrational sum-frequency generation (VSFG) spectroscopy and optical Kerr effect (OKE) spectroscopy. VSFG studies show that the alkyl tail of propionitrile tends to point into the vapor phase at the liquid/vapor and silica/vapor interfaces. At the silica/liquid interface, all vibrational resonances except for the methylene symmetric stretch exhibit strong cancellation in the VSFG signal. This result supports the existence of a lipid-bilayer-like organization at the silica/liquid interface, in agreement with simulation. OKE data for propionitrile confined in porous sol−gel glasses indicate that there is a surface layer, with a thickness of roughly 4 Å, that experiences inhibited orientational dynamics. The OKE data thus corroborate the picture of interfacial organization suggested by the VSFG results.

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Section: Resultsmentioning

confidence: 99%

Structure of Liquid Propionitrile at Interfaces. 2. Experiment

et al. 2012

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“…17,22 The hydrophilic silica surface, which was placed at z = 0, was constructed on the basis of the idealized β-cristobalite (C9) crystal from previous work of Lee and Rossky. 23 The simulation box contained 864 acetonitrile molecules.…”

Section: Simulation Detailsmentioning

confidence: 99%

Orientational Time Correlation Functions for Vibrational Sum-Frequency Generation. 1. Acetonitrile

Liu

Fourkas

2012

J. Phys. Chem. A

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Orientational time correlation functions (TCFs) are derived for vibrational sum-frequency generation (VSFG) spectroscopy of the symmetric and asymmetric stretches of high-symmetry oscillators such as freely rotating methyl groups, acetylenic C-H groups, and cyanide groups. Molecular dynamics simulations are used to calculate these TCFs and the corresponding elements of the second-order response for acetonitrile at the liquid/vapor and liquid/silica interfaces. We find that the influence of reorientation depends significantly on both the functional group in question and the polarization conditions used. Additionally, under some circumstances, reorientation can cause the VSFG response function to grow with time, partially counteracting the effects of other dephasing mechanisms.

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“…[4] Recent MD simulations on fused-silica/ethanol and fusedsilica/acetonitrile interfaces have yielded similar conclusions. [5,6] In this article, we report our study of the ethanol/α -Al 2 O 3 (1102 ) interface using SFVS. The system was chosen to see whether the anisotropic crystalline surface of α -Al 2 O 3 (1102 ) would induce an orientation order as well as an in-plane anisotropy in orientation in the interfacial layer of ethanol molecules.…”

Section: Introductionmentioning

confidence: 99%