Geometries and energetics of methanol–ethanol clusters: a VUV laser/time-of-flight mass spectrometry and density functional theory study

Liu, Y.; Consta, Styliani; Ogeer, F.; Shi, Yujun; Lipson, R. H.

doi:10.1139/v07-104

Cited by 13 publications

(26 citation statements)

References 24 publications

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“…Both TIP3P and OPLS-AA potentials were developed by Jorgensen et al 12 13 OPLS-AA potential parameters were originally developed for pure gas phase clusters or liquids, but it was shown that these parameters could be used to describe mixtures well. 15 The LJ parameters and atomic charges used in this work are listed in Table I. Molecular models were constructed by immersing a finite segment of single-wall CNT into an orthorhombic supercell filled with water and methanol molecules ( Fig.…”

Section: Computational Methods and Modelmentioning

confidence: 99%

Nanoimmiscibility: Selective Absorption of Liquid Methanol–Water Mixtures in Carbon Nanotubes

Liu¹,

Consta²,

Goddard³

2010

J. Nanosci. Nanotech.

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Despite the continuing research interests in CNT-liquid systems, the microscopic structure and transport behavior of liquid mixtures in carbon nanotubes (CNTs) remain poorly understood. Methanol and water liquids are completely miscible across the entire range of concentration; however, recent research reveals that they are immiscible at a molecular level. In this work, we carried out classical molecular dynamics to study the molecular distribution, structure ordering, clustering and transport behavior of liquid methanol-water mixtures within CNT confinement. We found that CNTs preferentially absorbed methanol over water molecule even though the latter has a smaller molecular size, indicating that chemical effect such as molecular hydrophilicity plays a crucial role in the molecular absorption of CNTs. Due to the selective absorption of CNTs, methanol aqueous solution changes from microscopically immiscible to macroscopically immiscible at nanoscale. This nanoscale immiscibility may be utilized in various applications of CNTs including direct methanol fuel cells, nanosensors, molecular sieves, nanofluidic chips, and capsules for drug delivery.

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Section: Computational Methods and Modelmentioning

confidence: 99%

Nanoimmiscibility: Selective Absorption of Liquid Methanol–Water Mixtures in Carbon Nanotubes

Liu¹,

Consta²,

Goddard³

2010

J. Nanosci. Nanotech.

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“…However the mechanism of the diffuse band formation and its structure are still the unsolved problems. e importance of the problems connected with the alcohol clustering and structure and, in particular, with the mechanisms of the diffuse absorption band formation is re�ected in the great number of experimental [1][2][3][4][5][6][7][8][9], theoretical [10][11][12][13][14], and combined works [15][16][17][18][19] published in the recent years.…”

Section: Introductionmentioning

confidence: 99%

Infrared Absorption Spectra of Monohydric Alcohols

Doroshenko

Pogorelov

Šablinskas

2013

Dataset Papers in Chemistry

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FTIR spectra of homologous series of monohydric alcohols which belong to the class of partly ordered liquids were registered. e molecules of monohydric alcohols containing hydroxyl group are able to form hydrogen-bonded clusters in the condensed phase. e existence of clusters is clearly observed from the position and the contour of the stretch OH band in the vibrational spectra of liquid alcohols. In this work, the experimentally registered FTIR spectra of liquid n-alcohols from methanol to decanol are presented as well as the same spectra of methanol, ethanol, propanol, butanol, pentanol, and hexanol in gas phase.

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“…Similarly, the ionized clusters (3, 0) + and (2, 1) + share the same neutral precursor (3,1). It is assumed that the reaction channel (3, 1) ) (2, 1) + + (1, 0) • + e -might be more efficient than (3, 1) ) (3, 0) + + (0, 1) • + e -, which would lead to more (2, 1) + relative to (3, 0) + in the methanol-rich M1E1 and M9E1 vapors.…”

Section: Figure 4 Size Distributions Of Neutral Clusters Me Mmentioning

confidence: 99%

“…These results are plotted in Figures 4-6 and tabulated in S4 in the Supporting Information). It is found that the probability of trimer formation in the methanol-rich vapors (M9E1 and M1E1) decreases in the order P(3, 0) > P(2, 1) > P(1, 2) > P(0, 3), whereas that in the ethanol-rich vapors (M1E9) decreases in the order P(0, 3) > P(1, 2) > P(2, 1) > P(3, 0). Similar trends are found for tetramers at higher pressures: P(4, 0) > P(3, 1) > P(2, 2) > P(1, 3) > P(0, 4) in the methanol-rich vapors (M9E1 Figure 3.…”

Section: Figurementioning

confidence: 99%

“…More detailed descriptions of the experimental apparatus and procedures can be found elsewhere. [1][2][3][4] It has been established for alcohols that protonated N-mers are predominately formed by the single-photon ionization of neutral (N + 1)-mer clusters. [1][2][3]5 In addition, pressure studies support our assertion that the neutral cluster distributions in the vacuum chamber prior to ionization reflect the equilibrium cluster distributions above liquid mixtures.…”

Section: Introductionmentioning

confidence: 99%

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Prediction of the Size Distributions of Methanol−Ethanol Clusters Detected in VUV Laser/Time-of-Flight Mass Spectrometry

et al. 2009

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The size distributions and geometries of vapor clusters equilibrated with methanol-ethanol (Me-Et) liquid mixtures were recently studied by vacuum ultraviolet (VUV) laser time-of-flight (TOF) mass spectrometry and density functional theory (DFT) calculations (Liu, Y.; Consta, S.; Ogeer, F.; Shi, Y. J.; Lipson, R. H. Can. J. Chem. 2007, 85, 843-852). On the basis of the mass spectra recorded, it was concluded that the formation of neutral tetramers is particularly prominent. Here we develop grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) frameworks to compute cluster size distributions in vapor mixtures that allow a direct comparison with experimental mass spectra. Using the all-atom optimized potential for liquid simulations (OPLS-AA) force field, we systematically examined the neutral cluster size distributions as functions of pressure and temperature. These neutral cluster distributions were then used to derive ionized cluster distributions to compare directly with the experiments. The simulations suggest that supersaturation at 12 to 16 times the equilibrium vapor pressure at 298 K or supercooling at temperature 240 to 260 K at the equilibrium vapor pressure can lead to the relatively abundant tetramer population observed in the experiments. Our simulations capture the most distinct features observed in the experimental TOF mass spectra: Et 3 H + at m/z ) 139 in the vapor corresponding to 10:90% Me-Et liquid mixture and Me 3 H + at m/z ) 97 in the vapors corresponding to 50:50% and 90:10% Me-Et liquid mixtures. The hybrid GCMC scheme developed in this work extends the capability of studying the size distributions of neat clusters to mixed species and provides a useful tool for studying environmentally important systems such as atmospheric aerosols.

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Geometries and energetics of methanol–ethanol clusters: a VUV laser/time-of-flight mass spectrometry and density functional theory study

Cited by 13 publications

References 24 publications

Nanoimmiscibility: Selective Absorption of Liquid Methanol–Water Mixtures in Carbon Nanotubes

Nanoimmiscibility: Selective Absorption of Liquid Methanol–Water Mixtures in Carbon Nanotubes

Infrared Absorption Spectra of Monohydric Alcohols

Prediction of the Size Distributions of Methanol−Ethanol Clusters Detected in VUV Laser/Time-of-Flight Mass Spectrometry

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