The Structure of Liquid Methanol

Ludwig, Ralf

doi:10.1002/cphc.200400663

Cited by 115 publications

(85 citation statements)

References 54 publications

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“…Indeed, even the most elementary alcohol molecules, such as methanol and tert-butanol, are known to form a rich variety of clusters in the dense liquid, such as zigzag chains, loops, and lassos. 1,2 This has been confirmed both from spectroscopic sources 1,2 and computer simulations. [3][4][5][6][7] The microstructure of the archetype of associating liquids, namely, water, is still under debate: is it a network of H bonds 8 or a mixture of tetrahedrally rich and poor phases, 9,10 or eventually both?…”

Section: Introductionsupporting

confidence: 81%

A simple lattice model for the microstructure of neat alcohols: Application to liquid methanol

Ciach

Perera²

2009

The Journal of Chemical Physics

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Simple lattice model for self-associating molecules such as methanol or tert-butanol is proposed and studied in mean-field (MF) approximation in the case of methanol. In addition to the isotropic van der Waals interaction, the hydrogen bonding is present in this model when the neighboring alcohol molecules are in appropriate orientations. The orientation of the polar molecule is given by the unit vector n parallel to the vector connecting the center of the tail group with the center of the head group of the molecule. Stability region of the uniform fluid phase against gas-liquid separation and order-disorder transition is obtained for neat methanol in MF approximation. In order to describe the self-association patterns in the liquid, we consider the grand-canonical ensemble average of the scalar product of the orientations of the molecules as a function of the vector Delta x describing the separation between the centers of the molecules. For methanol we find in MF oscillatory decay of for Delta x perpendicular n(x) and for Delta x parallel n(x); the wavelength is somewhat less than two molecular diameters in both cases, and the decay length is larger in the perpendicular direction. This indicates that on average alternating antiparallel and parallel orientations of the second molecule are found for increasing separation from the first molecule in both directions. Such local orientational ordering of the molecules is consistent with association into zigzag chainlike clusters found in recent spectroscopic measurements and computer simulations. In Fourier representation the above structure function assumes maximum for the wave number that coincides with the prepeak position for site-site correlations found in simulations. We argue that can provide a useful tool for discriminating between different local arrangements of any polar molecules.

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Section: Introductionsupporting

confidence: 81%

A simple lattice model for the microstructure of neat alcohols: Application to liquid methanol

Ciach

Perera²

2009

The Journal of Chemical Physics

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“…The zig-zag characteristics of successively deuterated methanol's boiling points could be explained in terms of zero-point energy contributions [30,31]. Matisz et al confirmed the dominance of the cyclic methanol clusters [20].…”

Section: Introductionmentioning

confidence: 85%

“…Varying electronic structure but fixed MP2/TZVPP frequency and same a mf methanol: Ludwig studied the structure [30] and isotope effects [31] of liquid methanol and found mainly ring structures to constitute the liquid phase contrary to molecular dynamics simulations based on the pairwise additivity approximation. The zig-zag characteristics of successively deuterated methanol's boiling points could be explained in terms of zero-point energy contributions [30,31].…”

Section: Introductionmentioning

confidence: 99%

What can clusters tell us about the bulk?

Kirchner

Spickermann

Lehmann

et al. 2011

Computer Physics Communications

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“…[1][2][3][4][5][6][7][8][9][10][11][12] Furthermore, it has been demonstrated that the QCE offers an alternative to established methods concerning the investigation of thermodynamic data as well as structural aspects. [13][14][15] In his original paper, Weinhold described how the well-known rigid-rotor-harmonic-oscillator models may be employed for the analysis of condensed phases based on a distinct number of oligomers of the investigated substance.…”

Section: Introductionmentioning

confidence: 99%

A one-parameter quantum cluster equilibrium approach

Brüssel

Perlt

Domaros

et al. 2012

The Journal of Chemical Physics

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The established quantum cluster equilibrium approach is further developed in this work. The equations are reformulated to result in a one-parameter expression, i.e., with one of two empirical parameters eliminated. Instead of a parametrized constant mean field interaction we present two further approaches using temperature dependent mean field functions. The suggested functions are assessed by means of two test systems, namely hydrogen fluoride and water which are investigated concerning their liquid phase properties as well as the phenomenon of evaporation. The obtained thermodynamic data are compared with each other for the different mean field functions including the conventional approach as well as to experimental data.

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The Structure of Liquid Methanol

Cited by 115 publications

References 54 publications

A simple lattice model for the microstructure of neat alcohols: Application to liquid methanol

A simple lattice model for the microstructure of neat alcohols: Application to liquid methanol

What can clusters tell us about the bulk?

A one-parameter quantum cluster equilibrium approach

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