Liquid acetone and chloroform: a comparison between Monte Carlo simulation, molecular Ornstein-Zernike theory, and site-site Ornstein-Zernike theory

Richardi, Johannes; Fries, Pascal; Fischer, R.; Rast, Sebastian; Krienke, Hartmut

doi:10.1080/00268979809482279

Cited by 53 publications

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“…With the recent progress in numerical techniques used to solve the MOZ theory 11,12 it is now possible to examine the liquid properties for the potential models which are usually employed in simulations. For models of acetone, 12 chloroform, 12 and acetonitrile, 13 the results of the MOZ theory were compared to those of simulations.…”

Section: Introductionmentioning

confidence: 99%

A molecular Ornstein–Zernike study of popular models for water and methanol

Richardi

Millot

Fries

1999

The Journal of Chemical Physics

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Some effective models of water ͑TIP3P, SPC, SPC/E, TIP4P͒ and methanol ͑OPLS, H1͒ are studied with the help of the molecular Ornstein-Zernike ͑MOZ͒ theory using the hypernetted chain ͑HNC͒ approximation. The quality of the results obtained within the HNC approximation is discussed by comparison with values from molecular dynamics ͑MD͒ simulations. The MOZ-HNC theory yields internal excess energies and dielectric constants which are about 20% smaller than the simulation results found in the literature. The relative trends of the properties observed by simulation for the different interaction models are correctly predicted. In order to calculate the rotational invariant coefficients which define the liquid structure, new MD simulations were carried out. The rotational invariant coefficients derived from the simulation and from the MOZ theory strongly differ. In particular, the center-center distribution functions show that the theory is not able to reproduce the tetrahedral structure of water. In this solvent a comparison of the O-H distribution function indicates that the MOZ theory underestimates the H bonding. The use of a spherically symmetric bridge function in the reference HNC approximation does not lead to an improvement of the MOZ results. The observed defects of the MOZ-HNC approach contrast with the good agreement found for aprotic solvents and are presumably due to the association by H bonds in water and methanol.

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Section: Introductionmentioning

confidence: 99%

A molecular Ornstein–Zernike study of popular models for water and methanol

Richardi

Millot

Fries

1999

The Journal of Chemical Physics

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“…[21][22][23][24][25][26][27][28][29][30][31][32][33] ACT has a triangular planar shape (C 2v geometry) with the central carbon on the geometric center of the triangle. The liquid is weakly structured, which is reflected in the small values of the properties listed in Table 1.…”

Section: Introductionmentioning

confidence: 99%

A Monte Carlo revisiting of N-methylformamide and acetone

Almeida¹,

Cordeiro²

2011

J. Braz. Chem. Soc.

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Os líquidos N-metilformamida e acetona foram revisitados através de simulações Monte Carlo feitas no ensemble NPT, a 1 atm e 25 °C. As moléculas são rígidas com todos os átomos explicitados e o potencial intermolecular utilizado é o clássico 6-12 Lennard-Jones mais Coulomb. Os g(r)'s teóricos dos dois líquidos foram comparados com aqueles obtidos através de difratometria de nêutrons e simulação de refinamento de estrutura. Os resultados indicam a existência de ligações de hidrogênio determinando a estrutura da N-metilformamida, enquanto que na acetona as correlações são orientadas pelo momento dipolar. A estrutura do líquido N-metilformamida é guiada por um dímero preponderante, no qual as moléculas estão posicionadas de maneira que o ângulo entre os vetores de dipolo é 73°, enquanto que no líquido acetona, que é muito menos organizado, a orientação dos dipolos das moléculas muda de antiparalela a curtas distâncias para mais paralela à medida que a distância aumenta.The pure liquids N-methylformamide and acetone have been revisited via Monte Carlo simulations in the NTP ensemble at 1 atm and 25 °C. The molecules are all-atom rigid structures, and the intermolecular potential used is the classical 6-12 Lennard-Jones plus Coulomb. The theoretical g(r)s of both liquids were compared with those obtained from neutron diffraction and empirical potential structure refinement simulations. The results point to the existence of H-bonds driving the N-methylformamide structure, while in acetone the correlations are dipole moment oriented. The structure of the liquid N-methylformamide is mainly guided by a dimer whose molecules are arranged in such a way that the angle between their dipole moments is 73°, while liquid acetone is much less organized and the orientation of the molecules changes from an antiparallel dipolar correlation at short distances to more parallel alignments of the molecular dipole moments for larger distances.Keywords: Monte Carlo, acetone, N-methylformamide, hydrogen bonds, liquid structure Introduction N-methylformamide (NMF) and acetone (ACT) belong to a group of dipolar organic solvents, which are common media for a variety of important chemical reactions. Table 1 shows some of the most common physical-chemistry properties of the liquids to give an idea of the differences.NMF is one of the simplest molecules among those that include a peptide bond in their structure. The molecule has long been of great interest because of the presence of that structure as a repeat unit in proteins and peptides. The liquid, either pure or as a component of mixtures, has been the subject of studies, theoretically [2][3][4][5][6][7][8][9][10] as well as experimentally. [11][12][13][14][15][16][17][18] The NMF molecules act as proton donors and acceptors via their C=O and H-N groups and consequently form C=O•••H-N hydrogen bonds (H-bond) with each other, the same type of H-bond that is known to play an important role in stabilizing the ordered intramolecular structure of peptides and proteins.19 Moreover, these molecule...

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“…[25][26][27] However, as mentioned by Lombardero et al, 9 development of an angular-dependence bridge function for the HNC approximation is necessary to reproduce the tetrahedral ordering of water at room temperature in the molecular OZ approach. Richardi et al 8 have suggested that applying integral equation methods, which explicitly account for association effects in liquids, [28][29][30][31][32] is an alternative because of the difficulties inherent in producing that bridge functions.…”

Section: Discussionmentioning

confidence: 98%

An interaction site model integral equation study of molecular fluids explicitly considering the molecular orientation

Sumi

Sekino

2006

The Journal of Chemical Physics

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We implemented an interaction site model integral equation for rigid molecules based on a density-functional theory where the molecular orientation is explicitly considered. In this implementation of the integral equation, multiple integral of the degree of freedom of the molecular orientation is performed using efficient quadrature methods, so that the site-site pair correlation functions are evaluated exactly in the limit of low density. We apply this method to Cl(2), HCl, and H(2)O molecular fluids that have been investigated by several integral equation studies using various models. The site-site pair correlation functions obtained from the integral equation are in good agreement with the one from a simulation of these molecules. Rotational invariant coefficients, which characterize the microscopic structure of molecular fluids, are determined from the integral equation and the simulation in order to investigate the accuracy of the integral equation.

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Liquid acetone and chloroform: a comparison between Monte Carlo simulation, molecular Ornstein-Zernike theory, and site-site Ornstein-Zernike theory

Cited by 53 publications

References 0 publications

A molecular Ornstein–Zernike study of popular models for water and methanol

A molecular Ornstein–Zernike study of popular models for water and methanol

A Monte Carlo revisiting of N-methylformamide and acetone

An interaction site model integral equation study of molecular fluids explicitly considering the molecular orientation

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