On the Structure Factors of Aqueous Mixtures of 1‐Propanol and 2‐Propanol: X‐Ray Diffraction Experiments and Molecular Dynamics Simulations

Méndez-Bermúdez, José Guillermo; Domínguez, Héctor; Temleitner, László; Pusztai, László

doi:10.1002/pssb.201800215

Cited by 12 publications

(10 citation statements)

References 30 publications

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“…There are several works that explore the structural and dynamical properties of isopropanol/water liquid mixtures using molecular dynamics simulation 12,23,30 . These simulations showed that recently employed force fields provide acceptable agreement over a wide composition range between calculated and measurable physico-chemical properties.…”

Section: Introductionmentioning

confidence: 99%

Molecular Dynamics Simulation Studies of the Temperature-Dependent Structure and Dynamics of Isopropanol–Water Liquid Mixtures at Low Alcohol Content

2019

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Series of molecular dynamics simulations for 2-propanol-water mixtures, as a function of temperature (between freezing and room temperature) and composition (x ip = 0, 0.5, 0.1 and 0.2) have been performed for temperatures reported in the only available experimental structure study. It is shown that when the all-atom OPLS-AA interatomic potentials for the alcohol are combined with the TIP4P/2005 water model then near-quantitative agreement with measured X-ray data, in the reciprocal space, can be achieved. Such an agreement justifies detailed investigations of structural, energetic and dynamic properties on the basis of the simulation trajectories. Here we focus on characteristics related to hydrogen bonds (HB): cluster-, and in particular, ring formation, energy distributions and lifetimes of HB-s have been scrutinized for the entire system, as well as for the water and isopropanol subsystems. It is demonstrated that, similarly to ethanol-water mixtures, the occurrence of 5-membered hydrogen bonded rings is significant, particularly at higher alcohol concentrations. Concerning HB energetics, an intriguing double maximum appears on the alcohol-alcohol HB energy distribution function. HB lifetimes have been found significantly longer in the mixtures than they are in the pure liquids. *

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Section: Introductionmentioning

confidence: 99%

Molecular Dynamics Simulation Studies of the Temperature-Dependent Structure and Dynamics of Isopropanol–Water Liquid Mixtures at Low Alcohol Content

2019

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“…The structure factors calculated from CPMD simulations were also compared with the experimental neutron/X-ray structure factor data for propanol, butanol, and pentanol (Supporting Information, Figure S4). − The fact that the rdfs and structure factors obtained from ab initio MD simulations are comparable with the experimental data gives us the confidence that simulations are representative of the liquid state of alcohols.…”

Section: Simulation Methodologymentioning

confidence: 66%

“…Core electrons were treated using the norm-conserving atomic pseudopotentials of Troullier–Martins, while valence electrons were represented in a plane-wave basis set truncated at an extended energy of 70 Ry . A 70 Ry cutoff has been widely used in the literature and has been considered as adequate in most studies. − , The value of the cutoff is a trade-off between accuracy and computational time required per MD step (see the Supporting Information, Figure S1). Before the ab initio molecular dynamics simulations, a classical MD (using Materials Studio software) simulation was run using universal force field (UFF) parameters.…”

Section: Simulation Methodologymentioning

confidence: 99%

Hydrogen Bonding in the Liquid State of Linear Alcohols: Molecular Dynamics and Thermodynamics

Jindal

Vasudevan

2020

J. Phys. Chem. B

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Linear monohydroxy alcohols are strongly hydrogen-bonded liquids that are considered to be homologues of water. Here, we report ab initio molecular dynamics simulations of the liquid alcohols, methanol to pentanol, and from the combined radial− angular probability distribution of the intermolecular O•••O distances and HO•••O angles determine the geometrical parameters that define the hydrogen bonds in these systems.The key feature of hydrogen bonds in the liquid alcohols, irrespective of the size of the alkyl group, is the strong orientation dependence with the donor−acceptor HO•••O angle being close to zero, similar to that observed in liquid water. Hydrogen bond formation is consequently considered to be the passage from a state where donor−acceptor pairs show no preferred orientation to one where they are almost linear. The potential of mean force, the reversible work associated with this process, is computed from the pair probability density distributions obtained from the simulations and that for a hypothetical state where donor−acceptor pairs are randomly oriented. We find that the magnitude of the free energy for hydrogen bond formation is maximum for ethanol and show that this arises from a larger electrostatic contribution to hydrogen bond formation in ethanol as compared to the other alcohols.

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“…In the AA model, the structure factors for pure substances in the original and the modified force fields were compared with the experimental spectrum obtained by X-ray diffraction [29], Fig. 2A.…”

Section: Structure Factor and Bond Distancementioning

confidence: 99%

Improving 1-propanol Force Field: a New Methodology

Alva-Tamayo

Guillén-Escamilla

Méndez-Maldonado

et al. 2021

Preprint

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A new force field for 1-propanol, in the united and all atom models, has been obtained by combining two different empirical methodologies. The first was developed by scaling atom charges, and Lennard-Jones parameters to fit the dielectric constant, surface tension, and density ((2018) J. Chem. Theory Comput. 14:5949-5958). The second methodology consists of moving these parameters and together with the bond distance to obtain the liquid-vapor phase diagram of the CO2 molecule ((1995) J. Phys. Chem. 99:12021-12024). The last methodology is used to obtain the self-diffusion coefficient, which was not considered in the first one. With this new methodology, the experimental density, dielectric constant, surface tension, and self-diffusion coefficient at ambient temperature could be achieved. Furthermore, we show the temperature dependence of the aforementioned properties. The static structure factors are in accordance with the experimental spectrum. Solubility is increased to the experimental value for the united atom model after applying this methodology and for all atom scheme, the experimental solubility value is maintained.

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On the Structure Factors of Aqueous Mixtures of 1‐Propanol and 2‐Propanol: X‐Ray Diffraction Experiments and Molecular Dynamics Simulations

Cited by 12 publications

References 30 publications

Molecular Dynamics Simulation Studies of the Temperature-Dependent Structure and Dynamics of Isopropanol–Water Liquid Mixtures at Low Alcohol Content

Molecular Dynamics Simulation Studies of the Temperature-Dependent Structure and Dynamics of Isopropanol–Water Liquid Mixtures at Low Alcohol Content

Hydrogen Bonding in the Liquid State of Linear Alcohols: Molecular Dynamics and Thermodynamics

Improving 1-propanol Force Field: a New Methodology

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