Hydrogen-bond network in an equimolar acetic acid-water mixture as studied by neutron scattering and density functional theory.

The present study explores the hydrogen-bond network in an equimolar mixture of acetic acid and water (AA-W). The investigation was conducted using a combination of neutron scattering and Density Functional Theory (DFT). New neutron scattering data at large scattering wave vectors were analyzed to determine the total structure factor SM(q) and the molecular form factor F1(q) of the system. DFT calculations using the 6-311++G(d, p) basis set were performed to optimize the monomers and various AA-W H-bonded clusters, including one acetic acid (AA) molecule connected to one, two, and three water molecules. Consequently, three dimers, three trimers, and one tetramer have been considered in order to describe the local order in the mixture. In addition, this study focused on the H-bond interactions in the most probable clusters in the solution, using the natural bond orbital and the atoms in molecules analyses. Our analysis particularly shows that stronger H-bond interactions occur in the ring structures.

H-Bonding network in fully deuterated N-methylformamide-water mixtures as studied by neutron scattering. Complementarity to X-ray study.

In complementarity with X-ray scattering and as extension of our previous publication, neutron scattering measurements are combined to DFT calculation to investigate the structural features of N-methylformamide-water mixtures (NMF-water) for three water molar fractions x w = 0.5 , 0.66 and x w = 0.75 . The recorded data at atmospheric pressure and room temperature are analyzed to yield the structure factor, the molecular form factor and the pair correlation function. Neutron investigations corroborate the X-ray ones and clearly show that liquid order in solutions is well accounted for by a tetramer. In this cluster, an NMF molecule is connected to three water molecules by one N-D···O and two O-D···O hydrogen bonds.

Structural investigations of N-methylformamide-water mixtures at various concentrations.

Structural investigations of N-methylformamide-water mixtures (NMF-water) are performed at room temperature and atmospheric pressure for two water molar fractions x w = 0.66 and x w = 0.75 . This paper extends our recent study on the equimolar system. H-bond networks are preferentially formed between NMF and water molecules. Among a large variety of DFT optimized models, X-ray scattering data shows that the local order of each mixture is better described by a tetramer where one NMF molecule is connected to three water molecules. No self-association is observed in the considered systems. The effect of hydration is compared to the temperature and pressure effects in some hydrogen-bonded liquids.

Neutron scattering experiments on fully deuterated liquid N-methylformamide DCONDCD3 at various temperatures and under pressure. Comparison to X-ray results.

Neutron scattering experiments are performed on fully deuterated liquid N-methylformamide (C2D5NO) at various temperatures and under pressure. The recorded data at atmospheric pressure and room temperature are analyzed to yield the molecular form factor and the distinct pair correlation function. Our measurements clearly show that the hydrogen-bond network, of which the parameters are deduced, persists locally in the liquid. The experimental structure factor could be explained in terms of short-range crystal structure. The r(N...O) distance decreases with increasing temperature from 293 to 398 K, whereas no significant variation of the intermolecular structure is detected when varying pressure from 1 bar to 4 kbar. Along the study, some comparison is made with complementary X-ray results.

Neutron scattering study of the H-bond network in amorphous N-methylformamide.

Original investigations of structural properties in noncrystalline solid N-methylformamide (HCONHCH(3)) are presented in this paper. After description of the sample preparation, the elastic neutron scattering formalism is applied to deduce the coherent scattering cross section for amorphous N-methylformamide. The contribution of each possible monomer (cis or trans) is computed and the corresponding distinct structure factor is deduced. Our measurements clearly show that the hydrogen-bond network occurs in amorphous N-methylformamide between C=O and N-H groups. The experimental spectra are consistent with an open-chain structure similar to the one existing in the crystalline form. The more probable clusters that have been identified in the liquid are also examined.