The Structure of Ethylbenzene, Styrene and Phenylacetylene Determined by Total Neutron Scattering

Szala-Bilnik, Joanna; Falkowska, Marta; Bowron, Daniel T.; Hardacre, Christopher; Youngs, Tristan G. A.

doi:10.1002/cphc.201700393

Cited by 13 publications

(15 citation statements)

References 56 publications

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“…Our previous experiments [15,16], alongside those of Falkowska and co-workers [17,18], have successfully used Neutron Diffraction with Isotopic Substitution (NDIS) interpreted using Empirical Potential Structure Refinement (EPSR) to understand the liquid structure of a number of small aromatics, including benzene, in unprecedented detail. The key feature of the liquid structure of benzene is perpendicular 'Y-stacking' molecules with two hydrogen atoms pointing towards the aromatic ring of the central molecule (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Temperature dependent structural changes in liquid benzene studied using neutron diffraction

Headen

2019

Molecular Physics

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We present neutron diffraction data for liquid benzene measured as a function of temperature from 10°C to 70°C. Isotopic substitution and Empirical Potential Structure Refinement were used to obtain a complete spatial and orientational understanding of nearest neighbour correlations. We find an increased prevalence of nearest neighbour molecules where the angle between the aromatic planes is perpendicular, and at an angle of around 60°, when the temperature is reduced. There is no significant change in prevalence parallel stacked arrangements of nearest neighbour molecules as a function of temperature. The structure of the increased local order is consistent with structural motifs observed in benzene dimers and clusters from quantum chemistry calculations in the literature. ARTICLE HISTORY

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Section: Introductionmentioning

confidence: 99%

Temperature dependent structural changes in liquid benzene studied using neutron diffraction

Headen

2019

Molecular Physics

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“…Neutron scattering is an unparalleled technique in the study of the structure of molecular liquids, and has recently been used to study a number of aromatic liquids. 42,[49][50][51] The neutron scattering length is dependent on the isotope. Isotopic substitution, particularly H/D and *N/ 15 N, can therefore be used to provide multiple datasets from the same underlying liquid structure.…”

Section: 17mentioning

confidence: 99%

The structures of liquid pyridine and naphthalene: the effects of heteroatoms and core size on aromatic interactions

Headen

Cullen

Patel

et al. 2018

Phys. Chem. Chem. Phys.

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Total neutron scattering has been used in conjunction with H/D and *N/ 15 N isotopic substitution to determine the detailed liquid-state structures of pyridine and naphthalene. Analysis of the data via an empirical potential-based structure refinement method has allowed us to interrogate the full six-dimensional spatial and orientational correlation surfaces in these systems, and thereby to deduce the fundamental effects of a heteroatom and aromatic core-size on intermolecular p-p interactions. We find that the presence of a nitrogen heteroatom, and concomitant dipole moment, in pyridine induces surprisingly subtle departures from the structural correlations observed in liquid benzene: in both cases the most probable local motif is based on perpendicular (edge-to-face) intermolecular contacts, while parallel-displaced configurations give rise to a clear shoulder in the correlation surface. However, the effect of the heteroatom is revealed through detailed analysis of the intermolecular orientational correlations. This analysis shows a tendency for neighbouring pyridine molecules to direct one meta-and one para-hydrogen towards the neighbouring aromatic p-orbitals in edge-to-face configurations, while head-to-tail alignment of adjacent nitrogen atoms is favoured in faceto-face configurations. In contrast to this, increasing aromatic core size from one to only two rings has a clear and profound effect on the p-p interactions and liquid structure. Our experiments show that naphthalenenaphthalene contacts are dominated by parallel-displaced configurations, akin to those found in graphite. This marks a fundamental difference with the structure of liquid benzene, in which perpendicular geometries are favoured. Furthermore, it is remarkable to note that in the systems studied, the most favoured spatioorientational configurations observed in the liquid state are not predicted from ab initio calculations and/or solid state crystallographic studies. This highlights the need for caution when extrapolating the results of crystallographic and computational studies to aromatic interactions in liquids and disordered systems.

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“…The shape of the first coordination peaks reported in This organization is quite similar to the one reported for benzene and toluene (and analogous derivated benzenes), where short distance parallelism and larger distance perpendicular organization (yet with some parallel component) were observed. 19,21,48 The structural organisation between neighbour molecules can be influenced also by other effects.…”

Section: Resultsmentioning

confidence: 99%

Structure of anisole derivatives by total neutron and X-ray scattering: Evidences of weak C H⋯O and C H⋯π interactions in the liquid state

Triolo

Celso

Plechkova

et al. 2020

Journal of Molecular Liquids

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High resolution, total neutron and x-ray scattering data have been used in synergy with Molecular Dynamics simulations to access atomistic scale insight into the structure of anisole and 2,3,5trimethylanisole, two aromatic compounds bearing an electron-donating methoxy group. A detailed description is provided for the main interactions occurring in these systems, including π-π stacking and weak hydrogen bonding correlations: C-H•••O and C-H••• π. The existence of preferential orientations of the first shell coordinating molecules and the specific nature of the interactions involving the π cloud and the polar methoxy group have been reported and discussed.

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The Structure of Ethylbenzene, Styrene and Phenylacetylene Determined by Total Neutron Scattering

Cited by 13 publications

References 56 publications

Temperature dependent structural changes in liquid benzene studied using neutron diffraction

Temperature dependent structural changes in liquid benzene studied using neutron diffraction

The structures of liquid pyridine and naphthalene: the effects of heteroatoms and core size on aromatic interactions

Structure of anisole derivatives by total neutron and X-ray scattering: Evidences of weak C H⋯O and C H⋯π interactions in the liquid state

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