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Molecular Physics
An International Journal at the Interface Between Chemistry and Physics
Volume 117, 2019 - Issue 22: Learning from Disorder – A Tribute to Alan Soper
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Molecular Liquids and Mixtures

Local structure and orientational ordering in liquid bromoform

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Pages 3337-3344 | Received 11 Feb 2019, Accepted 29 Mar 2019, Published online: 10 Sep 2019
 

Abstract

The neutron diffraction data of liquid bromoform (CHBr3) at 25°C was analysed using the Empirical Potential Structure Refinement technique in combination with H/D isotopic substitution. Compared to liquid chloroform (CHCl3), CHBr3 displays more spatially defined intermolecular contacts. A preference for polar stacking with collinear alignment of dipole moments is observed for the most closely approaching CHBr3 molecules, although to a lesser extent than in chloroform. Consistent with this, and in line with dielectric spectroscopy, the Kirkwood correlation factor from the structural model of CHBr3 is smaller than that of CHCl3. The net antiparallel alignment of dipole moments in CHBr3, as suggested by dielectric spectroscopy, must be due to weak but persistent long-range orientation correlations in CHBr3, which counteract the local polar stacking.

GRAPHICAL ABSTRACT

Acknowledgments

We thank the Royal Society for a University Research Fellowship (CGS), the EPSRC and Durham University for a PhD studentship (JJS), the ISIS neutron source for granting access to the SANDALS beamline, S. Imberti and S. Callear for help during the neutron diffraction experiment, and A. Soper for helpful discussions.

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

This work was supported by Engineering and Physical Sciences Research Council: [DTA studentship for JJS]; Royal Society: [grant number UF100144].

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