Local structure and orientational ordering in liquid bromoform

Shephard, Jacob J.; Evans, John S.O.; Salzmann, Christoph G.

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.

Citation

Shephard, J. J., Evans, J. S., & Salzmann, C. G. (2019). Local structure and orientational ordering in liquid bromoform. Molecular Physics, 117(22), 3337-3344. https://doi.org/10.1080/00268976.2019.1648897

• Journal Article Type: Article
• Acceptance Date: Mar 29, 2019
• Online Publication Date: Sep 10, 2019
• Publication Date: 2019
• Deposit Date: Oct 10, 2019
• Publicly Available Date: Sep 10, 2020
• Journal: Molecular Physics
• Print ISSN: 0026-8976
• Electronic ISSN: 1362-3028
• Publisher: Taylor and Francis Group
• Peer Reviewed: Peer Reviewed
• Volume: 117
• Issue: 22
• Pages: 3337-3344
• DOI: https://doi.org/10.1080/00268976.2019.1648897
• Public URL: https://durham-repository.worktribe.com/output/1288749