Can Charge Transfer Across C-H...O Hydrogen Bonds Stabilize Oil Droplets in Water?
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arXiv
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| Format: | Preprint |
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2025
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| _version_ | 1866914151988723712 |
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| author | Zhao, Ruoqi Shen, Hengyuan LaCour, R. Allen Heindel, Joseph P. Head-Gordon, Martin Head-Gordon, Teresa |
| author_facet | Zhao, Ruoqi Shen, Hengyuan LaCour, R. Allen Heindel, Joseph P. Head-Gordon, Martin Head-Gordon, Teresa |
| contents | Oil-water emulsions resist aggregation due to the presence of negative charges at their surface that leads to mutual repulsion between droplets, but the molecular origin of oil charge is currently under debate. While much evidence has suggested that ionic species must accumulate at the interface, an alternative perspective attributes the negative charge on the oil droplet to charge transfer of electron density from water to oil molecules. While the charge transfer mechanism is consistent with the correct sign of oil charge, it is just as important to provide good estimates of the charge magnitude to explain emulsion stability and electrophoresis experiments. Here we show using energy decomposition analysis that the amount of net flow of charge from water to oil is negligibly small due to nearly equal forward and backward charge transfer through weak oil-water interactions, such that oil droplets would be unstable and coalesce, contrary to experiment. The lack of charge transfer also explains why vibrational sum frequency scattering reports a blue shift in the oil C-H frequency when forming emulsions with water, which arises from Pauli repulsion due to localized confinement at the interface. Finally, unlike ions, neither charge transfer nor dynamic polarization can produce a finite conductivity needed to couple to electric fields that would explain electrophoretic mobility. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2504_11606 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Can Charge Transfer Across C-H...O Hydrogen Bonds Stabilize Oil Droplets in Water? Zhao, Ruoqi Shen, Hengyuan LaCour, R. Allen Heindel, Joseph P. Head-Gordon, Martin Head-Gordon, Teresa Chemical Physics Oil-water emulsions resist aggregation due to the presence of negative charges at their surface that leads to mutual repulsion between droplets, but the molecular origin of oil charge is currently under debate. While much evidence has suggested that ionic species must accumulate at the interface, an alternative perspective attributes the negative charge on the oil droplet to charge transfer of electron density from water to oil molecules. While the charge transfer mechanism is consistent with the correct sign of oil charge, it is just as important to provide good estimates of the charge magnitude to explain emulsion stability and electrophoresis experiments. Here we show using energy decomposition analysis that the amount of net flow of charge from water to oil is negligibly small due to nearly equal forward and backward charge transfer through weak oil-water interactions, such that oil droplets would be unstable and coalesce, contrary to experiment. The lack of charge transfer also explains why vibrational sum frequency scattering reports a blue shift in the oil C-H frequency when forming emulsions with water, which arises from Pauli repulsion due to localized confinement at the interface. Finally, unlike ions, neither charge transfer nor dynamic polarization can produce a finite conductivity needed to couple to electric fields that would explain electrophoretic mobility. |
| title | Can Charge Transfer Across C-H...O Hydrogen Bonds Stabilize Oil Droplets in Water? |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2504.11606 |