The Hydrophobic Interaction Induced Strengthening of Hydrogen Bond in Water-DMSO Binary Mixture
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arXiv
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| Format: | Preprint |
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2024
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| _version_ | 1866910415254978560 |
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| author | Mondal, Sangita Bagchi, Biman |
| author_facet | Mondal, Sangita Bagchi, Biman |
| contents | The lifetime of a hydrogen bond between water and dimethyl sulfoxide (DMSO) is found to be considerably longer than that between two water molecules in the neat water. This is counter-intuitive because the charge on the oxygen in DMSO is considerably less than that in water. Additionally, the strength of the water-dimethyl sulfoxide (w-D) hydrogen bond is found to be strongly composition dependent; the lifetime of the hydrogen bond is ten times larger at 30% over that at very low concentration. Using computer simulations, we perform microscopic structural and dynamic analysis to find that these anomalies arise at least partly from an action-at-a-distance effect where the attraction between the hydrophobic methyl groups results in self-aggregation of DMSO molecules that cages both rotational and linear motions of molecules involved. This is reflected in the observed strong correlation of the lifetime with the local coordination number of the associated methyl groups. The elongated w-D h-bond lifetime causes a slowdown of collective dynamics and affects the lifetime of the w-w h-bond. This nonlinear feedback mechanism explains the strong composition dependence of viscosity and anticipated to play a dominant role in many self-assemblies. Furthermore, the w-D hydrogen bond breaking mechanism changes from low to high DMSO concentration, a phenomenon not anticipated a priori. We introduce a new order parameter-based free energy surface of the bond breaking pathway. A two-dimensional transition state rate theory (TSRT) calculation is performed for the lifetime of the w-D h-bond that is found to be semi-quantitatively accurate |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2404_13001 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | The Hydrophobic Interaction Induced Strengthening of Hydrogen Bond in Water-DMSO Binary Mixture Mondal, Sangita Bagchi, Biman Soft Condensed Matter The lifetime of a hydrogen bond between water and dimethyl sulfoxide (DMSO) is found to be considerably longer than that between two water molecules in the neat water. This is counter-intuitive because the charge on the oxygen in DMSO is considerably less than that in water. Additionally, the strength of the water-dimethyl sulfoxide (w-D) hydrogen bond is found to be strongly composition dependent; the lifetime of the hydrogen bond is ten times larger at 30% over that at very low concentration. Using computer simulations, we perform microscopic structural and dynamic analysis to find that these anomalies arise at least partly from an action-at-a-distance effect where the attraction between the hydrophobic methyl groups results in self-aggregation of DMSO molecules that cages both rotational and linear motions of molecules involved. This is reflected in the observed strong correlation of the lifetime with the local coordination number of the associated methyl groups. The elongated w-D h-bond lifetime causes a slowdown of collective dynamics and affects the lifetime of the w-w h-bond. This nonlinear feedback mechanism explains the strong composition dependence of viscosity and anticipated to play a dominant role in many self-assemblies. Furthermore, the w-D hydrogen bond breaking mechanism changes from low to high DMSO concentration, a phenomenon not anticipated a priori. We introduce a new order parameter-based free energy surface of the bond breaking pathway. A two-dimensional transition state rate theory (TSRT) calculation is performed for the lifetime of the w-D h-bond that is found to be semi-quantitatively accurate |
| title | The Hydrophobic Interaction Induced Strengthening of Hydrogen Bond in Water-DMSO Binary Mixture |
| topic | Soft Condensed Matter |
| url | https://arxiv.org/abs/2404.13001 |