Dynamic anti-correlations of water hydrogen bonds
Abstract Water is characterized by strong intermolecular hydrogen bonds (H-bonds) between molecules. The two hydrogen atoms in one water molecule can form H-bonds of dissimilar length. Although intimately connected to water’s anomalous properties, the details and the origins of the asymmetry have re...
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| Format: | Article |
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Nature Portfolio
2024-12-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-54804-y |
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| author | Lucas Gunkel Amelie A. Ehrhard Carola S. Krevert Bogdan A. Marekha Mischa Bonn Maksim Grechko Johannes Hunger |
| author_facet | Lucas Gunkel Amelie A. Ehrhard Carola S. Krevert Bogdan A. Marekha Mischa Bonn Maksim Grechko Johannes Hunger |
| author_sort | Lucas Gunkel |
| collection | DOAJ |
| description | Abstract Water is characterized by strong intermolecular hydrogen bonds (H-bonds) between molecules. The two hydrogen atoms in one water molecule can form H-bonds of dissimilar length. Although intimately connected to water’s anomalous properties, the details and the origins of the asymmetry have remained elusive. We study water’s H-bonds using the O-D stretching vibrations as sensitive reporters of H-bonding of D2O and HOD in dimethylformamide. Broader inhomogeneous linewidths of the OD band of HOD compared to the symmetric and asymmetric OD stretching modes of D2O together with density functional theory calculations provide evidence for markedly anti-correlated H-bonds: water preferentially forms one weak and one strong H-bond. Coupling peaks in the spectra for D2O directly demonstrate anti-correlated H-bonds and these anti-correlations are modulated by thermal motions of water on a sub-picosecond timescale. Experimentally inferred H-bond distributions suggest that the anti-correlations are a direct consequence of the H-bonding potential of XH2 groups, which we confirm for the ND2 group of urea. These structural and dynamic insights into H-bonding are essential for understanding the relationship between the H-bonded structure and phase behavior of water. |
| format | Article |
| id | doaj-art-c1cdb74f36e44fd78b7fd0797e5f4014 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-c1cdb74f36e44fd78b7fd0797e5f40142024-12-01T12:33:31ZengNature PortfolioNature Communications2041-17232024-12-011511910.1038/s41467-024-54804-yDynamic anti-correlations of water hydrogen bondsLucas Gunkel0Amelie A. Ehrhard1Carola S. Krevert2Bogdan A. Marekha3Mischa Bonn4Maksim Grechko5Johannes Hunger6Max-Planck Institute for Polymer Research, Ackermannweg 10Max-Planck Institute for Polymer Research, Ackermannweg 10Max-Planck Institute for Polymer Research, Ackermannweg 10Max-Planck Institute for Polymer Research, Ackermannweg 10Max-Planck Institute for Polymer Research, Ackermannweg 10Max-Planck Institute for Polymer Research, Ackermannweg 10Max-Planck Institute for Polymer Research, Ackermannweg 10Abstract Water is characterized by strong intermolecular hydrogen bonds (H-bonds) between molecules. The two hydrogen atoms in one water molecule can form H-bonds of dissimilar length. Although intimately connected to water’s anomalous properties, the details and the origins of the asymmetry have remained elusive. We study water’s H-bonds using the O-D stretching vibrations as sensitive reporters of H-bonding of D2O and HOD in dimethylformamide. Broader inhomogeneous linewidths of the OD band of HOD compared to the symmetric and asymmetric OD stretching modes of D2O together with density functional theory calculations provide evidence for markedly anti-correlated H-bonds: water preferentially forms one weak and one strong H-bond. Coupling peaks in the spectra for D2O directly demonstrate anti-correlated H-bonds and these anti-correlations are modulated by thermal motions of water on a sub-picosecond timescale. Experimentally inferred H-bond distributions suggest that the anti-correlations are a direct consequence of the H-bonding potential of XH2 groups, which we confirm for the ND2 group of urea. These structural and dynamic insights into H-bonding are essential for understanding the relationship between the H-bonded structure and phase behavior of water.https://doi.org/10.1038/s41467-024-54804-y |
| spellingShingle | Lucas Gunkel Amelie A. Ehrhard Carola S. Krevert Bogdan A. Marekha Mischa Bonn Maksim Grechko Johannes Hunger Dynamic anti-correlations of water hydrogen bonds Nature Communications |
| title | Dynamic anti-correlations of water hydrogen bonds |
| title_full | Dynamic anti-correlations of water hydrogen bonds |
| title_fullStr | Dynamic anti-correlations of water hydrogen bonds |
| title_full_unstemmed | Dynamic anti-correlations of water hydrogen bonds |
| title_short | Dynamic anti-correlations of water hydrogen bonds |
| title_sort | dynamic anti correlations of water hydrogen bonds |
| url | https://doi.org/10.1038/s41467-024-54804-y |
| work_keys_str_mv | AT lucasgunkel dynamicanticorrelationsofwaterhydrogenbonds AT amelieaehrhard dynamicanticorrelationsofwaterhydrogenbonds AT carolaskrevert dynamicanticorrelationsofwaterhydrogenbonds AT bogdanamarekha dynamicanticorrelationsofwaterhydrogenbonds AT mischabonn dynamicanticorrelationsofwaterhydrogenbonds AT maksimgrechko dynamicanticorrelationsofwaterhydrogenbonds AT johanneshunger dynamicanticorrelationsofwaterhydrogenbonds |