Collective Hydrogen Bond Reorganization in Water Studied with Temperature-Dependent Ultrafast Infrared Spectroscopy
We use temperature-dependent ultrafast infrared spectroscopy of dilute HOD in H2O to study the picosecond reorganization of the hydrogen bond network of liquid water. Temperature-dependent two-dimensional infrared (2D IR), pump−probe, and linear absorption measurements are self-consistently analyzed...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society
2012
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| Online Access: | http://hdl.handle.net/1721.1/69860 |
| _version_ | 1811085345846984704 |
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| author | Nicodemus, Rebecca A. Corcelli, S. A. Skinner, J. L. Tokmakoff, Andrei |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Nicodemus, Rebecca A. Corcelli, S. A. Skinner, J. L. Tokmakoff, Andrei |
| author_sort | Nicodemus, Rebecca A. |
| collection | MIT |
| description | We use temperature-dependent ultrafast infrared spectroscopy of dilute HOD in H2O to study the picosecond reorganization of the hydrogen bond network of liquid water. Temperature-dependent two-dimensional infrared (2D IR), pump−probe, and linear absorption measurements are self-consistently analyzed with a response function formalism that includes the effects of spectral diffusion, population lifetime, reorientational motion, and nonequilibrium heating of the local environment upon vibrational relaxation. Over the range 278−345 K, we find the time scales of spectral diffusion and reorientational relaxation decrease from approximately 2.4 to 0.7 ps and 4.6 to 1.2 ps, respectively, which corresponds to barrier heights of 3.4 and 3.7 kcal/mol, respectively. We compare the temperature dependence of the time scales to a number of measures of structural relaxation and find similar effective activation barrier heights and slightly non-Arrhenius behavior, which suggests that the reaction coordinate for the hydrogen bond rearrangement in water is collective. Frequency and orientational correlation functions computed from molecular dynamics (MD) simulations over the same temperature range support our interpretations. Finally, we find the lifetime of the OD stretch is nearly the same from 278 K to room temperature and then increases as the temperature is increased to 345 K. |
| first_indexed | 2024-09-23T13:07:28Z |
| format | Article |
| id | mit-1721.1/69860 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:07:28Z |
| publishDate | 2012 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/698602022-10-01T13:13:27Z Collective Hydrogen Bond Reorganization in Water Studied with Temperature-Dependent Ultrafast Infrared Spectroscopy Nicodemus, Rebecca A. Corcelli, S. A. Skinner, J. L. Tokmakoff, Andrei Massachusetts Institute of Technology. Department of Chemistry Tokmakoff, Andrei Nicodemus, Rebecca A. Tokmakoff, Andrei We use temperature-dependent ultrafast infrared spectroscopy of dilute HOD in H2O to study the picosecond reorganization of the hydrogen bond network of liquid water. Temperature-dependent two-dimensional infrared (2D IR), pump−probe, and linear absorption measurements are self-consistently analyzed with a response function formalism that includes the effects of spectral diffusion, population lifetime, reorientational motion, and nonequilibrium heating of the local environment upon vibrational relaxation. Over the range 278−345 K, we find the time scales of spectral diffusion and reorientational relaxation decrease from approximately 2.4 to 0.7 ps and 4.6 to 1.2 ps, respectively, which corresponds to barrier heights of 3.4 and 3.7 kcal/mol, respectively. We compare the temperature dependence of the time scales to a number of measures of structural relaxation and find similar effective activation barrier heights and slightly non-Arrhenius behavior, which suggests that the reaction coordinate for the hydrogen bond rearrangement in water is collective. Frequency and orientational correlation functions computed from molecular dynamics (MD) simulations over the same temperature range support our interpretations. Finally, we find the lifetime of the OD stretch is nearly the same from 278 K to room temperature and then increases as the temperature is increased to 345 K. National Science Foundation (U.S.) (CHE-0750307) United States. Dept. of Energy (Grant DE-FG02-09ER16110) National Institutes of Health (U.S.) (Graduate Research Fellowship) United States. Dept. of Energy (Grant DE-FG02-99ER14988) 2012-03-26T18:54:09Z 2012-03-26T18:54:09Z 2011-03 Article http://purl.org/eprint/type/JournalArticle 1520-6106 1520-5207 http://hdl.handle.net/1721.1/69860 Nicodemus, Rebecca A. et al. “Collective Hydrogen Bond Reorganization in Water Studied with Temperature-Dependent Ultrafast Infrared Spectroscopy.” The Journal of Physical Chemistry B 115.18 (2011): 5604–5616. en_US http://dx.doi.org/10.1021/jp111434u Journal of Physical Chemistry B Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society Prof. Tokmakoff via Erja Kajosalo |
| spellingShingle | Nicodemus, Rebecca A. Corcelli, S. A. Skinner, J. L. Tokmakoff, Andrei Collective Hydrogen Bond Reorganization in Water Studied with Temperature-Dependent Ultrafast Infrared Spectroscopy |
| title | Collective Hydrogen Bond Reorganization in Water Studied with Temperature-Dependent Ultrafast Infrared Spectroscopy |
| title_full | Collective Hydrogen Bond Reorganization in Water Studied with Temperature-Dependent Ultrafast Infrared Spectroscopy |
| title_fullStr | Collective Hydrogen Bond Reorganization in Water Studied with Temperature-Dependent Ultrafast Infrared Spectroscopy |
| title_full_unstemmed | Collective Hydrogen Bond Reorganization in Water Studied with Temperature-Dependent Ultrafast Infrared Spectroscopy |
| title_short | Collective Hydrogen Bond Reorganization in Water Studied with Temperature-Dependent Ultrafast Infrared Spectroscopy |
| title_sort | collective hydrogen bond reorganization in water studied with temperature dependent ultrafast infrared spectroscopy |
| url | http://hdl.handle.net/1721.1/69860 |
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