Dynamical aspects of isomerization and melting transitions in [H2O]8
We present a transition path sampling study of the dynamics of isomerization between the S4 and the D2d cubic structures of the water octamer. The reaction mechanism involves a transition state characterized by a distorted face exhibiting a diagonal hydrogen bond. Analysis of an ensemble of trajecto...
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| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_10895639_v105_n12_p2646_Laria |
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todo:paper_10895639_v105_n12_p2646_Laria2023-10-03T16:04:27Z Dynamical aspects of isomerization and melting transitions in [H2O]8 Laria, D. Rodriguez, J. Dellago, C. Chandler, D. Melting transitions Entropy Hydrogen bonds Melting Molecules Protons Reaction kinetics Thermal effects Water Isomerization We present a transition path sampling study of the dynamics of isomerization between the S4 and the D2d cubic structures of the water octamer. The reaction mechanism involves a transition state characterized by a distorted face exhibiting a diagonal hydrogen bond. Analysis of an ensemble of trajectories shows that the isomerization requires concerted flips of double proton donor molecules and the interchange between dangling and bonding hydrogens in single proton donor molecules. At a total energy E = -60.5 kcal/mol, we calculated that the characteristic time for the interconversion is of the order of milliseconds. We have also investigated pathways for the melting transition at temperatures T ≈ 200 K. We find that the barrier for solid-liquid interconversions never exceeds 2kBT measured from the liquid side. Such transitions between liquid and solid do not involve the passage over an energetic barrier; instead, the stabilization of the liquid phase is the result of a cancellation between energetic and entropic contributions. © 2001 American Chemical Society. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_10895639_v105_n12_p2646_Laria |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Melting transitions Entropy Hydrogen bonds Melting Molecules Protons Reaction kinetics Thermal effects Water Isomerization |
| spellingShingle |
Melting transitions Entropy Hydrogen bonds Melting Molecules Protons Reaction kinetics Thermal effects Water Isomerization Laria, D. Rodriguez, J. Dellago, C. Chandler, D. Dynamical aspects of isomerization and melting transitions in [H2O]8 |
| topic_facet |
Melting transitions Entropy Hydrogen bonds Melting Molecules Protons Reaction kinetics Thermal effects Water Isomerization |
| description |
We present a transition path sampling study of the dynamics of isomerization between the S4 and the D2d cubic structures of the water octamer. The reaction mechanism involves a transition state characterized by a distorted face exhibiting a diagonal hydrogen bond. Analysis of an ensemble of trajectories shows that the isomerization requires concerted flips of double proton donor molecules and the interchange between dangling and bonding hydrogens in single proton donor molecules. At a total energy E = -60.5 kcal/mol, we calculated that the characteristic time for the interconversion is of the order of milliseconds. We have also investigated pathways for the melting transition at temperatures T ≈ 200 K. We find that the barrier for solid-liquid interconversions never exceeds 2kBT measured from the liquid side. Such transitions between liquid and solid do not involve the passage over an energetic barrier; instead, the stabilization of the liquid phase is the result of a cancellation between energetic and entropic contributions. © 2001 American Chemical Society. |
| format |
JOUR |
| author |
Laria, D. Rodriguez, J. Dellago, C. Chandler, D. |
| author_facet |
Laria, D. Rodriguez, J. Dellago, C. Chandler, D. |
| author_sort |
Laria, D. |
| title |
Dynamical aspects of isomerization and melting transitions in [H2O]8 |
| title_short |
Dynamical aspects of isomerization and melting transitions in [H2O]8 |
| title_full |
Dynamical aspects of isomerization and melting transitions in [H2O]8 |
| title_fullStr |
Dynamical aspects of isomerization and melting transitions in [H2O]8 |
| title_full_unstemmed |
Dynamical aspects of isomerization and melting transitions in [H2O]8 |
| title_sort |
dynamical aspects of isomerization and melting transitions in [h2o]8 |
| url |
http://hdl.handle.net/20.500.12110/paper_10895639_v105_n12_p2646_Laria |
| work_keys_str_mv |
AT lariad dynamicalaspectsofisomerizationandmeltingtransitionsinh2o8 AT rodriguezj dynamicalaspectsofisomerizationandmeltingtransitionsinh2o8 AT dellagoc dynamicalaspectsofisomerizationandmeltingtransitionsinh2o8 AT chandlerd dynamicalaspectsofisomerizationandmeltingtransitionsinh2o8 |
| _version_ |
1807324490378510336 |