Grand Canonical Investigation of the Quasi Liquid Layer of Ice: Is It Liquid?
In this study, the solid-vapor equilibrium and the quasi liquid layer (QLL) of ice Ih exposing the basal and primary prismatic faces were explored by means of grand canonical molecular dynamics simulations with the monatomic mW potential. For this model, the solid-vapor equilibrium was found to foll...
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todo:paper_15206106_v122_n18_p4880_Pickering2023-10-03T16:20:32Z Grand Canonical Investigation of the Quasi Liquid Layer of Ice: Is It Liquid? Pickering, I. Paleico, M. Sirkin, Y.A.P. Scherlis, D.A. Factorovich, M.H. Condensation Liquids Molecular dynamics Segregation (metallography) Capillary condensation Clausius Clapeyron relation Crystallization dynamics Experimental values Indentation experiment Molecular dynamics simulations Nanometer length scale Nanophase segregation Ice In this study, the solid-vapor equilibrium and the quasi liquid layer (QLL) of ice Ih exposing the basal and primary prismatic faces were explored by means of grand canonical molecular dynamics simulations with the monatomic mW potential. For this model, the solid-vapor equilibrium was found to follow the Clausius-Clapeyron relation in the range examined, from 250 to 270 K, with a δHsub of 50 kJ/mol in excellent agreement with the experimental value. The phase diagram of the mW model was constructed for the low pressure region around the triple point. The analysis of the crystallization dynamics during condensation and evaporation revealed that, for the basal face, both processes are highly activated, and in particular cubic ice is formed during condensation, producing stacking-disordered ice. The basal and primary prismatic surfaces of ice Ih were investigated at different temperatures and at their corresponding equilibrium vapor pressures. Our results show that the region known as QLL can be interpreted as the outermost layers of the solid where a partial melting takes place. Solid islands in the nanometer length scale are surrounded by interconnected liquid areas, generating a bidimensional nanophase segregation that spans throughout the entire width of the outermost layer even at 250 K. Two approaches were adopted to quantify the QLL and discussed in light of their ability to reflect this nanophase segregation phenomena. Our results in the μVT ensemble were compared with NPT and NVT simulations for two system sizes. No significant differences were found between the results as a consequence of model system size or of the working ensemble. Nevertheless, certain advantages of performing μVT simulations in order to reproduce the experimental situation are highlighted. On the one hand, the QLL thickness measured out of equilibrium might be affected because of crystallization being slower than condensation. On the other, preliminary simulations of AFM indentation experiments show that the tip can induce capillary condensation over the ice surface, enlarging the apparent QLL. © 2018 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_15206106_v122_n18_p4880_Pickering |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Condensation Liquids Molecular dynamics Segregation (metallography) Capillary condensation Clausius Clapeyron relation Crystallization dynamics Experimental values Indentation experiment Molecular dynamics simulations Nanometer length scale Nanophase segregation Ice |
| spellingShingle |
Condensation Liquids Molecular dynamics Segregation (metallography) Capillary condensation Clausius Clapeyron relation Crystallization dynamics Experimental values Indentation experiment Molecular dynamics simulations Nanometer length scale Nanophase segregation Ice Pickering, I. Paleico, M. Sirkin, Y.A.P. Scherlis, D.A. Factorovich, M.H. Grand Canonical Investigation of the Quasi Liquid Layer of Ice: Is It Liquid? |
| topic_facet |
Condensation Liquids Molecular dynamics Segregation (metallography) Capillary condensation Clausius Clapeyron relation Crystallization dynamics Experimental values Indentation experiment Molecular dynamics simulations Nanometer length scale Nanophase segregation Ice |
| description |
In this study, the solid-vapor equilibrium and the quasi liquid layer (QLL) of ice Ih exposing the basal and primary prismatic faces were explored by means of grand canonical molecular dynamics simulations with the monatomic mW potential. For this model, the solid-vapor equilibrium was found to follow the Clausius-Clapeyron relation in the range examined, from 250 to 270 K, with a δHsub of 50 kJ/mol in excellent agreement with the experimental value. The phase diagram of the mW model was constructed for the low pressure region around the triple point. The analysis of the crystallization dynamics during condensation and evaporation revealed that, for the basal face, both processes are highly activated, and in particular cubic ice is formed during condensation, producing stacking-disordered ice. The basal and primary prismatic surfaces of ice Ih were investigated at different temperatures and at their corresponding equilibrium vapor pressures. Our results show that the region known as QLL can be interpreted as the outermost layers of the solid where a partial melting takes place. Solid islands in the nanometer length scale are surrounded by interconnected liquid areas, generating a bidimensional nanophase segregation that spans throughout the entire width of the outermost layer even at 250 K. Two approaches were adopted to quantify the QLL and discussed in light of their ability to reflect this nanophase segregation phenomena. Our results in the μVT ensemble were compared with NPT and NVT simulations for two system sizes. No significant differences were found between the results as a consequence of model system size or of the working ensemble. Nevertheless, certain advantages of performing μVT simulations in order to reproduce the experimental situation are highlighted. On the one hand, the QLL thickness measured out of equilibrium might be affected because of crystallization being slower than condensation. On the other, preliminary simulations of AFM indentation experiments show that the tip can induce capillary condensation over the ice surface, enlarging the apparent QLL. © 2018 American Chemical Society. |
| format |
JOUR |
| author |
Pickering, I. Paleico, M. Sirkin, Y.A.P. Scherlis, D.A. Factorovich, M.H. |
| author_facet |
Pickering, I. Paleico, M. Sirkin, Y.A.P. Scherlis, D.A. Factorovich, M.H. |
| author_sort |
Pickering, I. |
| title |
Grand Canonical Investigation of the Quasi Liquid Layer of Ice: Is It Liquid? |
| title_short |
Grand Canonical Investigation of the Quasi Liquid Layer of Ice: Is It Liquid? |
| title_full |
Grand Canonical Investigation of the Quasi Liquid Layer of Ice: Is It Liquid? |
| title_fullStr |
Grand Canonical Investigation of the Quasi Liquid Layer of Ice: Is It Liquid? |
| title_full_unstemmed |
Grand Canonical Investigation of the Quasi Liquid Layer of Ice: Is It Liquid? |
| title_sort |
grand canonical investigation of the quasi liquid layer of ice: is it liquid? |
| url |
http://hdl.handle.net/20.500.12110/paper_15206106_v122_n18_p4880_Pickering |
| work_keys_str_mv |
AT pickeringi grandcanonicalinvestigationofthequasiliquidlayeroficeisitliquid AT paleicom grandcanonicalinvestigationofthequasiliquidlayeroficeisitliquid AT sirkinyap grandcanonicalinvestigationofthequasiliquidlayeroficeisitliquid AT scherlisda grandcanonicalinvestigationofthequasiliquidlayeroficeisitliquid AT factorovichmh grandcanonicalinvestigationofthequasiliquidlayeroficeisitliquid |
| _version_ |
1807321815016538112 |