A study of the influence of isotopic substitution on the melting point and temperature of maximum density of water by means of path integral simulations of rigid models

Literature Information

Publication Date 2012-09-14
DOI 10.1039/C2CP42393F
Impact Factor 3.676
Authors

Carl McBride, Juan L. Aragones, Eva G. Noya, Carlos Vega


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Abstract

The melting point of ice Ih, as well as the temperature of maximum density (TMD) in the liquid phase, has been computed using the path integral Monte Carlo method. Two new models are introduced, TIP4PQ_D2O and TIP4PQ_T2O, which are specifically designed to study D2O and T2O respectively. We have also used these models to study the “competing quantum effects” proposal of Habershon, Markland and Manolopoulos; the TIP4PQ/2005, TIP4PQ/2005 (D2O) and TIP4PQ/2005 (T2O) models are able to study the isotopic substitution of hydrogen for deuterium or tritium whilst constraining the geometry, while the TIP4PQ_D2O and TIP4PQ_T2O models, where the O–H bond lengths are progressively shortened, permit the study of the influence of geometry (and thus dipole moment) on the isotopic effects. For TIP4PQ_D2O–TIP4PQ/2005 we found a melting point shift of 4.9 K (experimentally the value is 3.68 K) and a TMD shift of 6 K (experimentally 7.2 K). For TIP4PQ_T2O–TIP4PQ/2005 we found a melting point shift of 5.2 K (experimentally the value is 4.49 K) and a TMD shift of 7 K (experimentally 9.4 K).

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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