Elisa Steinrücken, Max Weigler, Sebastian Kloth, Michael Vogel
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引用次数: 0
Abstract
We investigate water dynamics in mesoporous silica across partial crystallization by combining broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR), and molecular dynamics simulations (MDS). Exploiting the fact that not only BDS but also NMR field-cycling relaxometry and stimulated-echo experiments provide access to dynamical susceptibilities in broad frequency and temperature ranges, we study both the fully liquid state above the melting point Tm and the dynamics of coexisting water and ice phases below this temperature. It is found that partial crystallization leads to a change in the temperature dependence of rotational correlation times τ, which occurs in addition to previously reported dynamical crossovers of confined water and depends on the pore diameter. Furthermore, we observe that dynamical susceptibilities of water are strongly asymmetric in the fully liquid state, whereas they are much broader and nearly symmetric in the partially frozen state. Finally, water in the nonfreezable interfacial layer below Tm does not exhibit a much debated dynamical crossover at ∼220 K. We argue that its dynamics is governed by a static energy landscape, which results from the interaction with the bordering silica and ice surfaces and features a Gaussian-like barrier distribution. Consistently, our MDS analysis of the motional mechanism reveals a hopping motion of water in thin interfacial layers. The rotational correlation times of the confined ice phases follow Arrhenius laws. While the values of τ depend on the pore diameter, freezable water in various types of confinements and mixtures shows similar activation energies of Ea ≈ 0.43 eV.
期刊介绍:
The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance.
Topical coverage includes:
Theoretical Methods and Algorithms
Advanced Experimental Techniques
Atoms, Molecules, and Clusters
Liquids, Glasses, and Crystals
Surfaces, Interfaces, and Materials
Polymers and Soft Matter
Biological Molecules and Networks.