Liquid water dynamic structure

Curioni et al.148 studied the protonation of 1,3-dioxane and 1,3,5-trioxane by means of CP molecular dynamics similations. The dynamics of both molecules was continued for few ps following protonation. The simulation provided a detailed picture the evolution of both the geometry and the electronic structure, which helped to rationalize some experimental observations. CP molecular dynamics simulations were applied by Tuckerman et al.149,150 to study the dynamics of hydronium (H30+) and hydroxyl (OH-) ions in liquid water. These ions are involved in charge transfer processes in liquid water H20 H+. .. OH2 - H20. .. H+-OH2, and HOH. . . OH- -> HO-. . . HOH. For the solvatetd H30+ ion, a picture consistent with experiment emerged from the simulation. The simulation showed that the HsO+ ion forms a complex with water molecules, the structure of which oscillates between the ones of H502 and I L/ij clusters as a result of frequent proton transfers. During a consid-... 

Liquid water is an essential component of most terrestrial chemical processes, including those of living organisms. The cooperativity of H-bonding in water clusters is therefore of primary importance for understanding the structure and dynamics of pure water, as well as a vast spectrum of aqueous solvation phenomena in biotic and abiotic systems. In the present section we examine cooperativity effects for a... 

The resulting overall picture of liquid water is that of a very dynamical macromolecular system, where clusters of different size and structure coexist in different subvolumes of the liquid and each has characteristic lifetimes and specific temperature dependences. In our opinion, if we would... 

Vibrational spectroscopy can help us escape from this predicament due to the exquisite sensitivity of vibrational frequencies, particularly of the OH stretch, to local molecular environments. Thus, very roughly, one can think of the infrared or Raman spectrum of liquid water as reflecting the distribution of vibrational frequencies sampled by the ensemble of molecules, which reflects the distribution of local molecular environments. This picture is oversimplified, in part as a result of the phenomenon of motional narrowing The vibrational frequencies fluctuate in time (as local molecular environments rearrange), which causes the line shape to be narrower than the distribution of frequencies [3]. Thus in principle, in addition to information about liquid structure, one can obtain information about molecular dynamics from vibrational line shapes. In practice, however, it is often hard to extract this information. Recent and important advances in ultrafast vibrational spectroscopy provide much more useful methods for probing dynamic frequency fluctuations, a process often referred to as spectral diffusion. Ultrafast vibrational spectroscopy of water has also been used to probe molecular rotation and vibrational energy relaxation. The latter process, while fundamental and important, will not be discussed in this chapter, but instead will be covered in a separate review [4],... 

Bjerrum has been used for molecular dynamics simulations of liquid water, to calculate its thermodynamic and structural properties. It turns out that this very important liquid is extremely difficult to model theoretically. 

The values of rc of the solvation shells are surprisingly long in comparison to the value of rc of 500 100 fs of the O-H- -O hydrogen bond in bulk liquid water, but are quite comparable to the recently calculated residence time of 18 ps of water in the solvation shell of Br- [10]. However, one should be very careful with this comparison since the characteristic time of the fluctuations of the hydrogen bond is not the same as the residence time in the solvation shell because the breaking of the hydrogen bond does not automatically mean that the water molecule really leaves the shell. The narrow width and long rc of the O-H- Y absorption component imply that the first solvation shell forms a stable and well-defined structure. The solvation shells of F and of the cations likely show similar dynamics, but unfortunately these dynamics could not be measured because the O-H stretch vibrational lifetime of the water molecules in these solvation shells is comparable to that of bulk HDO D20. 

The complexity of the physical properties of liquid water is largely determined by the presence of a three-dimensional hydrogen bond (HB) network [1]. The HB s undergo continuous transformations that occur on ultrafast timescales. The molecular vibrations are especially sensitive to the presence of the HB network. For example, the spectrum of the OH-stretch vibrational mode is substantially broadened and shifted towards lower frequencies if the OH-group is involved in the HB. Therefore, the microscopic structure and the dynamics of water are expected to manifest themselves in the IR vibrational spectrum, and, therefore, can be studied by methods of ultrafast infrared spectroscopy. It has been shown in a number of ultrafast spectroscopic experiments and computer simulations that dephasing dynamics of the OH-stretch vibrations of water molecules in the liquid phase occurs on sub-picosecond timescales [2-14],... 

In this chapter, the development of a mesoscopic modeling formalism is presented in order to gain fundamental insight into the structure-wettability influence on the underlying liquid water transport and interfacial dynamics in the PEFC CL and GDL. 

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