Liquid water molecular motion

Surface tension accounts for a number of everyday phenomena. For example, a droplet of liquid suspended in air or on a waxy surface is spherical because the surface tension pulls the molecules into the most compact shape, a sphere (Fig. 5.14). The attractive forces between water molecules are greater than those between water and wax, which is largely hydrocarbon. Surface tension decreases as the temperature rises and the interactions between molecules are overcome by the increased molecular motion. 

The diffusion of one liquid into another also demonstrates molecular motion. Figure 2 shows that if a drop of ink is added to a beaker of still water, the color slowly but surely spreads throughout the water. The water molecules and the molecules that give ink its color move continuously. As they slide by one another, the ink molecules eventually become distributed uniformly throughout the volume of liquid. 

A molecular perspective reveals why energy must be supplied to boil water. A molecule of water cannot escape the liquid phase unless it has enough energy of motion to overcome the hydrogen bonding forces that hold liquid water together. About 40 kJ of heat must be supplied to transfer 1 mol of water molecules from the liquid phase into the vapor phase. 

Let us now turn our attention to liquid water. Just as in ice I, molecular motions may be divided into rapid vibrations and slower diffusional motions. In the liquid, however, vibrations are not centred on essentially fixed lattice sites, but around temporary equilibrium positions that are themselves subject to movement. Water at any instant may thus be considered to have an I-structure. An instant later, this I-structure will be modified as a result of vibrations, but not by any additional displacements of the molecules. This, together with the first I-structure, is one of the structures that may be averaged to allow for vibration, thereby contributing to the V-structure. Lastly, if we consider the structure around an individual water molecule over a long time-period, and realize that there is always some order in the arrangement of adjacent molecules in a liquid even over a reasonable duration, then we have the diffusionally averaged D-structure. 

FIG. 23 A schematic illustration of the molecular motions and associated T2 relaxation curve behavior for the three major domains in foods—liquid, viscous liquid, and solid (crystalline and glassy). Typical H T2 NMR relaxation time values observed in these domains, and values specific for water in liquid and crystalline domains, are listed. 

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],... 

Given the character of the water-water interaction, particularly its strength, directionality and saturability, it is tempting to formulate a lattice model, or a cell model, of the liquid. In such models, local structure is the most important of the factors determining equilibrium properties. This structure appears when the molecular motion is defined relative to the vertices of a virtual lattice that spans the volume occupied by the liquid. In general, the translational motion of a molecule is either suppressed completely (static lattice model), or confined to the interior of a small region defined by repulsive interactions with surrounding molecules (cell model). Clearly, the nature of these models is such that they describe best those properties which are structure determined, and describe poorly those properties which, in some sense, depend on the breakdown of positional and orientational correlations between molecules. 

The molecular mobility of water in Nafion was investigated using NMR spectroscopy, by Starkweather and Chang,Boyle et al., and Bunce et al. The overall conclusion of these studies was that water possessed less mobility than that of liquid water and that there were cooperative motions among the molecules and strong interactions with the ion exchange groups. 

Figure 8.11 shows that between 0°C and 4°C liquid water contractsas its temperature is raised. This contraction, however, continues only up to 4°C. As nearfreezing water is heated, there is a simultaneous tendency for the water to expand due to greater molecular motion. Between 0°C and 4°C, the decrease in volume caused by collapsing ice crystals is greater than the increase in volume caused by the faster-moving molecules. As a result, the water volume continues to decrease. At temperatures just above 4°C, expansion overrides contraction because most of the ice crystals have collapsed. 

Above 4°C, liquid water expands as it is heated because of greater molecular motion. 

It is important to remember that all materials have a characteristic response time, varying from picoseconds for simple liquids like water to years for more traditional solids. If a sample appears to be a mobile liquid as it is disturbed in its container, then it will have a characteristic time of well under a second. If a sample appears to be an immobile solid, then it will have a characteristic time of several minutes or hours. Increasing the temperature of the sample will speed up molecular motion and thus decrease (shorten) the characteristic response time. Cooling the sample will have the opposite effect. If heating the sample is not an option, the only recourse is a long experiment ... 

The frequencies of rotational transitions are much smaller than vibrational frequencies, which means that the rotational motion is slower than the vibrational one. For a free molecule, the period of rotational motion is within 10 12-10 9 s. In condensed media the rotational motion is even slower, its period being respectively greater. At this stage it is more correct to speak of the relaxation time of the molecules. The latter essentially depends on the phase state of the medium. For example, in liquid water the relaxation time of molecular dipoles in an external electric field is about 10 11 s, whereas in ice (at 0°C) it is — 1 () 5 s. 

It should, however, be noted that there exist rather complex and nontransparent descriptions made [15] in terms of the absorption vibration spectroscopy of water. This approach takes into account a multitude of the vibration lines calculated for a few water molecules. However, within the frames of this method for the wavenumber1 v < 1000 cm-1, it is difficult to get information about the time/spatial scales of molecular motions and to calculate the spectra of complex-permittivity or of the complex refraction index—in particular, the low-frequency dielectric spectra of liquid water. 

Section IX. We discuss a principally new way, initiated only recently [12, 12a], of modeling of intermolecular interactions. Namely, we start from a very simplified molecular structure of liquid water depicted in Fig. 2e. An approximate solution of the equations of motion of a single polar molecule is found. The key aspect of this approach is that the H-bond resembles a... 

Diffusion is a physical process that involves the random motion of molecules as they collide with other molecules (Brownian motion) and, on a macroscopic scale, move from one part of a system to another. The average distance that molecules move per unit time is described by a physical constant called the diffusion coefficient, D (in units of mm2/s). In pure water, molecules diffuse at a rate of approximately 3xl0"3 mm2 s 1 at 37°C. The factors influencing diffusion in a solution (or self-diffusion in a pure liquid) are molecular weight, intermolecular... 

It is well known that both nanometre and nanosecond-picosecond resolutions at an interface can be achieved by total internal reflection (TIR) fluorescence spectroscopy. Unlike steady-state fluorescence spectroscopy, fluorescence dynamics is highly sensitive to microscopic environments, so that time-resolved TIR fluorometry at water/oil interfaces is worth exploring to obtain a clearer picture of the interfacial phenomena [1]. One of the interesting targets to be studied is the characteristics of dynamic motions of a molecule adsorbed on a water/oil interface. Dynamic molecular motions at a liquid/liquid interface are considered to be influenced by subtle changes in the chemical/physical properties of the interface, particularly in a nanosecond-picosecond time regime. Therefore, time-resolved spectroscopy is expected to be useful to study the nature of a water/oil interface. 

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