Translational jumping

Each of the membranes acts like a hard wall for dimer molecules. Consequently, in parts I and III we observe accumulation of dimer particles at the membrane. The presence of this layer can prohibit translation of particles through the membrane. Moreover, in parts II and IV of the box, at the membranes, we observe a depletion of the local density. This phenomenon can artificially enhance diffusion in the system. In order to avoid the problem, a double translation step has been applied. In one step the maximum displacement allows a particle to jump through the surface layer in the second step the maximum translation is small, to keep the total acceptance ratio as desired. 

As the translational energy of the impacting ion increases, the G-S cross section will rapidly fall off until at energies above 10 e.v., the electron jump model for the reaction will predominate. That mechanism does not seem to depend strongly on translational energy. 

Studies of the effect of permeant s size on the translational diffusion in membranes suggest that a free-volume model is appropriate for the description of diffusion processes in the bilayers [93]. The dynamic motion of the chains of the membrane lipids and proteins may result in the formation of transient pockets of free volume or cavities into which a permeant molecule can enter. Diffusion occurs when a permeant jumps from a donor to an acceptor cavity. Results from recent molecular dynamics simulations suggest that the free volume transport mechanism is more likely to be operative in the core of the bilayer [84]. In the more ordered region of the bilayer, a kink shift diffusion mechanism is more likely to occur [84,94]. Kinks may be pictured as dynamic structural defects representing small, mobile free volumes in the hydrocarbon phase of the membrane, i.e., conformational kink g tg ) isomers of the hydrocarbon chains resulting from thermal motion [52] (Fig. 8). Small molecules can enter the small free volumes of the kinks and migrate across the membrane together with the kinks. 

We now discuss the translation of the MC time-step into physical time units. It is desirable to map the mobility of the lattice model (due to jumps of the effective monomers) onto the average jump rate of the torsional degrees of freedom, since these motions dominate the relaxation of the overall configuration of the chain. This means that we must allow for a temperature-depen-dent time unit tmc(T) which one attempted MCS per monomer corresponds to, via the formula ... 

Molecules translate, rotate and vibrate at any temperature (except absolute zero), jumping between the requisite quantum-mechanically allowed energy levels. We call the common pool of energy enabling translation, rotation and vibration the thermal energy . In fact, we can now rephrase the statement on p. 34, and say that temperature is a macroscopic manifestation of these motions. Energy can be readily distributed and redistributed at random between these different modes. 

Pulsed field gradient (PFG)-NMR experiments have been employed in the groups of Zawodzinski and Kreuer to measure the self-diffusivity of water in the membrane as a function of the water content. From QENS, the typical time and length scales of the molecular motions can be evaluated. It was observed that water mobility increases with water content up to almost bulk-like values above T 10, where the water content A = nn o/ nsojH is defined as the ratio of the number of moles of water molecules per moles of acid head groups (-SO3H). In Perrin et al., QENS data for hydrated Nation were analyzed with a Gaussian model for localized translational diffusion. Typical sizes of confining domains and diffusion coefficients, as well as characteristic times for the elementary jump processes, were obtained as functions of A the results were discussed with respect to membrane structure and sorption characteristics. ... 

The value of the jump distance in the )0-relaxation of PIB found from the study of the self-motion of protons (2.7 A) is much larger than that obtained from the NSE study on the pair correlation function (0.5-0.9 A). This apparent paradox can also be reconciled by interpreting the motion in the j8-regime as a combined methyl rotation and some translation. Rotational motions aroimd an axis of internal symmetry, do not contribute to the decay of the pair correlation fimction. Therefore, the interpretation of quasi-elastic coherent scattering appears to lead to shorter length scales than those revealed from a measurement of the self-correlation function [195]. A combined motion as proposed above would be consistent with all the experimental observations so far and also with the MD simulation results [198]. 

Consider now a one-dimensional lattice of parameter /. The distance of each atomic jump depends on the rate of de-excitation once the adatom is excited and is translating along the lattice. This de-excitation process can be described by a characteristic life time r in the symmetric random walk, as in many other solid state excitation phenomena. The initial position of the adatom is taken to be the origin, denoted by an index 0. The adatom accomplishes a jump of distance il if it is de-excited within (i — i)l and (i + i)l, where / is the lattice parameter, or the nearest neighbor distance of the one-dimensional lattice, and i is an integer. The probability of reaching a distance il in one jump is given by... 

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