Random walk of small atomic clusters

In a molecular dynamic simulation147 of bulk atomic diffusion by a vacancy mechanism, two atoms may occasionally jump together as a pair. The temperature of the simulation is close to the melting point of the crystal. In FTM studies of single atom and atomic cluster diffusion, the temperature is only about one tenth the melting point of the substrate. All cluster diffusion, except that in the (1 x 1) to (1 x 2) surface reconstruction of Pt and Ir (110) surfaces already discussed in Section 4.1.2(b), are consistent with mechanisms based on jumps of individual atoms.148,149 In fact, jumps of individual atoms in the coupled motion of adatoms in the adjacent channel of the W (112) surface can be directly seen in the FTM if the temperature of the tip is raised to near 270 K.150 

Atomic jumps in random walk diffusion of closely bound atomic clusters on the W (110) surface cannot be seen. A diatomic cluster always lines up in either one of the two (111) surface channel directions. But even in such cases, theoretical models of the atomic jumps can be proposed and can be compared with experimental results. For diffusion of diatomic clusters on the W (110) surface, a two-jump mechanism has been proposed by Bassett151 and by Cowan.152 Experimental studies are reported by Bassett and by Tsong Casanova.153 Bassett measured the probability of cluster orientation changes as a function of the mean square displacement, and compared the data with those derived with a Monte Carlo simulation based on the two-jump mechanism. The two results agree well only for very small displacements. Tsong Casanova, on the other hand, measured two-dimensional displacement distributions. They also introduced a correlation factor for these two atomic jumps, which resulted in an excellent agreement between their experimental and simulated results. We now discuss briefly this latter study. 

There are two possible directions for both the atoms in both the first and second atomic jumps. If the jumping direction is completely random and the two atoms have the same probability of performing a jump, then these atomic jumps are said to be uncorrelated. A correlation factor, /, has been introduced for the two atomic jumps, which is defined as the extra probability that the atom making the first jump will also make the second jump in the forward direction. The rest of the probability, (1 — /), is then shared equally for either of the two atoms jumping in either of the two directions. Two experimental displacement distributions measured at 299 K and 309 K fit best with a Monte Carlo simulation with / = 0.1 and /=0.36, respectively. The correlation factor increases with diffusion temperature as can be expected. It is interesting to note that when/= 1, only a and steps can occur. 

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