Rigorously speaking, entropy is slightly non-extensive, and this non-extensiveness, which characterizes the degree of fluctuations, can contribute to effective interactions between mesoscopic objects. In this paper, we consider a pair of macroions, each accompanied by 1000 counterions, and with a cell-model description we demonstrate that the slow variation of non-extensiveness in counterion entropy over macroionic distance leads to an effective long-range attraction between the macroions. With the aid of Monte Carlo simulation and a Bragg-Williams theory including counterion number fluctuations, we find the depth of attraction in free energy to be approximately 0.2k(B)T. The observation in our cell-model study provides an insight for further understanding of effective interactions in real macroionic systems.
What if we played the Rubik's cube game by simple intuition? We would rotate the cube, probably in the hope of getting a more organized pattern in each next step. Yet frustration occurs easily, and we soon find ourselves trapped as the game progresses no further. Played in this completely strategy-less style, the entire problem of the Rubik's cube game can be compared to that of complex chemical reactions such as protein folding, only with less guidance in the searching process. In this work we look into this random-searching process by means of thermodynamics and compare the game's dynamics with that of a faithful stochastic model constructed from the statistical energy landscape theory (SELT). This comparison reveals the peculiar nature of SELT, which relies on the random energy approximation and often chops up energy correlations among nearby configurations. Our observation provides a general insight for the use of SELT in the studies of these frustrated systems.
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