Free energy loss calculation

To conclude, the calculation using a worm-hke chain model gives further evidence for the formation of small loops, but suggests that these loops are not necessarily limited by the chemical structure. This is easy to understand, since the free energy loss for pulling one segment out of the crystaUine phase is only of the order of kT (or less) at experimental temperatures. 

At the antipodes of the latter description, there is a continuous need for better low-resolution models that involve, for instance, coarse graining of molecules, or implicit solvation. This need is motivated by the expectation that the free energy of a large system can be calculated with sufficient accuracy without requiring that all its components be described at the atomic level. In many cases, this is equivalent to the assumption that a mean-field approximation works, or that many fast degrees of freedom can be removed from the system, yet without any appreciable loss of... 

Since it has been shown that nonideal mixing occurs in the 2.5-15.0 dyn cm 1 range, the excess free energies of interaction were calculated for compressions of each pure component and their mixtures to each of these surface pressures. In addition, these surface pressures are below the ESPs and/or monolayer stability limits so that dynamic processes arising from reorganization, relaxation, or film loss do not contribute significantly to the work of compression. 

Under these conditions, the formation rate constant, k, can be estimated from the product of the outer sphere stability constant, Kos, and the water loss rate constant, h2o, (equation (28) Table 2). The outer sphere stability constant can be estimated from the free energy of electrostatic interaction between M(H20)q+ and L and the ionic strength of the medium [5,164,172,173]. Consequently, Kos does not depend on the chemical nature of the ligand. A similar mechanism will also apply to a coordination complex with polydentate ligands, if the rate-limiting step is the formation of the first metal-ligand bond [5]. Values for the dissociation rate constants, k, are usually estimated from the thermodynamic equilibrium constant, using calculated values of kf ... 

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