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  1. The role that van der Waals (vdW) attractive forces play in the hydration and association of atomic hydrophobic solutes such as argon (Ar) in water is reanalyzed using the local molecular field (LMF) theory of those interactions. In this problem, solute vdW attractive forces can reduce or mask hydrophobic interactions as measured by contact peak heights of the ArAr correlation function compared to reference results for purely repulsive core solutes. Nevertheless, both systems exhibit a characteristic hydrophobic inverse temperature behavior in which hydrophobic association becomes stronger with increasing temperature through a moderate temperature range. The new theoretical approximation obtained heremore » is remarkably simple and faithful to the statistical mechanical LMF assessment of the necessary force balance. In conclusion, our results extend and significantly revise approximations made in a recent application of the LMF approach to this problem and, unexpectedly, support a theory of nearly 40 years ago.« less
  2. In this paper, electrochemical double-layer capacitances of charged carbon nanotube (CNT) forests with tetraethyl ammonium tetrafluoro borate electrolyte in propylene carbonate are studied on the basis of molecular dynamics simulation. Direct molecular simulation of the filling of pore spaces of the forest is feasible even with realistic, small CNT spacings. The numerical solution of the Poisson equation based on the extracted average charge densities then yields a regular experimental dependence on the width of the pore spaces, in contrast to the anomalous pattern observed in experiments on other carbon materials and also in simulations on planar slot-like pores. The capacitancesmore » obtained have realistic magnitudes but are insensitive to electric potential differences between the electrodes in this model. This agrees with previous calculations on CNT forest supercapacitors, but not with experiments which have suggested electrochemical doping for these systems. Finally, those phenomena remain for further theory/modeling work.« less
  3. Laying a basis for molecularly specific theory for the mobilities of ions in solutions of practical interest, we report a broad survey of velocity autocorrelation functions (VACFs) of Li + and PF 6 - ions in water, ethylene carbonate, propylene carbonate, and acetonitrile solutions. We extract the memory function, γ(t), which characterizes the random forces governing the mobilities of ions. Here, we provide comparisons controlling for the effects of electrolyte concentration and ion-pairing, van der Waals attractive interactions, and solvent molecular characteristics. For the heavier ion (PF 6 -), velocity relaxations are all similar: negative tail relaxations for the VACFmore » and a clear second relaxation for γ(t), observed previously also for other molecular ions and with n-pentanol as the solvent. For the light Li + ion, short time-scale oscillatory behavior masks simple, longer time-scale relaxation of γ(t). But the corresponding analysis of the solventberg Li + (H 2O) 4 does conform to the standard picture set by all the PF 6 - results.« less
  4. Extensive all-atom molecular dynamics calculations on the water–squalane interface for nine different loadings with sorbitan monooleate (SPAN80), at T = 300 K, are analyzed for the surface tension equation of state, desorption free-energy profiles as they depend on loading, and to evaluate escape times for adsorbed SPAN80 into the bulk phases. These results suggest that loading only weakly affects accommodation of a SPAN80 molecule by this squalane–water interface. Specifically, the surface tension equation of state is simple through the range of high tension to high loading studied, and the desorption free-energy profiles are weakly dependent on loading here. The perpendicularmore » motion of the centroid of the SPAN80 headgroup ring is well-described by a diffusional model near the minimum of the desorption free-energy profile. Lateral diffusional motion is weakly dependent on loading. Escape times evaluated on the basis of a diffusional model and the desorption free energies are 7 × 10 -2 s (into the squalane) and 3 × 10 2 h (into the water). Finally, the latter value is consistent with desorption times of related lab-scale experimental work.« less
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  5. We use ab initio molecular dynamics (AIMD) calculations and quasi-chemical theory (QCT) to study the inner-shell structure of F-(aq) and to evaluate that single-ion free energy under standard conditions. Following the “no split occupancies” rule, QCT calculations yield a free energy value of -101 kcal/mol under these conditions, in encouraging agreement with tabulated values (-111 kcal/mol). The AIMD calculations served only to guide the definition of an effective inner-shell constraint. QCT naturally includes quantum mechanical effects that can be concerning in more primitive calculations, including electronic polarizability and induction, electron density transfer, electron correlation, molecular/atomic cooperative interactions generally, molecular flexibility,more » and zero-point motion. No direct assessment of the contribution of dispersion contributions to the internal energies has been attempted here, however. We anticipate that other aqueous halide ions might be treated successfully with QCT, provided that the structure of the underlying statistical mechanical theory is absorbed, i.e., that the “no split occupancies” rule is recognized.« less

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