Communication: Kirkwood-Buff integrals in the thermodynamic limit from small-sized molecular dynamics simulations.

We present an accurate and efficient method to obtain Kirkwood-Buff (KB) integrals in the thermodynamic limit from small-sized molecular dynamics simulations. By introducing finite size effects into integral equations of statistical mechanics, we derive an analytical expression connecting the KB integrals of the bulk system with the fluctuations of the number of molecules in the corresponding closed system. We validate the method by calculating the activity coefficients of aqueous urea mixtures and the KB integrals of Lennard-Jones fluids. Moreover, our results demonstrate how to identify simulation conditions under which computer simulations reach the thermodynamic limit.

The glass transition and the distribution of voids in room-temperature ionic liquids: a molecular dynamics study.

The glass transition in prototypical room temperature ionic liquids has been investigated by molecular dynamics simulations based on an Amber-like empirical force field. Samples of [C(4)mim][PF(6)], [C(4)mim][Tf(2)N], and [C(3)mim][Tf(2)N] have been quenched from the liquid phase at T = 500 to a glassy state at T ∼ 0 K in discontinuous steps of 20 K every 1.2 ns. The glass temperature estimated by simulation (T(g) = 209 K for [C(4)mim][PF(6)], T(g) = 204 K for [C(4)mim][Tf(2)N], and T(g) = 196 K for [C(3)mim][Tf(2)N]) agrees semi-quantitatively with the experimental values (T(g) = 193÷196 K for [C(4)mim][PF(6)], T(g) = 186÷189 K for [C(4)mim][Tf(2)N], and T(g) = 183 K for [C(3)mim][Tf(2)N]). A model electron density is introduced to identify voids in the system. The temperature dependence of the size distribution of voids provided by simulation reproduce well the experimental results of positron annihilation lifetime spectroscopy reported in G. Dlubek, Y. Yu, R. Krause-Rehberg, W. Beichel, S. Bulut, N. Pogodina, I. Krossing, and Ch. Friedrich, J. Chem. Phys. 133, 124502 (2010), with only one free parameter needed to fit the experimental data.

Density-functional-theory approach to the Hamiltonian adaptive resolution simulation method.

In the Hamiltonian adaptive resolution simulation method (H-AdResS) it is possible to simulate coexisting atomistic (AT) and ideal gas representations of a physical system that belong to different subdomains within the simulation box. The Hamiltonian includes a field that bridges both models by smoothly switching on (off) the intermolecular potential as particles enter (leave) the AT region. In practice, external one-body forces are calculated and applied to enforce a reference density throughout the simulation box, and the resulting external potential adds up to the Hamiltonian. This procedure suggests an apparent dependence of the final Hamiltonian on the system's thermodynamic state that challenges the method's statistical mechanics consistency. In this paper, we explicitly include an external potential that depends on the switching function. Hence, we build a grand canonical potential for this inhomogeneous system to find the equivalence between H-AdResS and density functional theory (DFT). We thus verify that the external potential inducing a constant density profile is equal to the system's excess chemical potential. Given DFT's one-to-one correspondence between external potential and equilibrium density, we find that a Hamiltonian description of the system is compatible with the numerical implementation based on enforcing the reference density across the simulation box. In the second part of the manuscript, we focus on assessing our approach's convergence and computing efficiency concerning various model parameters, including sample size and solute concentrations. To this aim, we compute the excess chemical potential of water, aqueous urea solutions and Lennard-Jones (LJ) mixtures. The results' convergence and accuracy are convincing in all cases, thus emphasising the method's robustness and capabilities.

Surface of Half-Neutralized Diamine Triflate Ionic Liquids. A Molecular Dynamics Study of Structure, Thermodynamics, and Kinetics of Water Absorption and Evaporation.

Surface properties of room temperature ionic liquids (RTILs) consisting of half neutralized diamine cations (H2N-(CH2)n-NH3+, n = 2, 4) and triflate anions have been investigated by molecular dynamics simulations, based on an empirical atomistic force field. Planar slabs periodically repeated in 2D have been considered, and the temperature range 260 ≤ T ≤ 360 K has been covered, extending from below the melting and glass point to the equilibrium liquid range of the diamine compounds under investigation. Addition of water at 1% weight concentration allowed us to investigate the kinetics of water absorption through the RTIL surface, and to characterize the structural and dynamical properties of subsurface water. Animations of the simulation trajectory highlight the quick absorption of water molecules, progressing downhill in free energy and taking place without apparent intermediate kinetic stages. To verify and quantify these observations, a variant of the umbrella sampling algorithm has been applied to compute the variation of excess free energy upon displacing a water molecule along the normal to the surface, from the center of the slab to the vapor phase. The results provide a comprehensive picture of the thermodynamic properties underlying the kinetics of water absorption and evaporation through the surface, and they also provide the ratio of the equilibrium density of water in the vapor and liquid phase at the average concentration considered by simulations. A variety of properties such as the surface energy, the 90-10% width of the profile, the layering of different species at the interface, and the electrostatic double layer at the surface are computed and discussed, focusing on the effect of water contamination on all of them.

Molecular dynamics simulations of the formation of 1D spin-valves from stretched Au-Co and Pt-Co nanowires.

We have performed molecular dynamics (MD) simulations of stretched Aux-Co1 - x and Ptx-Co1 - x nanowires to investigate the formation of bimetallic monoatomic wires between two electrodes. We have considered nanowires with two concentrations x = 0.2 and 0.8, aspect ratio of 13, a cross section of 1 nm(2) and a wide range of temperatures (from 10 to 400 K). For the MD simulations we have used a semi-empirical interatomic potential based on the second moment approximation (SMA) of the density of states to the tight-binding Hamiltonian.For Au-Co alloys, Au atoms tends to migrate towards the narrowed region to form almost pure Au wires. In the PtCo case the formed chains usually consist of Pt enriched alternating structures. The most striking result is probably the Au(0.2)-Co(0.8) alloy where pure monoatomic Au chains form between two Co electrodes constituting a potential 1D spin valve. Despite the known ease with which the 5d metals (Pt, Ir, and Au) form monoatomic chains (MACS), our results show that in the presence of Co (x = 0.2), the percentage of chain formation is higher than in the Pt and Au rich cases (x = 0.8).

Spontaneous spin polarization and charge localization in metal nanowires: the role of a geometric constriction.

An idealized jellium model of conducting nanowires with a geometric constriction is investigated by density functional theory (DFT) in the local spin density (LSD) approximation. The results reveal a fascinating variety of spin and charge patterns arising in wires of sufficiently low (r(s) ≥ 15) average electron density, pinned at the indentation by an apparent attractive interaction with the constriction. The spin-resolved frequency-dependent conductivity shows a marked asymmetry in the two spin channels, reflecting the spontaneous spin polarization around the wire neck. The relevance of the computational results is discussed in relation to the so-called 0.7 anomaly found by experiments in the low-frequency conductivity of nanowires at near-breaking conditions (see 2008 J. Phys.: Condens Matter 20, special issue on the 0.7 anomaly). Although our mean-field approach cannot account for the intrinsic many-body effects underlying the 0.7 anomaly, it still provides a diagnostic tool to predict impending transitions in the electronic structure.