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The phenomenon of underscreening in concentrated electrolyte solutions leads to a larger decay length of the charge–charge correlation than the prediction of Debye–Hückel (DH) theory and has found a resurgence of both theoretical and experimental interest in the chemical physics community. To systematically understand and investigate this phenomenon in electrolytes requires a theory of concentrated electrolytes to describe charge–charge correlations beyond the DH theory. We review the theories of electrolytes that can transition from the DH limit to concentrations where charge correlations dominate, giving rise to underscreening and the associated Kirkwood Transitions (KTs). In this perspective, we provide a conceptual approach to a theoretical formulation of electrolyte solutions that exploits the competition between molecular-informed short-range (SR) and long-range interactions. We demonstrate that all deviations from the DH limit for real electrolyte solutions can be expressed through a single function Σ Q that can be determined both theoretically and numerically. Importantly, Σ Q can be directly related to the details of SR interactions and, therefore, can be used as a tool to understand how differences in representations of interaction can influence collective effects. The precise function form of Σ Q can be inferred through a Gaussian field theory of both the number and charge densities. The resulting formulation is validated by experiment and can accurately describe the collective phenomenon of screening in concentrated bulk electrolytes. Importantly, the Gaussian field theory predictions of the screening lengths appear to be less than ∼1 nm at concentrations above KTs. [ABSTRACT FROM AUTHOR]

We establish the connection between the measured small angle x-ray scattering signal and the charge–charge correlations underlying Kirkwood transitions (KTs) in 1:1, 2:1, and 3:1 aqueous electrolytes. These measurements allow us to obtain underscreening lengths for bulk electrolytes independently verified by theory and simulations. Furthermore, we generalize the concept of KTs beyond those theoretically predicted for 1:1 electrolytes, which involves the inverse screening length, a0, and the inverse periodicity length, Q0. Above the KTs, we find a universal scaling of a 0 ∝ c − ζ / 3 and Q0 ∝ c1/3 for the studied electrolyte solutions, where ζ is the ionic strength factor. [ABSTRACT FROM AUTHOR]

Proper statistical mechanics understanding of nanoparticle solvation processes requires an accurate description of the molecular structure of the solvent. Achieving this goal with standard molecular dynamics (MD) simulation methods is challenging due to large length scales. An alternative approach to this problem can be formulated using classical density functional theory (cDFT), where a full configurational description of the positions of all the atoms is replaced by collective atomic site densities in the molecule. Using an example of the negatively charged silica-like system in an aqueous polar environment represented by a two-site water model, we demonstrate that cDFT can reproduce MD data at a fraction of the computational cost. An important implication of this result is the ability to understand how the solvent molecular features may affect the system's properties at the macroscopic scale. A concrete example highlighted in this work is the analysis of nanoparticle interactions with sizes of up to 100 nm in diameter. [ABSTRACT FROM AUTHOR]

The low thermal conductance of polymers is one of the major drawbacks for many polymer-based products. However, a single polymer chain when stretched can have high thermal conductivities. We use non-equilibrium molecular dynamics simulations to study the steady-state thermal conductance along finite macromolecules under mechanical control of the end-to-end distance. We find that the nature of heat transport along such chains strongly depends on mechanical tuning, leading to significantly different heat conductions and temperature profiles along the chain in the compressed-chain and stretched-chain limits. This transition between modes of behaviors appears to be a threshold phenomenon: at relatively small end-to-end distances, the thermal conductance remains almost constant as one stretches the polymer chain. At given critical end-to-end distances, thermal conductances start to increase, reaching the fully extended chain values. Correlated with this behavior are two observations: first, the temperature bias falls mostly at contacts in the fully stretched chain, while part of it falls along the molecule in the compressed limit. Second, the heat conduction does not change significantly with the chain length in the stretched-chain limit but decreases dramatically when this length increases in the compressed molecule. This suggests that heat transfer along stretched chains is mostly ballistic, while in the compressed chain, heat is transferred by diffusive mechanisms. Significantly, these trends persist also for a large range of molecular structures and force fields, and the changing behavior correlates well with mode localization properties. Similar studies conducted with disordered chains and bundles of several chains show remnants of the same behavior. [ABSTRACT FROM AUTHOR]

The separation of slownuclear and fast electronic polarization in problems related to electron mobility in polarizable media was considered by Pekar 70 years ago. Within dielectric continuum models, this separation leads to the Pekar factor in the free energy of solvation by the nuclear degrees of freedom. The main qualitative prediction of Pekar's perspective is a significant, by about a factor of two, drop of the nuclear solvation free energy compared to the total (electronic plus nuclear) free energy of solvation. The Pekar factor enters the solvent reorganization energy of electron transfer reactions and is a significant mechanistic parameter accounting for the solvent effect on electron transfer. Here, we study the separation of the fast and slow polarization modes in polar molecular liquids (polarizable dipolar liquids and polarizablewater force fields) without relying on the continuum approximation.We derive the nonlocal free energy functional and use atomistic numerical simulations to obtain nonlocal, reciprocal space electronic and nuclear susceptibilities. A consistent transition to the continuum limit is introduced by extrapolating the results of finite-size numerical simulation to zero wavevector. The continuum nuclear susceptibility extracted from the simulations is numerically close to the Pekar factor. However, we derive a new functionality involving the static and highfrequency dielectric constants. The main distinction of our approach from the traditional theories is found in the solvation free energy due to the nuclear polarization: the anticipated significant drop of its magnitude with increasing liquid polarizability does not occur. The reorganization energy of electron transfer is either nearly constant with increasing the solvent polarizability and the corresponding highfrequency dielectric constant (polarizable dipolar liquids) or actually noticeably increases (polarizable force fields of water). [ABSTRACT FROM AUTHOR]

Since the seminal paper by Panagiotopoulos [Mol. Phys. 61, 813 (1997)], the Gibbs ensemble Monte Carlo (GEMC) method has been the most popular particle-based simulation approach for the computation of vapor-liquid phase equilibria. However, the validity of GEMC simulations in the near-critical region has been questioned because rigorous finite-size scaling approaches cannot be applied to simulations with fluctuating volume. Valleau [Mol. Simul. 29, 627 (2003)] has argued that GEMC simulations would lead to a spurious overestimation of the critical temperature. More recently, Patel et al. [J. Chem. Phys. 134, 024101 (2011)] opined that the use of analytical tail corrections would be problematic in the near-critical region. To address these issues, we perform extensive GEMC simulations for Lennard-Jones particles in the near-critical region varying the system size, the overall system density, and the cutoff distance. For a system with N = 5500 particles, potential truncation at 8s and analytical tail corrections, an extrapolation of GEMC simulation data at temperatures in the range from 1.27 to 1.305 yields Tc = 1.3128 ± 0.0016, ρc = 0.316 ± 0.004, and pc = 0.1274 ± 0.0013 in excellent agreement with the thermodynamic limit determined by Potoff and Panagiotopoulos [J. Chem. Phys. 109, 10914 (1998)] using grand canonical Monte Carlo simulations and finite-size scaling. Critical properties estimated using GEMC simulations with different overall system densities (0.296 ℸ ρt ℸ 0.336) agree to within the statistical uncertainties. For simulations with tail corrections, data obtained using rcut = 3.5σ yield Tc and pc that are higher by 0.2% and 1.4% than simulations with rcut = 5 and 8σ but still with overlapping 95% confidence intervals. In contrast, GEMC simulations with a truncated and shifted potential show that rcut = 8σ is insufficient to obtain accurate results. Additional GEMC simulations for hard-core square-well particles with various ranges of the attractive well and for n-decane molecules represented by the TraPPE force field yield data that support the trends observed for Lennard-Jones particles. The finite-size dependence of the critical properties obtained from GEMC simulations is significantly smaller than those from grand-canonical ensemble simulations. Thus, when resources are not available for a rigorous finite-size scaling study,GEMCsimulations provide a straightforward route to determine fairly accurate critical properties using relatively small system sizes. [ABSTRACT FROM AUTHOR]

Coarse-graining (CG) procedures provide computationally efficient methods for investigating the corresponding long time- and length-scale processes. In the bottom-up approaches, the effective interactions between the CG sites are obtained using the information from the atomistic simulations, but reliable CG procedures are required to preserve the structure and thermodynamics. In this regard, the integral equation coarse-graining (IECG) method is a promising approach that uses the first-principles Ornstein-Zernike equation in liquid state theory to determine the effective potential between CG sites. In this work, we present the details of the IECG method while treating the density as an intrinsic property and active variable of the CG system. Performing extensive simulations of polymer melts, we show that the IECG theory/simulation and atomistic simulation results are consistent in structural properties such as the pair-correlation functions and form factors, and also thermodynamic properties such as pressure. The atomistic simulations of the liquids show that the structure is largely sensitive to the repulsive part of the potential. Similarly, the IECG simulations of polymeric liquids show that the structure can be determined by the relatively short-range CG repulsive interactions, but the pressure is only accurately determined once the long-range, weak CG attractive interactions are included. This is in agreement with the seminal work by Widom on the influence of the potential on the phase diagram of the liquid [Widom, B. Science 1967, 157, 375-382]. Other aspects of the IECG theory/simulations are also discussed. [ABSTRACT FROM AUTHOR]

Signatures of nonlinear and non-Gaussiandynamics in time-resolved linear and nonlinear (correlation) 2D spectraare analyzed in a model considering a linear plus quadratic dependenceof the spectroscopic transition frequency on a Gaussian nuclear coordinateof the thermal bath (quadratic coupling). This new model is contrastedto the commonly assumed linear dependence of the transition frequencyon the medium nuclear coordinates (linear coupling). The linear couplingmodel predicts equality between the Stokes shift and equilibrium correlationfunctions of the transition frequency and time-independent spectralwidth. Both predictions are often violated, and we are asking herethe question of whether a nonlinear solvent response and/or non-Gaussiandynamics are required to explain these observations. We find thatcorrelation functions of spectroscopic observables calculated in thequadratic coupling model depend on the chromophore’s electronicstate and the spectral width gains time dependence, all in violationof the predictions of the linear coupling models. Lineshape functionsof 2D spectra are derived assuming Ornstein–Uhlenbeck dynamicsof the bath nuclear modes. The model predicts asymmetry of 2D correlationplots and bending of the center line. The latter is often used toextract two-point correlation functions from 2D spectra. The dynamicsof the transition frequency are non-Gaussian. However, the effectof non-Gaussian dynamics is limited to the third-order (skewness)time correlation function, without affecting the time correlationfunctions of higher order. The theory is tested against moleculardynamics simulations of a model polar–polarizable chromophoredissolved in a force field water. [ABSTRACT FROM AUTHOR]

Stability constants of simple reactions involving addition of the NO 3 - ion to hydrated metal complexes, [M(H 2 O) x ] n + are calculated with a computational workflow developed using cloud computing resources. The computational workflow performs conformational searches for metal complexes at both low and high levels of theories in conjunction with a continuum solvation model (CSM). The low-level theory is mainly used for the initial conformational searches, which are complemented with high-level density functional theory conformational searches in the CSM framework to determine the coordination chemistry relevant for stability constant calculations. In this regard, the lowest energy conformations are found to obtain the reaction free energies for the addition of one NO 3 - to [M(H 2 O) x ] n + complexes, where M represents Fe(II), Fe(III), Sr(II), Ce(III), Ce(IV), and U(VI), respectively. Structural analysis of hundreds of optimized geometries at high-level theory reveals that NO 3 - coordinates with Fe(II) and Fe(III) in either a monodentate or bidentate manner. Interestingly, the lowest-energy conformations of Fe(II) metal-nitrate complexes exhibit monodentate or bidentate coordination with a coordination number of 6 while the bidentate seven-coordinated Fe(II) metal-nitrate complexes are approximately 2 kcal mol -1 higher in energy. Notably, for Fe(III) metal-nitrate complexes, the bidentate seven-coordinated configuration is more stable than the six-coordinated Fe(II) complexes (monodentate or bidentate) by a few thermal energy units. In contrast, Sr(II), Ce(III), Ce(IV), and U(VI) metal ions predominantly coordinate with NO 3 - in a bidentate manner, exhibiting typical coordination numbers of 7, 9, 9, and 5, respectively. Stability constants are accordingly calculated using linear free energy approaches to account for the systematic errors and good agreements are obtained between the calculated stability constants and the available experimental data.