Andrey I. Frolov

Electrode screening by ionic liquids

In this work we are concerned with the short-range screening provided by the ionic liquid dimethylimidazolium chloride near a charged wall. We study the free energy profiles (or potentials of mean force) for charged and neutral solutes as a function of distance from a charged wall. Four different wall charge densities are used in addition to a wall with zero charge. The highest magnitude of the charge densities is ±1 e nm(-2) which is close to the maximum limit of charge densities accessible in experiments, while the intermediate charges ±0.5 e nm(-2) are in the range of densities typically used in most of the experimental studies. Positively and negatively charged solutes of approximately the size of a BF ion and a Cl(-) ion are used as probes. We find that the ionic liquid provides excellent electrostatic screening at a distance of 1-2 nm. The free energy profiles show minima which are due to layering in the ionic liquid near the electrodes. This indicates that the solute ions tend to displace ionic liquid ions in the layers when approaching the electrode. The important role of non-electrostatic forces is demonstrated by the oscillations in the free energy profiles of uncharged solutes as a function of distance from the wall.

Hydration Thermodynamics Using the Reference Interaction Site Model: Speed or Accuracy?

We report a method to dramatically improve the accuracy of hydration free energies (HFE) calculated by the 1D and 3D reference interaction site models (RISM) of molecular integral equation theory. It is shown that the errors in HFEs calculated by RISM approaches using the Gaussian fluctuations (GF) free energy functional are not random, but can be decomposed into linear combination of contributions from different structural elements of molecules (number of double bonds, number of OH groups, etc.). Therefore, by combining RISM/GF with cheminformatics, one can develop an accurate method for HFE prediction. We call this approach the structural description correction model (SDC) ( Ratkova et al. J. Phys. Chem. B 2010 , 114 , 12068 ). In this work, we investigated the prediction quality of the SDC model combined with 1D and 3D RISM approaches. In parallel, we analyzed the computational performance of these two methods. The SDC model parameters were obtained by fitting against a training set of 53 simple organic molecules. To demonstrate that the values of these parameters were transferable between different classes of molecules, the models were tested against 98 more complex molecules (including 38 polyfragment compounds). The results show that the 3D RISM/SDC model predicts the HFEs with very good accuracy (RMSE of 0.47 kcal/mol), while the 1D RISM approach provides only moderate accuracy (RMSE of 1.96 kcal/mol). However, a single 1D RISM/SDC calculation takes only a few seconds on a PC, whereas a single 3D RISM/SDC HFE calculation is approximately 100 times more computationally expensive. Therefore, we suggest that one should use the 1D RISM/SDC model for large-scale high-throughput screening of molecular hydration properties, while further refinement of these properties for selected compounds should be carried out with the more computationally expensive but more accurate 3D RISM/SDC model.

Ion interactions with the carbon nanotube surface in aqueous solutions: understanding the molecular mechanisms

We study the molecular mechanisms of alkali halide ion interactions with the single-wall carbon nanotube surface in water by means of fully atomistic molecular dynamics simulations. We focus on the basic physical-chemical principles of ion-nanotube interactions in aqueous solutions and discuss them in light of recent experimental findings on selective ion effects on carbon nanotubes.

Toward a Universal Model To Calculate the Solvation Thermodynamics of Druglike Molecules: The Importance of New Experimental Databases

We demonstrate that a new free energy functional in the integral equation theory of molecular liquids gives accurate calculations of hydration thermodynamics for druglike molecules. The functional provides an improved description of excluded volume effects by incorporating two free coefficients. When the values of these coefficients are obtained from experimental data for simple organic molecules, the hydration free energies of an external test set of druglike molecules can be calculated with an accuracy of about 1 kcal/mol. The 3D RISM/UC method proposed here is easily implemented using existing computational software and allows in silico screening of the solvation thermodynamics of potential pharmaceutical molecules at significantly lower computational expense than explicit solvent simulations.

Prediction of cosolvent effect on solvation free energies and solubilities of organic compounds in supercritical carbon dioxide based on fully atomistic molecular simulations.

The solubility of organic compounds in supercritical fluids can be dramatically affected by addition of a suitable cosolvent (entrainer) at small concentrations. This makes the screening of the best-suited cosolvent an important task for the supercritical technology. The present study aims to improve our fundamental understanding of solvation in supercritical CO2 with cosolvents. We address the following questions: (1) How does the solvation free energy depend on the chemical class of an organic solute and the chemical nature of co-solvents? (2) Which intermolecular interactions determine the effect of a cosolvent on the solubility of organic compounds? We performed extensive calculations of solvation free energies of monofunctional organic molecules at infinite dilution in supercritical media by the Bennetts acceptance ratio method based on fully atomistic molecular dynamics sampling. Sixteen monofunctional organic molecules were solvated in pure sc-CO2 and sc-CO2 with addition of 6 molar % of cosolvents of different chemical nature: ethanol, acetone, and n-hexane. Cosolvent-induced solubility enhancement (CISE) factors were also calculated. It was found that formation of significant number of hydrogen bonds between a solute and cosolvent molecules leads to a profound solubility enhancement. The cosolvent effect is proportional to the number of hydrogen bonds. When polar cosolvents do not form hydrogen bonds with solutes, the CISE correlates with the dipole moment of solute molecules. However, the electrostatic interactions have a small impact on the solubility enhancement compared to hydrogen bonding. Addition of a nonpolar cosolvent, n-hexane, has a very little effect on the solvation Gibbs free energy of studied small organic molecules. The observed trends were discussed in line with available experimental data.

Salting out in organic solvents: a new route to carbon nanotube bundle engineering

In this study we investigate salt effects on bundle formation of carbon nanotubes (CNTs) dispersed in an organic solvent, N-methyl-2-pyrrolidone (NMP). Addition of NaI salt leads to self-assembly of CNTs into well-recognizable bundles. It is possible to control the size of the CNT bundles by varying the salt concentration.

Assessment of the Spatial Distribution in Sub- and Supercritical CO2 Using the Nearest Neighbor Approach: A Molecular Dynamics Analysis

The nearest neighbor approach was used to characterize the local structure of CO(2) fluid along its coexistence curve (CC) and along the critical isochore (CI). The distributions of the distances, orientations, and interaction energies between a reference CO(2) molecule and its subsequent nearest neighbors were calculated. Our results show that the local structure may be resolved into two components or subshells: one is characterized by small radial fluctuations, the parallel orientation and a dominance of the attractive part of both the electrostatic (EL) and Lennard-Jones (LJ) to the total interaction energy. Conversely, the second subshell is characterized by large radial fluctuations, a perpendicular orientation, and a concomitant increase of the repulsive contribution of the EL interaction and a shift to less attractive character of the LJ contribution. When the temperature increases along the liquid-gas CC, the first subshell undergoes large changes which are characterized by an obvious increase of the radial fluctuations, by an increase of the random character of the orientation distribution except for the first nearest neighbor which maintains its parallel orientation, and by a drastic decrease of the EL interaction contribution to the total interaction energy. When the temperature is close to the critical isochore, the local structure is no longer resolved into two subshells. Starting from the idea that the profile of vibration modes is sensitive to the local structure as revealed from the nearest neighbor approach, the hypothesis that the CO(2) vibration profile may be deconvoluted into two contributions is discussed in a qualitative manner.

Na+/K+ selectivity in the formation of ion pairs in aqueous solutions

The integral equations of liquids (RISM) and molecular dynamics method were used to calculate the mean force potential for the SO3 and COO hydrophilic groups and the CH3 hydrophobic group in the acetate, methyl sulfonate, and hydrosulfate anions, which form ion pairs with sodium and potassium cations in water. The carboxyl group selectively binds sodium ions from solutions containing Na+ and K+ ions, in spite of their equal charges, because the potassium ion experiences stronger steric hindrances near this group compared with sodium. The biophysical consequences of the revealed selectivity are discussed.

A universal bridge functional for infinitely diluted solutions: A case study for Lennard-Jones spheres of different diameters

We propose a universal bridge functional for closure of the Ornstein-Zernike (OZ) equation for infinitely diluted solutions of Lennard-Jones spheres of different sizes in a Lennard-Jones fluid. The bridge functional is parameterized using data from molecular dynamics (MD) simulations. We show that for all of the investigated systems, the bridge functional can be efficiently parameterized with an exponential function that depends only on the ratio of the sizes of solute and solvent atoms. To check the parameterization, we solve the OZ equation with a closure that includes the parametrized functional, and with a closure without the bridge functional (a hypernetted chain closure). We show that introducing the bridge functional allows us to obtain radial distribution functions (RDFs) close to the MD results, and to improve substantially predictions of the location and height of the first peak of an RDF.