Hybrid Solvation Model with First Solvation Shell for Calculation of Solvation Free Energy

We present a hybrid solvation model with first solvation shell to calculate solvation free energies. This hybrid model combines the quantum mechanics and molecular mechanics methods with the analytical expression based on the Born solvation model to calculate solvation free energies. Based on calculated free energies of solvation and reaction profiles in gas phase, we set up a unified scheme to predict reaction profiles in solution. The predicted solvation free energies and reaction barriers are compared with experimental results for twenty bimolecular nucleophilic substitution reactions. These comparisons show that our hybrid solvation model can predict reliable solvation free energies and reaction barriers for chemical reactions of small molecules in aqueous solution.     

Solvation in supercritical water

Solvation in supercritical water under equilibrium and nonequilibrium conditions is studied via molecular dynamics simulations. The influence of solute charge distributions and solvent density on the solvation structures and dynamics is examined with a diatomic probe solute molecule. It is found that the solvation structure varies dramatically with the solute dipole moment, especially in low-density water, in accord with many previous studies on ion solvation. This electrostrictive effect has important consequences for solvation dynamics. In the case of a nonequilibrium solvent relaxation, if there are sufficiently many water molecules close to the solute at the outset of the relaxation, the solvent response measured as a dynamic Stokes shift is almost completely governed by inertial rotations of these water molecules. By contrast, in the opposite case of a low local solvent density near the solute, not only rotations but also translations of water molecules play an important role in solvent relaxation dynamics. The applicability of a linear response is found to be significantly restricted at low water densities.     

Preferential Solvation in Mixed Solvents

The Kirkwood–Buff integrals and the volume-corrected preferential solvation parameters for the first solvation shell of binary mixtures of tetrahydrofuran with many organic solvents, calculated from reported thermodynamic data at the temperatures for which these data were available, are reported. The co-solvents include c-hexane, methyl-c-hexane, n-heptane, i-octane, benzene, toluene, ethylbenzene, 1-chlorobutane, dichloromethane, 1,2-dichloroethane, chloroform, 1,1,1-trichloroethane, tetrachlorom-ethane, tetrachloroethene, hexafluoro benzene, ethanol, 1-propanol, 2-propanol, dibutyl ether, acetic acid, acetone, dimethyl sulfoxide, tetramethylene sulfone (sulfolane), acetonitrile, pyrrolidine, and triethylamine. The preferential solvation parameters of these mixtures are discussed in terms of the interactions that occur.     

Solvation forces in asymmetrically charged electrolytes

Density functional theories of solvation forces in charged fluids which self-consistently include the effects of finitesized ions are extended to treat asymmetrically charged electrolytes. For a given electrolyte concentration both the electric potential and the solvation force between charged surfaces are seen to deviate from the results of the classical DLVO theory more markedly for asymmetrically charged electrolytes than for a 1 : 1 electrolyte.     

Solvation effects in near-critical binary mixtures

A Ginzburg-Landau theory is presented to investigate solvation effects in near-critical polar fluid binary mixtures. Concentration dependence of the dielectric constant gives rise to a shell region around a charged particle within which solvation occurs preferentially. As the critical point is approached, the concentration has a long-range Ornstein-Zernike tail representing strong critical electrostriction. If salt is added, strong coupling arises among the critical fluctuations and the ions. The structure factors of the critical fluctuations and the charge density are calculated and the phase transition behavior is discussed.     

Diffusion with molecular association in chloroform + triethylamine and chloroform + dioxane mixtures

The Taylor dispersion method is used to measure the binary mutual diffusion coefficients of chloroform + triethylamine and chloroform +1,4-dioxane at 25°C. The components of these mixtures associate, forming chloroform-triethylamine and chloroform-dioxane, (chloroform)₂-dioxane molecular complexes. A modified Hartley-Crank equation is developed to express the binary diffusion coefficient as a weighted average of the diffusion coefficients of the free molecules and the molecular complexes. Counterintuitively, the contribution made by each molecular complex to the overall diffusion coefficient vanishes when the concentration of the complex reaches its maximum value. The measured and fitted diffusion coefficients agree within 3% or better over the complete composition range.     

Solvation in homogeneous and heterogeneous media

A short account on solvation of solute in Homogeneous and Heterogeneous Media has been presented. Basic concepts of specific and nonspecific interactions with some specific examples are discussed based on Koppel and Palm (KP) and Abaham, Kamlet and Taft (AKT) approaches. List of AKT parameters describing specific and non-specific solvation parameters for homogeneous media (pure solvents) and heterogeneous media (micelles) has been presented in tables.     

Die Graduiertenschule Solvation Science

The GSS offers its members an excellent infrastructure for their PhD research and a unique, international and interdisciplinary training program in the area of Solvation Science. With 30% international members and a training program in English internationality and intercultural diversity is part of everyday life in the GSS. The about 100 GSS members, working in the fields of chemistry, physics, biology and engineering, discuss their work during regular events and workshops and thereby learn to think interdisciplinary from the beginning of their PhD thesis.     

Solvation of Piperidine in Nonaqueous Solvents

Russian Journal of Physical Chemistry A - The enthalpies of solvation of piperidine (Ppd) in methanol (MeOH), ethanol (EtOH), N,N‑dimethylformamide (DMF), and dimethylsulfoxide (DMSO) are...     

Solvation of p-coumaric acid in water

The photoactive yellow protein (PYP) is an important model protein for many (photoactive) signaling proteins. Key steps in the PYP photocycle are the isomerization and protonation of its chromophore, p-coumaric acid (pCA). In the ground state of the protein, this chromophore is in the trans configuration with its phenolic oxygen deprotonated. For this paper, we studied four different configurations of pCA solvated in water with ab initio molecular dynamics simulations as implemented in CP2K/Quickstep. We researched the influence of the protonation and isomerization state of pCA on its hydrogen-bonding properties and on the Mulliken charges of the atoms in the simulation. The chromophore isomerization state influenced the hydrogen-bonding less than its protonation state. In general, more charge yielded a higher hydrogen-bond coordination number. Where deprotonation increases both the coordination number and the residence time of the water molecules around the chromophore, protonation showed a somewhat lower coordination number on two of the three pCA oxygens but much higher residence times on all of them. This could be explained by the increased polarization of the OH groups of the molecule. The presence of the chromophore also influenced the charge and polarization of the water molecules around it. This effect was different in the four systems studied and mainly localized in the first solvation shell. We also performed a proton-transfer reaction from hydronium through various other water molecules to the chromophore. In this small charge-separated system, the protonation occurred within 6.5 ps. We identified the transition state for the final step in this protonation series.     

Solvation of tetraphenylphosphonium dicyanamide

NMR and IR spectroscopy have been used to study the solvation of the dicyanamide ion in solvents with different chemical natures. The occurrence of two kinds of interaction of the N(CN)₂ ^–ion with the solvents has been established: by means of hydrogen bonds (alcohols, chloroform) and by ion-dipole interaction (aprotic solvents).Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 3, pp. 361–366, May–June, 1988.     

Ionic Solvation in Aqueous and Nonaqueous Solutions

Summary.  The history of studies on ionic solvation is briefly reviewed, and structural and dynamic properties of solvated ions in aqueous and nonaqueous solutions are discussed. An emphasis is placed on ionic solvation in nonaqueous mixed solvents in which preferential solvation of ions takes place. A new parameter for expressing the degree of preferential solvation of an ion is proposed. Received January 16, 2001. Accepted January 31, 2001     

Solvation of Na+ in argon clusters

The structures and stabilities of Ar(n)Na+ clusters (n < or = 54) are investigated using atomistic potentials fitted to reproduce ab initio calculations performed at the coupled-cluster level on the smaller clusters. Polarization effects are described using either the interaction between dipoles induced by the sodium ion, or a small charge transfer in the framework of a fluctuating charges model. In both models, extra three-body contributions of the Axilrod-Teller type are also included between the sodium ion and all pairs of argon atoms. The two models predict essentially similar growth patterns, and a transition in the metal ion coordination from 8 (square antiprism) to 12 (icosahedron) is seen to occur near n = 50, in response to the intrasolvent constraints.     

Solvation of Metal Cations in Non-aqueous Liquids

The role that alkali cations in non-aqueous solvents play in organic reactions continues to be a topic of interest. In particular it has been observed that these cations can alter the stereoselectivity of organic reactions. Our interest is to first understand the nature of cation–ether complexes, then to investigate the role that the cation plays in the reaction. We have used the electronic structure techniques Hartree-Fock (HF), Second-order Møller-Plesset perturbation theory (MP2), and the Becke three-parameter exchange functional coupled with the nonlocal correlation functional of Lee, Yang, and Parr (B3LYP) to study the structure and properties of tetrahydrofuran (THF) and dimethyl ether (DME) solvation complexes with Li⁺, Na⁺, K⁺, Cu⁺, and MgCl⁺. The values calculated for DME complexes were compared with existing experimentally determined data. The B3LYP/6-31⁺G^? model chemistry was found to be the most accurate and efficient method of modeling the cation–DME molecular system. The energetic trends observed in the DME results were also observed in the THF data. Based on the accuracy of the calculations and the computational cost of the calculations, B3LYP was found to be the most desirable method of modeling these types of systems.     

Solvation Structure of Uracil in Ionic Liquids

The local solvation environment of uracil dissolved in the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate has been studied using neutron diffraction techniques. At solvent:solute (ionic liquid:uracil) ratios of 3:1 and 2:1, little perturbation of the ion–ion correlations compared to those of the neat ionic liquid are observed. We find that solvation of the uracil is driven predominantly by the acetate anion of the solvent. While short distance correlations exist between uracil and the imidazolium cation, the geometry of these contacts suggest that they cannot be considered as hydrogen bonds, in contrast to other studies by Araújo et al. (J. M. Araújo, A. B. Pereiro, J. N. Canongia‐Lopes, L. P. Rebelo, I. M. Marrucho, J. Phys. Chem. B 2013, 117, 4109–4120 ). Nevertheless, this combination of interactions of the solute with both the cation and anion components of the solvents helps explain the high solubility of the nucleobase in this media. In addition, favourable uracil–uracil contacts are observed, of similar magnitude to those between cation and uracil, and are also likely to aid dissolution.