The dielectric continuum solvent model adapted for treating preferential solvation effects

Basilevsky, M. V.; Odinokov, A. V.; Nikitina, E. A.; Petrov, N. Kh.

doi:10.1016/j.jelechem.2010.09.022

Cited by 11 publications

(14 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In micro-heterogeneous environment, DMSO molecules get preferentially favoured in the solvation shell, forming micro-clusters surrounding the RIPs [25][26][27][28][29][30]. The results have been published in ref 8, the authors used the dielectric continuum model suggested by Basilevsky et al [31] to simulate the local concentration of DMSO, y(r), surrounding RIP in TO/DMSO mixtures (r is inter-radical separation). The polar micro-domains are surrounding radical ions and the space in between two radical ions.…”

Section: Resultsmentioning

confidence: 99%

Magnetic field effect on exciplex-forming organic acceptor/donor system: a powerful tool for understanding the preferential solvation

Hoang

Pham

2016

Sci. Tech. Dev. J.

View full text Add to dashboard Cite

Many acceptor/donor systems can form excited-state charge-transfer complexes (exciplexes) in photo-induced electron transfer reactions. Exciplex can be detected by their luminescence. In addition, the exciplex luminescence is magneto-sensitive. Here, we employ an approach based on the magnetic field effect on the exciplex of 9,10- dimethylanthracene/N,N-dimethylaniline pair in micro-homogeneous and micro-heterogeneous binary solvents to investigate the effects of the preferential solvation processes on solute molecules in solutions. Micro-homogeneous solvent mixtures of propyl acetate (PA)/butyronitrile (BN) allow for a systematic variation of the static dielectric constants, s , in the range from 6.0 to 24.6. The mixtures of toluene (TO)/dimethylsulfoxide (DMSO) with varying the s values in the range from 4.3 to 15.5 are used as micro-heterogeneous binary solvents. In micro-heterogeneous environment, DMSO molecules get preferentially favoured in the solvation shell, forming micro-clusters surrounding the solute molecules. This solvation effect is reflected in the altered magnetic field effects, lifetimes and dissociation rate constants of the exciplexes.

show abstract

Section: Resultsmentioning

confidence: 99%

Magnetic field effect on exciplex-forming organic acceptor/donor system: a powerful tool for understanding the preferential solvation

Hoang

Pham

2016

Sci. Tech. Dev. J.

View full text Add to dashboard Cite

show abstract

“…We have also not yet tested the model on mixtures of polar and non-polar solvents. There exist several implicit-solvent models for such mixtures, 54,55,102 and whether SLIC works for these solutions is not known. Other current work extends our analysis here to a SLIC variant that can model dissolved ions in the solvent mixture using the linearized Poisson-Boltzmann equation.…”

Section: Discussionmentioning

confidence: 99%

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

Tabrizi

Goossens

Rahimi

et al. 2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics (Gibbs free energies, entropies, and heat capacities) in numerous polar solvents. We are also able to predict ion solvation free energies in water-co-solvent mixtures over available concentration series. The first modification to the classical dielectric Poisson model is a perturbation of the macroscopic dielectric-flux interface condition at the solute-solvent interface: we add a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is including the microscopic interface potential (static potential) in our model. We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water-co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. These and previous tests of the SLIC model indicate that it is a promising dielectric continuum model for accurate predictions in a wide range of conditions. Published by AIP Publishing. [http://dx.

show abstract

“…The radical pair was assumed to diffuse in a potential of mean force approximately accounting for the microheterogeneous environment. This potential was calculated following an approach based on the D – E 0 theorem as outlined in refs (18) and (20). Note that more elaborate schemes of treating the diffusion-influenced reversible exciplex kinetics have been derived on the basis of the integral encounter theory.…”

Section: Methodsmentioning

confidence: 99%

“…Illustration of the structure of the microheterogeneous solvent surrounding a radical ion pair (contact distance: 6.8 Å) as predicted by the continuum solvation model described in ref (18). (a) Local mole fraction of DMSO in DMSO/toluene mixtures of bulk concentration x DMSO = 0.2 (left; ε s = 7.3) and 0.4 (right; ε s = 13).…”

Section: Methodsmentioning

confidence: 99%

“…The approach has been applied to homogeneous solvents as well as under conditions of preferential solvation, which often occur in binary solvent mixtures of solvents of vastly different polarity. 13−18 The term “preferential solvation” subsumes nonspecific and specific interactions of solutes with specific components of binary solvent mixtures. It often induces microheterogeneity in the solvent, which is characterized by the spatially nonuniform distribution of the solvent components in the vicinity of polar or ionic solutes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Effects of Preferential Solvation Revealed by Time-Resolved Magnetic Field Effects

et al. 2017

View full text Add to dashboard Cite

External magnetic fields can impact recombination yields of photoinduced electron transfer reactions by affecting the spin dynamics in transient, spin-correlated radical pair intermediates. For exciplex-forming donor–acceptor systems, this magnetic field effect (MFE) can be investigated sensitively by studying the delayed recombination fluorescence. Here, we investigate the effect of preferential solvation in microheterogeneous solvent mixtures on the radical pair dynamics of the system 9,10-dimethylanthracene (fluorophore)/N,N-dimethylaniline (quencher) by means of time-resolved magnetic field effect (TR-MFE) measurements, wherein the exciplex emission is recorded in the absence and the presence of an external magnetic field using time-correlated single photon counting (TCSPC). In microheterogeneous environments, the MFE of the exciplex emission occurs on a faster time scale than in iso-dielectric homogeneous solvents. In addition, the local polarity reported by the exciplex is enhanced compared to homogeneous solvent mixtures of the same macroscopic permittivity. Detailed analyses of the TR-MFE reveal that the quenching reaction directly yielding the radical ion pair is favored in microheterogeneous environments. This is in stark contrast to homogeneous media, for which the MFE predominantly involves direct formation of the exciplex, its subsequent dissociation to the magneto-sensitive radical pair, and re-encounters. These observations provide evidence for polar microdomains and enhanced caging, which are shown to have a significant impact on the reaction dynamics in microheterogeneous binary solvents.

show abstract

The dielectric continuum solvent model adapted for treating preferential solvation effects

Cited by 11 publications

References 56 publications

Magnetic field effect on exciplex-forming organic acceptor/donor system: a powerful tool for understanding the preferential solvation

Magnetic field effect on exciplex-forming organic acceptor/donor system: a powerful tool for understanding the preferential solvation

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

Effects of Preferential Solvation Revealed by Time-Resolved Magnetic Field Effects

Contact Info

Product

Resources

About