Dielectric constant of mixed solvents based on perturbation theory

Neumaier, Lisa; Schilling, Johannes; Bardow, André; Groß, Joachim

doi:10.1016/j.fluid.2021.113346

Cited by 13 publications

(36 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The extended permittivity model has three parameters: the dipole scaling parameter a 11 , which corresponds to the parameter a 1 of our earlier work; 41 the polarizability scaling parameter a 12 ; and the correlation integral parameter a 2 . In addition to the permanent dipole moment μ, polarizability α is needed.…”

Section: Perturbation Theory For the Relative Static Permittivity: Mo...mentioning

confidence: 99%

“…We determine this threshold value of μ = 1 D by analyzing the dipole moments of all well-measured substances with five or more data points parametrized with schemes NP and P (cf., Supporting Information, section S2.1). If only one data point is available, we fix the correlation integral parameter a 2 to the value of water (a 2 = 0.12) for the scheme P to obtain a oneparameter model, as shown in Neumaier et al 41 3.1.2. Liquid-Density Correlation.…”

Section: Parametrization Schemesmentioning

confidence: 99%

“…In previous work, we developed a model for the permittivity of pure and mixed solvents based on perturbation theory. 41 For this purpose, we modified the perturbation theory approach by Tani et al 42 for real fluids and extended it to mixtures. Our model is third order in dipole density and exhibits lean parametrization with only two parameters adjusted to pure component experimental permittivity data.…”

Section: Introductionmentioning

confidence: 99%

“…In this work, we present a broadly applicable model for relative static permittivity ε r (T, ρ) with promising predictive capabilities. First, we extend our previous model 41 to nonpolar substances to expand its applicability (section 2). Then, we investigate the performance of our model over a wide range of permittivities ε r (T, ρ(T)) by parametrizing 785 substances in the liquid phase, neglecting pressure dependence (sections 3.1 and 4.1).…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Predicting the Relative Static Permittivity: a Group Contribution Method Based on Perturbation Theory

Rueben,

Schilling,

Rehner

et al. 2023

J. Chem. Eng. Data

Self Cite

View full text Add to dashboard Cite

The computer-aided design of (bio)chemical processes requires models that predict thermodynamic properties with as little experimental effort as possible. For the important class of electrolyte systems, the relative static permittivity of the solvent is an important thermodynamic property that depends on the temperature, pressure, composition, and molecular structure of the solvent. This work presents a broadly applicable model for the temperature-dependent relative static permittivity of pure and mixed solvents based on perturbation theory, including a group contribution method. For this purpose, we extend our previous model for polar substances to nonpolar substances. The developed model is parametrized for 785 substances, where permittivity and density data are available in the Dortmund Data Bank and the ThermoML database. Subsequently, a group contribution method is developed to predict the permittivity parameters from the molecular structure. With a mean absolute deviation of 0.2 averaged over all 785 substances, the parametrized model accurately correlates the relative static permittivity over a wide range of permittivities and temperatures. Moreover, the group contribution method achieves a mean absolute deviation of 0.6 for the substances in the training set. A leave-one-out cross-validation shows that the group contribution method accurately predicts substances not included in the training set.

show abstract

Section: Perturbation Theory For the Relative Static Permittivity: Mo...mentioning

confidence: 99%

Section: Parametrization Schemesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Predicting the Relative Static Permittivity: a Group Contribution Method Based on Perturbation Theory

Rueben,

Schilling,

Rehner

et al. 2023

J. Chem. Eng. Data

Self Cite

View full text Add to dashboard Cite

show abstract

“…For mixed solvents, the dielectric constant is defined by mixing the dielectric constants of several pure solvents according to the volume ratio. However, numerous studies have demonstrated that the dielectric constants of mixed solvents do not combine linearly with those of pure solvents. ,− In explicit solvent models, solvent molecules are treated explicitly, and the free energy is typically evaluated by analyzing the trajectory of time evolution of phase space obtained via MC simulations or molecular dynamics (MD) . Since this approach can provide more molecular details, ab initio MD (AIMD) ,− and mixed QM/MM methods ,− have been extensively applied to get insight into solvent effects on the chemical reaction.…”

Section: Introductionmentioning

confidence: 99%

Demystifying Solvent Effects on Diels–Alder Reactions in Pure and Mixed Solvents: A Combined Electronic DFT and QM/MM Study

Zhang

Tang

Xie

et al. 2023

Ind. Eng. Chem. Res.

View full text Add to dashboard Cite

Although solvent effects on chemical reactions in pure solvents are well elucidated, both reaction mechanisms and solvent effects in mixed solvents remain poorly understood. Herein, the free energy profiles and the solute–solvent energy pair distribution of the Diels–Alder reaction in pure water, acetonitrile (ACN), carbon tetrachloride (CTC), and their mixtures ACN-water and ACN-CTC are calculated using the quantum and molecular mechanical (QM/MM) Monte Carlo method. The results show that the presence of solvent can significantly reduce the reaction free energy barrier, and the barrier in the mixed solvent is intermediate between the two pure solvents. Additionally, the free energy decomposition analysis demonstrated that the QM region dominates the reaction free energy. Electronic DFT calculations are employed to delineate the interactions between reactants and solvent molecules in pure and mixed solvents, with a particular focus on the role of electrostatic potential characteristics and an independent gradient model based on Hirshfeld partition. By rigorously analyzing these interactions, this study demystifies the mechanism underlying the phenomenon of preferential solvation and competition for reacting sites in mixed solvents, which alters the microenvironment of the solute.

show abstract

Bromine Substitution Improves the Photothermal Performance of π‐Conjugated Phototheranostic Molecules

Wan,

Wang,

et al. 2023

Chemistry A European J

View full text Add to dashboard Cite

NIR‐II fluorescence imaging‐guided photothermal therapy (PTT) has been widely investigated due to its great application potential in tumor theranostics. PTT is an effective and non‐invasive tumor treatment method that can adapt to tumor hypoxia; nevertheless, simple and effective strategies are still desired to develop new materials with excellent PTT properties to meet the clinical requirements. In this work, we arise a bromine‐substitution strategy to enhance the PTT of A‐D‐A’‐D‐A π‐conjugated molecules. The experimental results reveal that bromine‐substitution can notably enhance the absorptivity (ε) and photothermal conversion efficiency (PCE) of the π‐conjugated molecules, resulting in the brominated molecules generating two‐fold more heat (ε808 nm × PCE) compared with the non‐substituted counterpart. We declare that the enhanced photothermal properties of bromine‐substituted π‐conjugated molecules are a combined outcome of the heavy‐atom effect, enhanced ICT effect, and bromine‐mediate more intense intermolecular π‐π stacking. Finally, the NIR‐II tumor imaging capability and efficient PTT tumor ablation of the brominated π‐conjugated materials demonstrate that bromine‐substitution will become a promising strategy for developing high‐performance NIR‐II imaging‐guided PTT agents in the future.

show abstract

Dielectric constant of mixed solvents based on perturbation theory

Cited by 13 publications

References 44 publications

Predicting the Relative Static Permittivity: a Group Contribution Method Based on Perturbation Theory

Predicting the Relative Static Permittivity: a Group Contribution Method Based on Perturbation Theory

Demystifying Solvent Effects on Diels–Alder Reactions in Pure and Mixed Solvents: A Combined Electronic DFT and QM/MM Study

Bromine Substitution Improves the Photothermal Performance of π‐Conjugated Phototheranostic Molecules

Contact Info

Product

Resources

About