Search results for "solvation"
showing 10 items of 157 documents
Analysis of a solute polarity parameter in reversed-phase liquid chromatography on a linear solvation relationship basis
2004
Abstract A study was made to correlate an overall solute polarity descriptor ( p ) with several molecular parameters: excess molar refraction ( E ), dipolarity/polarizability ( S ), effective hydrogen-bond acidity ( A ) and basicity ( B ), and McGowan volume ( V ), through the linear solvation model ( p = c + eE + sS + aA + bB + vV ). The achieved values of p were introduced in a retention model developed previously for reversed-phase liquid chromatography (RPLC), which describes the retention according to the polarity contributions of solute, mobile phase and stationary phase. The retention behaviour (log k ) of a solute in a given chromatographic system (i.e. column/organic solvent) is a…
Ion Pairing in the Analysis of Voltammetric Data at the ITIES: RbTPB and RbTPBCl in 1,2-dichloroethane
1995
The association of rubidium-tetraphenylborate (RbTPB) and rubidium-tetrakis(-chlorophenyl)borate (RbTPBCl) ion pairs in the organic solvent 1,2-dichloroethane (DCE) have been obtained from condutivity and voltammetric data. Conductivity measurements given K RbTPBCl =43 100 M -1 and yield a lower bound for K RbTPB (K RbTPB > 70000 M -1 ). The latter association constant is at variance with the previously accepted value. A method for analysing voltammetric data which allows for the determination of the association constants is presented. The positive polarization limit where the transfer of Rb + takes place is shifted by ca. 200 mV when changing the anion of the organic base electrolyte from …
Rational computing of energy levels for organic electronics: the case of 2-benzylidene-1,3-indandiones
2016
Device engineering in organic electronics, an active area of research, requires knowledge of the energy levels of organic materials (traditionally but ambiguously denoted as HOMO and LUMO). These can be effectively determined by electrochemical investigation, but yet more effective would be quantum chemical (QC) computation of these quantities. However, there is no consensus on the computational method in the research community. Ongoing discussions often focus on choosing the right density functional method, but neglect other model parameters, in particular, the basis set. This study considers comparison of various methodologies and parameters for predicting ionization energy I and electron…
A new discretization for the polarizable continuum model within the domain decomposition paradigm
2016
International audience; We present a new algorithm to solve the polarizable continuum model equation in a framework compatible with the strategy previously developed by us for the conductor-like screening model based on Schwarz’s domain decomposition method (ddCOSMO). The new discretization is systematically improvable and is fully consistent with ddCOSMO so that it reproduces ddCOSMO results for large dielectric constants.
Perspective: Polarizable continuum models for quantum-mechanical descriptions
2016
Polarizable continuum solvation models are nowadays the most popular approach to describe solvent effects in the context of quantum mechanical calculations. Unexpectedly, despite their widespread use in all branches of quantum chemistry and beyond, important aspects of both their theoretical formulation and numerical implementation are still not completely understood. In particular, in this perspective we focus on the numerical issues of their implementation when applied to large systems and on the theoretical framework needed to treat time dependent problems and excited states or to deal with electronic correlation. Possible extensions beyond a purely electrostatic model and generalization…
The influence of the solvent's mass on the location of the dividing surface for a model Hamiltonian
2019
The Transition State dividing surface is a key concept, not only for the precise calculation of the rate constant of a reaction, but also for the proper prediction of product ratios. The correct location of this surface is defined by the requirement that reactive trajectories do not recross it. In the case of reactions in solution the solvent plays an important role in the location of the dividing surface. In this paper we show with the aid of a model Hamiltonian that the effective mass of the solvent can dramatically change the location of the dividing surface. Keywords: Dynamical systems, Dividing surface, Reactions in solution, 2019 MSC: 00-01, 99-00
Effect of Packing on Cluster Solvation of Nanotubes
2006
It is discussed the possibility of the existence of single-wall carbon nanotubes (SWNTs) in organic solvents in the form of clusters, containing a number of SWNTs. A theory is developed based on a bundlet model for clusters, which enables describing the distribution function of clusters by size. Comparison of the calculated values of solubility with experimental data would permit obtaining energetic parameters characterizing the interaction of an SWNT with its surrounding, in a solid phase or solution. Fullerenes—SWNTs are unique objects, whose behaviour in many physical situations is characterized by remarkable peculiarities. Peculiarities in solutions show up first in that fullerenes—SWNT…
An Analysis of the Concentration Effects on Elution Volumes by Using the Preferential Solvation Parameter in Two SEC Packings
2002
Size exclusion chromatography (SEC) elution behavior of different solvent/polymer systems has been analyzed from chromatographic, thermodynamic, and hydrodynamic points of view in two organic column packings based on polystyrene/divinylbenzene (PS/DVB) copolymer, μ-styragel and TSK-Gel H HR . Although both packings present similar chromatographic properties, some differences arise when eluting the same systems. The values of the adsorption distribution coefficients, K p , have been correlated with the preferential solvation coefficient, λ (see Figure), for both packings, showing that those systems with lower and negative λ values (denoting higher preferential solvation of the polymer by the…
Investigation of compatibility of a dicyanate ester monomer and polysulfone by size-exclusion chromatography and viscometry
2003
The influence of solvent on the compatibility behaviour of Arocy B10, a cyanate ester monomer, and polysulfone (PSF) was investigated by means of dilute solution viscometry and of the preferential solvation parameter at 25 °C. The ternary systems under study are: tetrahydrofuran/Arocy B10/polysulfone (PSF), N,N-dimethylformamide/Arocy B10/PSF and dichloromethane/Arocy B10/PSF. Values of the specific viscosity of PSF in a ‘binary solvent’ formed by Arocy B10 + solvent have been used to determine the compatibility of the polymer blend Arocy B10/PSF. An interaction parameter Δb that depends on concentration has been determined. The preferential solvation parameter was measured by size-exclusio…
Learning from nature: beta-sheet-mimicking copolymers get organized.
2007
The solution structures formed by coil-coil copolymers arise from the selective solvation of one of the two blocks and have been well described. In most cases in such relatively simple synthetic structures there are no specific attractive forces that can aid the aggregation process. Nature, however, provides plenty of inspiring polymeric architectures that are shaped and ordered hierarchically by noncovalent forces. The high level of structural definition displayed by proteins, for example, is unmatched by synthetic polymers. An emerging area of interest in polymer science tries to combine the best of both worlds, the natural and the synthetic, by conjugating synthetic polymers and beta-she…