6.2.2. Definition of Effective Properties 3064 6.3. Response Properties to Magnetic Fields 3066 6.3.1. Nuclear Shielding 3066 6.3.2. Indirect Spin−Spin Coupling 3067 6.3.3. EPR Parameters 3068 6.4. Properties of Chiral Systems 3069 6.4.1. Electronic Circular Dichroism (ECD) 3069 6.4.2. Optical Rotation (OR) 3069 6.4.3. VCD and VROA 3070 7. Continuum and Discrete Models 3071 7.1. Continuum Methods within MD and MC Simulations 3072

/pdf/quantum-mechanical-continuum-solvation-models-3edv963g14.pdf

Quantum mechanical continuum solvation models.

https://dspace.library.uu.nl/bitstream/handle/1874/23806/brug_84_the+analysis+of+electrode+impedances.pdf?sequence=1

The analysis of electrode impedances complicated by the presence of a constant phase element

Real surface area measurements in electrochemistry

Until recently, “room-temperature” (<100–150 °C) liquid-state electrochemistry was mostly electrochemistry of diluted electrolytes(1)–(4) where dissolved salt ions were surrounded by a considerable amount of solvent molecules. Highly concentrated liquid electrolytes were mostly considered in the narrow (albeit important) niche of high-temperature electrochemistry of molten inorganic salts(5-9) and in the even narrower niche of “first-generation” room temperature ionic liquids, RTILs (such as chloro-aluminates and alkylammonium nitrates).(10-14) The situation has changed dramatically in the 2000s after the discovery of new moisture- and temperature-stable RTILs.(15, 16) These days, the “later generation” RTILs attracted wide attention within the electrochemical community.(17-31) Indeed, RTILs, as a class of compounds, possess a unique combination of properties (high charge density, electrochemical stability, low/negligible volatility, tunable polarity, etc.) that make them very attractive substances from fundamental and application points of view.(32-38) Most importantly, they can mix with each other in “cocktails” of one’s choice to acquire the desired properties (e.g., wider temperature range of the liquid phase(39, 40)) and can serve as almost “universal” solvents.(37, 41, 42) It is worth noting here one of the advantages of RTILs as compared to their high-temperature molten salt (HTMS)(43) “sister-systems”.(44) In RTILs the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules.

/pdf/ionic-liquids-at-electrified-interfaces-4n93eaytys.pdf

Ionic Liquids at Electrified Interfaces

The response of a model microelectrochemical system to a time-dependent applied voltage is analyzed. The article begins with a fresh historical review including electrochemistry, colloidal science, and microfluidics. The model problem consists of a symmetric binary electrolyte between parallel-plate blocking electrodes, which suddenly apply a voltage. Compact Stern layers on the electrodes are also taken into account. The Nernst-Planck-Poisson equations are first linearized and solved by Laplace transforms for small voltages, and numerical solutions are obtained for large voltages. The "weakly nonlinear" limit of thin double layers is then analyzed by matched asymptotic expansions in the small parameter epsilon= lambdaD/L, where lambdaD is the screening length and L the electrode separation. At leading order, the system initially behaves like an RC circuit with a response time of lambdaDL/D (not lambdaD2/D), where D is the ionic diffusivity, but nonlinearity violates this common picture and introduces multiple time scales. The charging process slows down, and neutral-salt adsorption by the diffuse part of the double layer couples to bulk diffusion at the time scale, L2/D. In the "strongly nonlinear" regime (controlled by a dimensionless parameter resembling the Dukhin number), this effect produces bulk concentration gradients, and, at very large voltages, transient space charge. The article concludes with an overview of more general situations involving surface conduction, multicomponent electrolytes, and Faradaic processes.

http://web.mit.edu/bazant/www/papers/pdf/Bazant_2004_Phys_Rev_E_DD1.pdf

Diffuse-charge dynamics in electrochemical systems.

Differential Capacity of Mercury in Aqueous Sodium Fluoride Solutions. I. Effect of Concentration at 25

Components of Charge and Potential in the Inner Region of the Electrical Double Layer: Aqueous Potassium Chloride Solutions in Contact with Mercury at 25°

Equations are derived for the variation of potential with distance and for the components of charge and capacity in the diffuse double layer at a plane interface for electrolytes of the 1:2 and 2:1 valence types. Some additional relations are also deduced for other valence types.

Diffuse Double Layer Theory for Electrolytes of Unsymmetrical Valence Types

Components of Charge and Potential in the Non-diffuse Region of the Electrical Double Layer: Potassium Iodide Solutions in Contact with Mercury at 25°1

The rate of change with concentration of the capacity of the electrical double layer on mercury has been measured. From this there have been calculated Γ+, the excess of cations in the double layer, and Γ—, the excess of anions. The latter has been subdivided into η—d, the excess of anions in the diffuse double layer, and η—i, the excess of anions in the inner part of the double layer. From these data it has also been possible to evaluate ψ0, the potential of the outer Helmholtz plane.It is found that fluoride ion remains unadsorbed on mercury at all potentials investigated, including potentials anodic to the e.c.max. Other anions are strongly adsorbed (chemisorbed) when the mercury is positively charged, and sometimes even when it is negatively charged. The ``hump'' in the capacity curves of salts of such anions as chloride, bromide, acetate, and nitrate, are found to be present in curves of C—, the capacity attributable to anions alone. No chemisorption of monatomic cations could be detected.The kinetic...

David C. Grahame

Papers

Differential Capacity of Mercury in Aqueous Sodium Fluoride Solutions. I. Effect of Concentration at 25

Components of Charge and Potential in the Inner Region of the Electrical Double Layer: Aqueous Potassium Chloride Solutions in Contact with Mercury at 25°

Diffuse Double Layer Theory for Electrolytes of Unsymmetrical Valence Types

Components of Charge and Potential in the Non-diffuse Region of the Electrical Double Layer: Potassium Iodide Solutions in Contact with Mercury at 25°1

Ionic Components of Charge in the Electrical Double Layer