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The derivative discontinuity is a key concept in electronic structure theory in general and density functional theory in particular. The electronic energy of a quantum system exhibits derivative discontinuities with respect to different…
Using the example of a proton adsorption process, we analyze and compare two prominent modelling approaches in computational electrochemistry at metallic electrodes - electronically canonical, constant-charge and electronically…
Supercell modelling of an electrical double layer (EDL) at electrified solid-electrolyte interfaces is a challenge. The net polarization of EDLs arising from the fixed chemical composition setup leads to uncompensated EDLs under periodic…
We introduce 'single-particle-exact density functional theory' (1pEx-DFT), a novel density functional approach that represents all single-particle contributions to the energy with exact functionals. Here, we parameterize interaction energy…
The density-functional approach to quantum electrodynamics is extending traditional density-functional theory and opens the possibility to describe electron-photon interactions in terms of effective Kohn-Sham potentials. In this work, we…
Density functional theory (DFT) underpins modern atomistic simulations of transition-metal surfaces. It can predict key properties linked to catalytic performance, such as adsorption energies and barrier heights, enabling new paradigms in…
Classical dynamical density functional theory (DDFT) is one of the cornerstones of modern statistical mechanics. It is an extension of the highly successful method of classical density functional theory (DFT) to nonequilibrium systems.…
Catalysis lies at the heart of chemical reactivity, yet its foundational principles remain fragmented across the distinct domains of homogeneous, heterogeneous, and enzymatic systems Here, we propose a unifying theoretical model that…
A new variational method for studying the equilibrium states of an interacting particles system has been proposed. The statistical description of the system is realized by means of a density matrix. This method is used for description of…
We present a quaternion inspired formalism specifically developed to evaluate the intensity of the electrical current that traverses a single molecule connected to two semi-infinite electrodes as the applied external bias is varied. The…
We formulate and implement Cyclic Density Functional Theory (Cyclic DFT) -- a self-consistent first principles simulation method for nanostructures with cyclic symmetries. Using arguments based on Group Representation Theory, we rigorously…
With the eigenfunctional theory, we study a general interacting electron system, and give a rigorous expression of its ground state energy which is composed of two parts, one part is contributed by the non-interacting electrons, and another…
Chemical reactions involve the movement of charges, and this work presents a mathematical model for describing chemical reactions in electrolytes. The model is developed using an energy variational method that aligns with classical…
We start from microscopic approach to many body physics and show the analytical steps and approximations required to arrive at the concept of quantum capacitance. These approximations are valid only in the semi-classical limit and the…
The electric field dielectric polarization-based separations mechanism represents a novel method for separating solutions at small length scales. An electric field gradient with a maximum strength of $\mathrm{0.4~MV/m}$ applied across a…
Porous electrode theory, pioneered by John Newman and collaborators, provides a useful macroscopic description of battery cycling behavior, rooted in microscopic physical models rather than empirical circuit approximations. The theory…
Many key industrial processes, from electricity production, conversion and storage to electrocatalysis or electrochemistry in general, rely on physical mechanisms occurring at the interface between a metallic electrode and an electrolyte…
Capacitance measurements from cyclic voltammetry, galvanostatic chronopotentiometry and calculation of capacitance from imaginary part of impedance are widely used in investigations of supercapacitors. The methods assume the supercapacitor…
Except for small molecules, it is impossible to solve many electrons systems without imposing severe approximations. If the configuration interaction approaches (CI) or Coupled Clusters techniques \cite{FuldeBook} are applicable for…
The fundamental quantity governing the mechanical and thermodynamic properties of a crystalline solid is its electronic charge density. Yet, its direct use for the rapid prediction of materials properties remains challenging due to its high…