Related papers: Theory of coupled ion-electron transfer kinetics
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…
We present theoretical models for the time-dependent voltage of an electrochemical cell in response to a current step, including effects of diffuse charge (or "space charge") near the electrodes on Faradaic reaction kinetics. The full model…
The rate of electron transfer between a molecular species and a metal, each at a different local temperature, is examined theoretically through implementation of a bithermal (characterized by two temperatures) Marcus formalism. Expressions…
The morphology of interfaces is known to play fundamental role on the efficiency of energy-related applications, such light harvesting or ion intercalation. Altering the morphology on demand, however, is a very difficult task. Here, we show…
We present a thermodynamic analysis of the driving forces for intercalation and conversion reactions in battery cathodes across a range of possible working ion, transition metal, and anion chemistries. Using this body of results, we analyze…
Ultrahigh rate performance of active particles used in lithium-ion battery electrodes has been revealed by single-particle measurements, which indicates a huge potential for developing high-power batteries. However, the charging/discharging…
Electron Transfer (ET) reactions are modeled by the dynamics of a quantum two-level system (representing the electronic state) coupled to a thermalized bath of classical harmonic oscillators (representing the nuclei degrees of freedom).…
Interfacial charge transfer is widely assumed to obey Butler-Volmer kinetics. For certain liquid-solid interfaces, Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report…
The unified 3D phase-field model for the description of the lithium-ion cell as a whole is developed. The model takes into account the realistic distribution of particles in porous electrodes, percolative transport of ions, and the…
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…
The proposed switching mechanism is based on an electronically-induced metal-insulator transition occurring in conditions of the excess non-equilibrium carrier density under the applied electric field. First, this mechanism is developed on…
Dynamics of ionic-to-neutral and neutral-to-ionic phase transitions induced by intrachain charge-transfer photoexcitations are studied in a quasi-one-dimensional extended Hubbard model with alternating potentials and an electron-lattice…
We study the model of a molecular switch comprised of a molecule with a soft vibrational degree of freedom coupled to metallic leads. In the presence of strong electron-ion interaction, different charge states of the molecule correspond to…
Marcus theory is fundamental to describing electron transfer reactions and quantifying their rates, effectively representing the energy surface associated with an electron transfer from the reactant to the product ionic state via parabolas…
Beyond the dielectric continuum description initiated by Marcus theory, the nowadays standard theoretical approach to study electron transfer (ET) reactions in solution or at interfaces is to use classical force field or ab initio Molecular…
Transfer-ionization in fast collisions between a bare ion and an atom, in which one of the atomic electrons is captured by the ion whereas another one is emitted, crucially depends on dynamic electron-electron correlations. We show that in…
Quantum rate theory is based on a first-principle quantum mechanical rate concept that comprises with the Planck-Einstein relationship $E = h\nu$, where $\nu = e^2/hC_q$ is a frequency associated with the quantum capacitance $C_q$ and $E =…
In the present work, a theoretical study of electron-phonon (electron-ion) coupling rates in semiconductors driven out of equilibrium is performed. Transient change of optical coefficients reflects the band gap shrinkage in covalently…
The stability of high vs. low spin states of transition metal complexes has been interpreted by ligand field theory, which is a perturbation theory of the electron-electron interaction. The present first principles calculation of a series…
Atomic clocks based on an Al$^+$ ion sympathetically cooled by a laser-cooled alkaline-earth ion have achieved unprecedented accuracy. Here, we investigate theoretically interactions and charge transfer dynamics of an Al$^+$ ion immersed in…