DFT modelling of explicit solid–solid interfaces in batteries: methods and challenges
Density Functional Theory (DFT) calculations of electrode material properties in high energy density storage devices like lithium batteries have been standard practice for decades.
Temperature effects on the ionic conductivity in concentrated alkaline electrolyte solutions
Reactive molecular dynamics simulations show how ion-paring, cross-correlated ion motions and proton transfer contribute to the ionic conductivity in concentrated NaOH solutions at elevated temperatures.
Polaronic structure of excess electrons and holes for a series of bulk iron oxides
With the use of a gap-optimized hybrid functional and large supercells, it is found that while the electron hole polaron generally localises onto a single iron site, the electron polaron localises across two iron sites of the same spin layer.
Revisiting nuclear tunnelling in the aqueous ferrous–ferric electron transfer
We find that golden-rule quantum transition-state theory predicts nearly an order of magnitude less tunnelling than some of the previous estimates. This may indicate that the spin-boson model of electron transfer is not valid in the quantum regime.
Modeling Interfacial electrochemistry: concepts and tools
A first-principles investigation of the structural and electrochemical properties of biredox ionic species in acetonitrile
Ab initio molecular dynamics allow understanding of electron transfer reactions for a series of systems involved in redox supercapacitors.
Spontaneous Liquid Water Dissociation on Hybridised Boron Nitride and Graphene atomic layers from Ab Initio Molecular Dynamics Simulations
Enhanced conductivity of water at the electrified air-water interface: a DFT-MD characterization
Carbon Dioxide, Bicarbonate and Carbonate Ions in Aqueous Solutions at Deep Earth Conditions
Electromechanics of the liquid water vapour interface
The response of the anisotropic stress at the liquid water vapor interface to a finite electric suggests that the surface potential of water can be seen as an electro-capillary effect coupled to the Maxwell stress tensor.
Aqueous solvation of the chloride ion revisited with density functional theory: impact of correlation and exchange approximations
Aqueous chloride is simulated using PBE-D3, PBE0-D3, and SCAN to investigate the impact of exchange and correlation approximations; we find the exact exchange fraction strongly impacts the energetics and polarizability of solvated chloride.
Ionization energies in solution with the QM:QM approach
Fragment-based QM:QM technique provides an efficient and accurate way for calculating energetics of vertical processes such as ionization.
Revisiting the Volmer–Heyrovský mechanism of hydrogen evolution on a nitrogen doped carbon nanotube: constrained molecular dynamics versus the nudged elastic band method
This study presents the first direct simulation of the hydrogen evolution reaction using a fully explicit, dynamic DFT approach and highlights the importance of incorporating solvent dynamics in the rigorous description of electrochemical reactions.
Water structures on a Pt(111) electrode from ab initio molecular dynamic simulations for a variety of electrochemical conditions
Water structures on a Pt(111) metal electrode critically depend on the electrochemical conditions, as shown by ab initio molecular dynamics simulations.
Exciton transfer free energy from Car–Parrinello molecular dynamics
Free energies profiles for exciton transfer processes are calculated within ab initio molecular dynamics by applying restraining potentials to the Wannier centres of molecular orbitals corresponding to an electron-hole pair.
Rapid and accurate molecular deprotonation energies from quantum alchemy
Deprotonation energies calculated from alchemical electron density derivatives.
Benchmark and performance of long-range corrected time-dependent density functional tight binding (LC-TD-DFTB) on rhodopsins and light-harvesting complexes
In the present work, we perform a benchmark study on both the isolated chromophores retinal and BChl a as well as on the biological systems, to determine the accuracy of LC-TD-DFT and LC-TD-DFTB for describing color-tuning effects.
Quantum kinetic energy and isotope fractionation in aqueous ionic solutions
Decomposition of the quantum kinetic energy and isotope fractionation ratios uncovers the local solvation structures in aqueous ionic solutions.
Electron transfer in nonpolar media
Electron transfer in nonpolar media violates the temperature scaling predicted by the fluctuation–dissipation theorem.
Charge fluctuations from molecular simulations in the constant-potential ensemble
Statistical mechanics of constant-potential molecular simulations yields a new fluctuation–dissipation relation for the differential capacitance.
Quantifying the hydration structure of sodium and potassium ions: taking additional steps on Jacob's Ladder
The ability to reproduce the experimental structure of water around the sodium and potassium ions is a key test of the quality of interaction potentials due to the central importance of these ions in a wide range of important phenomena.
Assessing the properties of supercritical water in terms of structural dynamics and electronic polarization effects
Evolution of water's structural dynamics from ambient liquid to supercritical dense liquid-like and dilute gas-like conditions.
Thermodynamics of the formation of surface PtO2 stripes on Pt(111) in the absence of subsurface oxygen
This paper examines the thermodynamics of PtO2 stripes formed as intermediates of Pt(111) surface oxidation as a function of the degree of dilation parallel to the stripes, using density functional theory and atomistic thermodynamics.
The Lennard-Jones potential: when (not) to use it
The Lennard-Jones 12-6 potential is widely used in simulations… or is it? We propose reconsidering when to use it.
Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment
The TiO2–Pt–water interface is of great relevance in photocatalysis where Pt is widely used as a co-catalyst for enhancing hydrogen evolution in aqueous TiO2.
Electron transfer in extended systems: characterization by periodic density functional theory including the electronic coupling
CP2K implementation describing electron transfer in extended systems treated by periodic-DFT, including the calculation of electronic coupling transition element VAB.
Interactions of ions across carbon nanotubes
The interactions between a pair of ions across CNTs have been investigated by DFT. The electrostatic field of the ion is almost completely screened outside of the tube but an effective attraction between the ions has arisen.
About this collection
Predictive molecular simulation of condensed matter at finite temperature has come a long way from the first practical implementations of ab-initio or Car-Parrinello molecular dynamics thirty years ago.
This themed collection provides a representative snapshot of latest and upcoming techniques and their applications at the forefront of this research area with a specific focus on the simulation of solvated ions, molecules and interfaces.
Guest Edited by: Jochen Blumberger (University College London), Marie-Pierre Gaigeot (Université d’Evry val d’Essonne and Université Paris-Saclay), Marialore Sulpizi (Johannes Gutenberg Universität Mainz) and Rodolphe Vuilleumier (Sorbonne University).