Themed collection Frontiers in Molecular Simulation of Solvated Ions, Molecules and Interfaces

This themed collection is a collection of articles on frontiers in molecular simulation of solvated ions, molecules and interfaces.

Ab initio molecular dynamics simulations of ambient liquid water and energy decomposition analysis have recently shown that water molecules exhibit significant asymmetry between the strengths of the two donor and/or the two acceptor interactions.

Density Functional Theory (DFT) calculations of electrode material properties in high energy density storage devices like lithium batteries have been standard practice for decades.

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.

Using deep neural networks to model the polarizability and potential energy surfaces, we compute the Raman spectrum of liquid water at several temperatures with ab initio molecular dynamics accuracy.

Density-functional theory calculations augmented with a continuum description of the electrochemical environment are implemented to simulated X-ray absorption spectra as a function of the applied potential.

Electrocatalytic reduction of CO₂ to manufacture fuels and other useful chemicals is one of the appealing methods to reuse CO₂.

In this work I investigate the effect of the swapping time frequency in parallel tempering (or replica exchange molecular dynamics, REMD) on the sampled equilibrium distributions at the different temperatures.

Monte Carlo simulations indicate that an anion's propensity for interfacial adsorption increases with its size and is associated with an enthalpic gain and entropic cost for the largest anion.

Atomistic molecular dynamics simulations unveil a minor role of metal polarisation at ionic liquid/gold interface and provide a novel description of the interface where long range effects are seen in dynamical properties up to 10 nm from surface.

DFT calculation based free energy profile for Li-ion transport across graphite anode/Li₂CO₃ SEI interface, indicating how to understand the profile change between discharging and charging in battery.

The Fe₂(bdt)(CO)₆ [bdt = benzenedithiolato] complex, a synthetic mimic of the [FeFe] hydrogenase enzyme can electrochemically convert protons into molecular hydrogen. The free energy landscape reveals a different mechanism for the biomimetic cycle.

A symplectic, time-reversible algorithm for adiabatically separated systems that exactly samples the Born–Oppenheimer probability distribution is presented and its numerical efficiency is demonstrated on an orbital-free DFT simulation of solid Na.

The high temperature phases of the solid acids CsHSeO₄, CsHSO₄ and CsH₂PO₄ show extraordinary high proton conductivities, which are enabled by the interplay of high proton transfer rates and frequent anion reorientation.

Simulations show that hydrated excess protons in non-ionic reverse micelles resides near the interface, contrary to some experimental assumptions.

The molecular level specification of glucose monomers in ionic liquids and their mixtures with water helps understanding cellulose processing in these liquids.

Changes in water reorientation dynamics at electrified graphene interfaces arise from the interfaces’ impact on water hydrogen-bond exchanges; the asymmetric behavior with electrode potential sign is quantitatively described by an extended jump model.

This paper presents a grand canonical formalism and provides tools to investigate electrochemical effects at interfaces.

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.

Ab initio molecular dynamics allow understanding of electron transfer reactions for a series of systems involved in redox supercapacitors.

By means of ab initio simulations we unveil the high reactivity of boron nitride–graphene planar heterostructure immersed in liquid water: an interfacial water molecule is found to spontaneously chemisorb and deprotonate at one composite border.

DFT-based molecular dynamics simulations of the electrified air–liquid water interface are presented, where a homogeneous field is applied parallel to the surface plane (i.e. parallel to the 2D-HBonded-Network/2DN).

We investigate the effect of pressure, temperature and acidity on the composition of water-rich carbon-bearing fluids under thermodynamic conditions that correspond to the Earth's deep crust and upper mantle.

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.

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.

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.

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.

Fragment-based QM:QM technique provides an efficient and accurate way for calculating energetics of vertical processes such as ionization.

Water structures on a Pt(111) metal electrode critically depend on the electrochemical conditions, as shown by ab initio molecular dynamics simulations.

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.

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.

Decomposition of the quantum kinetic energy and isotope fractionation ratios uncovers the local solvation structures in aqueous ionic solutions.

Electron transfer in nonpolar media violates the temperature scaling predicted by the fluctuation–dissipation theorem.

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.

Deprotonation energies calculated from alchemical electron density derivatives.

Statistical mechanics of constant-potential molecular simulations yields a new fluctuation–dissipation relation for the differential capacitance.

Evolution of water's structural dynamics from ambient liquid to supercritical dense liquid-like and dilute gas-like conditions.

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 12-6 potential is widely used in simulations… or is it? We propose reconsidering when to use it.

CP2K implementation describing electron transfer in extended systems treated by periodic-DFT, including the calculation of electronic coupling transition element V_AB.

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.

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.