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

42 items
Editorial

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.

Graphical abstract: Frontiers in molecular simulation of solvated ions, molecules and interfaces
Open Access Perspective

Tumbling with a limp: local asymmetry in water's hydrogen bond network and its consequences

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.

Graphical abstract: Tumbling with a limp: local asymmetry in water's hydrogen bond network and its consequences
From the themed collection: 2020 PCCP HOT Articles
Perspective

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.

Graphical abstract: DFT modelling of explicit solid–solid interfaces in batteries: methods and challenges
From the themed collection: 2020 PCCP HOT Articles
Open Access Communication

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.

Graphical abstract: Temperature effects on the ionic conductivity in concentrated alkaline electrolyte solutions
From the themed collection: 2020 PCCP HOT Articles
Paper

Raman spectrum and polarizability of liquid water from deep neural networks

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.

Graphical abstract: Raman spectrum and polarizability of liquid water from deep neural networks
From the themed collection: 2020 PCCP HOT Articles
Paper

Operando XANES from first-principles and its application to iridium oxide

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.

Graphical abstract: Operando XANES from first-principles and its application to iridium oxide
Paper

DFT insights into electrocatalytic CO2 reduction to methanol on α-Fe2O3(0001) surfaces

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

Graphical abstract: DFT insights into electrocatalytic CO2 reduction to methanol on α-Fe2O3(0001) surfaces
Paper

Correlation effects in parallel tempering and the role of the swapping frequency

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.

Graphical abstract: Correlation effects in parallel tempering and the role of the swapping frequency
Paper

Temperature effects on the spatial distribution of electrolyte mixtures at the aqueous liquid–vapor interface

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.

Graphical abstract: Temperature effects on the spatial distribution of electrolyte mixtures at the aqueous liquid–vapor interface
Paper

Role of image charges in ionic liquid confined between metallic interfaces

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.

Graphical abstract: Role of image charges in ionic liquid confined between metallic interfaces
Paper

Li-ion transport at the interface between a graphite anode and Li2CO3 solid electrolyte interphase: ab initio molecular dynamics study

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.

Graphical abstract: Li-ion transport at the interface between a graphite anode and Li2CO3 solid electrolyte interphase: ab initio molecular dynamics study
Open Access Paper

Unraveling the mechanism of biomimetic hydrogen fuel production – a first principles molecular dynamics study

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.

Graphical abstract: Unraveling the mechanism of biomimetic hydrogen fuel production – a first principles molecular dynamics study
Paper

Adiabatic motion and statistical mechanics via mass-zero constrained dynamics

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.

Graphical abstract: Adiabatic motion and statistical mechanics via mass-zero constrained dynamics
Paper

Effect of anion reorientation on proton mobility in the solid acids family CsHyXO4 (X = S, P, Se, y = 1, 2) from ab initio molecular dynamics simulations

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.

Graphical abstract: Effect of anion reorientation on proton mobility in the solid acids family CsHyXO4 (X = S, P, Se, y = 1, 2) from ab initio molecular dynamics simulations
Paper

Interfacial solvation and slow transport of hydrated excess protons in non-ionic reverse micelles

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

Graphical abstract: Interfacial solvation and slow transport of hydrated excess protons in non-ionic reverse micelles
Paper

Glucose in dry and moist ionic liquid: vibrational circular dichroism, IR, and possible mechanisms

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

Graphical abstract: Glucose in dry and moist ionic liquid: vibrational circular dichroism, IR, and possible mechanisms
Paper

Water dynamics at electrified graphene interfaces: a jump model perspective

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.

Graphical abstract: Water dynamics at electrified graphene interfaces: a jump model perspective
Paper

Modeling interfacial electrochemistry: concepts and tools

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

Graphical abstract: Modeling interfacial electrochemistry: concepts and tools
From the themed collection: 2020 PCCP HOT Articles
Open Access Paper

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.

Graphical abstract: Polaronic structure of excess electrons and holes for a series of bulk iron oxides
Paper

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.

Graphical abstract: A first-principles investigation of the structural and electrochemical properties of biredox ionic species in acetonitrile
From the themed collection: 2020 PCCP HOT Articles
Paper

Spontaneous liquid water dissociation on hybridised boron nitride and graphene atomic layers from ab initio molecular dynamics simulations

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.

Graphical abstract: Spontaneous liquid water dissociation on hybridised boron nitride and graphene atomic layers from ab initio molecular dynamics simulations
Paper

Enhanced conductivity of water at the electrified air–water interface: a DFT-MD characterization

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).

Graphical abstract: Enhanced conductivity of water at the electrified air–water interface: a DFT-MD characterization
From the themed collection: 2020 PCCP HOT Articles
Paper

Carbon dioxide, bicarbonate and carbonate ions in aqueous solutions under deep Earth conditions

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.

Graphical abstract: Carbon dioxide, bicarbonate and carbonate ions in aqueous solutions under deep Earth conditions
Open Access Paper

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.

Graphical abstract: Revisiting nuclear tunnelling in the aqueous ferrous–ferric electron transfer
Paper

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.

Graphical abstract: Aqueous solvation of the chloride ion revisited with density functional theory: impact of correlation and exchange approximations
Paper

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.

Graphical abstract: Electromechanics of the liquid water vapour interface
Open Access Paper

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.

Graphical abstract: Revisiting the Volmer–Heyrovský mechanism of hydrogen evolution on a nitrogen doped carbon nanotube: constrained molecular dynamics versus the nudged elastic band method
From the themed collection: 2020 PCCP HOT Articles
Paper

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.

Graphical abstract: Ionization energies in solution with the QM:QM approach
From the themed collection: 2020 PCCP HOT Articles
Paper

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.

Graphical abstract: Water structures on a Pt(111) electrode from ab initio molecular dynamic simulations for a variety of electrochemical conditions
Paper

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.

Graphical abstract: Exciton transfer free energy from Car–Parrinello molecular dynamics
From the themed collection: 2020 PCCP HOT Articles
Open Access Paper

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.

Graphical abstract: Benchmark and performance of long-range corrected time-dependent density functional tight binding (LC-TD-DFTB) on rhodopsins and light-harvesting complexes
From the themed collection: 2020 PCCP HOT Articles
Paper

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.

Graphical abstract: Quantum kinetic energy and isotope fractionation in aqueous ionic solutions
From the themed collection: 2020 PCCP HOT Articles
Paper

Electron transfer in nonpolar media

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

Graphical abstract: Electron transfer in nonpolar media
Paper

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.

Graphical abstract: Quantifying the hydration structure of sodium and potassium ions: taking additional steps on Jacob's Ladder
Open Access Paper

Rapid and accurate molecular deprotonation energies from quantum alchemy

Deprotonation energies calculated from alchemical electron density derivatives.

Graphical abstract: Rapid and accurate molecular deprotonation energies from quantum alchemy
From the themed collection: 2020 PCCP HOT Articles
Paper

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.

Graphical abstract: Charge fluctuations from molecular simulations in the constant-potential ensemble
From the themed collection: 2020 PCCP HOT Articles
Paper

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.

Graphical abstract: Assessing the properties of supercritical water in terms of structural dynamics and electronic polarization effects
Open Access Paper

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.

Graphical abstract: Thermodynamics of the formation of surface PtO2 stripes on Pt(111) in the absence of subsurface oxygen
Paper

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.

Graphical abstract: The Lennard-Jones potential: when (not) to use it
Paper

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.

Graphical abstract: Electron transfer in extended systems: characterization by periodic density functional theory including the electronic coupling
Paper

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.

Graphical abstract: Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment
Paper

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.

Graphical abstract: Interactions of ions across carbon nanotubes
42 items

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).

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