Themed collection 2022 PCCP HOT Articles
Understanding the n → π* non-covalent interaction using different experimental and theoretical approaches
A comprehensive perspective of the n → π* non-covalent interaction obtained using various experimental and theoretical approaches is presented.
Differential dynamic microscopy for the characterisation of motility in biological systems
Differential Dynamic Microscopy (DDM) is a relatively new technique which measures the dynamics of suspended particles using a dynamic light scattering formalism.
The hitchhiker's guide to dynamic ion–solvent clustering: applications in differential ion mobility spectrometry
This article provides atomistic insight into the dynamic microsolvation processes occurring in differential mobility spectrometry (DMS), which can be used to (1) reproduce an ion's DMS behaviour, and (2) predict an ion's condensed-phase properties.
Time-resolved photoelectron spectroscopy: the continuing evolution of a mature technique
In this perspective, we discuss the current state of the art of time-resolved photoelectron spectroscopy to probe nonadiabatic dynamics, including ab initio approaches for its simulation and new experimental efforts.
Velocity correlated emission of secondary clusters by a single surface impact of a polyatomic ion: a new mechanism of cluster emission and subpicosecond probing of extreme spike conditions
Velocity correlated cluster emission (VCCE) effect: all large clusters emitted from a given target following a fullerene ion impact move with nearly the same velocity. A hot moving precursor is proposed as the source of the outgoing clusters.
Exploiting mixed conducting polymers in organic and bioelectronic devices
Mixed ionic-electronic conduction is a critical feature in a wide range of emerging electrochemical devices based on conjugated polymers exploiting transport, coupling, and charge carrier concentration modulation of both electronic and ionic charges.
Atomically thin 2D photocatalysts for boosted H2 production from the perspective of transient absorption spectroscopy
The efficiency of a 2D photocatalyst is largely dependent on the excited state charge carrier behavior at short time scale, which can be accessed and used for the betterment of the photocatalyst via only transient absorption spectroscopy.
Advanced cathodic free-standing interlayers for lithium–sulfur batteries: understanding, fabrication, and modification
This perspective demonstrates the novelty of the understanding, fabrication, notification and outlook of the free-standing cathodic interlayer in Li-S batteries.
The evolution of paramagnetic NMR as a tool in structural biology
Paramagnetic NMR observables provide accurate long-range structural information and act as a loupe on the metal coordination site.
Atom–surface scattering in the classical multiphonon regime
Many experiments that utilize beams of incident atoms colliding with surfaces as a probe of surface properties are carried out at large energies, high temperatures and with large mass atoms.
Grazing incidence fast atom and molecule diffraction: theoretical challenges
In this article, we review the theoretical methods used to simulate and analyze grazing-incidence fast atom and molecule diffraction, focusing on their weaknesses and strengths, as well as the theoretical challenges that still need to be addressed.
Computational vibrational spectroscopy of molecule–surface interactions: what is still difficult and what can be done about it
Anharmonic effects are important in adsorbed molecules even as harmonic calculations continue to dominate computed vibrational spectra in applications. We consider perspectives of application of anharmonic methods to adsorbed molecules.
Supraballs as spherical solid 3D superlattices of hydrophobic nanocrystals dispersed in water: nanoarchitectonics and properties
Nanoheaters: FCC solid spherical nanocrystal assemblies either dispersed in solution or internalized in tumor cells.
Ab initio calculation of X-ray and related core-level spectroscopies: Green's function approaches
Green's function approaches facilitate efficient and accurate calculations of X-ray spectra that include key many-body effects.
Photoionization of the aqueous phase: clusters, droplets and liquid jets
This perspective article reviews specific challenges associated with photoemission spectroscopy of bulk liquid water, aqueous solutions, water droplets and water clusters.
Current understanding and insights towards protein stabilization and activation in deep eutectic solvents as sustainable solvent media
Deep eutectic solvents (DESs) have emerged as a new class of green, designer and biocompatible solvents, an alternative to conventional organic solvents and ionic liquids (ILs) which are comparatively toxic and non-biodegradable.
Advances in the OCEAN-3 spectroscopy package
An overview of the OCEAN code for calculating near-edge X-ray spectroscopy, including X-ray absorption and resonant inelastic X-ray scattering, using the Bethe-Salpeter equation approach.
Chemical potential, derivative discontinuity, fractional electrons, jump of the Kohn–Sham potential, atoms as thermodynamic open systems, and other (mis)conceptions of the density functional theory of electrons in molecules
Objections are raised against the straight-line behavior of the energy for fractional electron number and its basis in thermodynamical (grand canonical ensemble) considerations. It is not “the exact DFT for noninteger electron systems”.
Understanding specific ion effects and the Hofmeister series
This perspective reviews the historical explanations for specific ion effects, and explores the frontiers of the field before summarising its challenges and opportunities.
Quantitative molecular simulations
All-atom simulations can provide molecular-level insights into the dynamics of gas-phase, condensed-phase and surface processes.
On surface chemical reactions of free-base and titanyl porphyrins with r-TiO2(110): a unified picture
Free-base porphyrins on TiO2(110) anchor to Obr rows, where they capture diluted hydrogen underneath and favour outdiffusion of Ti interstitials by self-metalation; Ti metalated species may also capture oxygen from hydroxyl adsorbates on Ti5f rows.
Setting up the HyDRA blind challenge for the microhydration of organic molecules
The first theory blind challenge addressing the effect of microsolvation on water vibrations is launched.
Laser pulses into bullets: tabletop shock experiments
A tabletop pulsed laser can launch a hypervelocity flyer plate to create high temperatures and pressures in a nanosecond in an array of solid or liquid samples.
Multiscale computational investigations of the translesion synthesis bypass of tobacco-derived DNA adducts: critical insights that complement experimental biochemical studies
Computational modelling complements experimental biochemical studies on DNA adduct mutagenicity by providing structural insights for a diverse set of lesions resulting from tobacco products.
Reaction dynamics within a cluster environment
This perspective article reviews experimental and theoretical works where rare gas clusters and helium nanodroplets are used as a nanoreactor to investigate chemical dynamics in a solvent environment.
Small-molecule ambipolar transistors
Small-molecule materials showing ambipolar transistor properties are reviewed.
Zooming in on the initial steps of catalytic NO reduction using metal clusters
The study of reactions relevant to heterogeneous catalysis on metal clusters with full control over the number of constituent atoms and elemental composition can lead to a detailed insight into the interactions governing catalytic functionality.
Metal-nanocluster science and technology: my personal history and outlook
This personal account describes my motivation for each previous subject on metal nanoclusters, what type of research I want to perform, and how I consider the outlook of the field.
Electromagnetic bioeffects: a multiscale molecular simulation perspective
We summarise methodologies, challenges and opportunities for theoretical modelling to advance current understanding of electromagnetic bioeffects for biomedicine and industry.
Electron diffraction as a structure tool for charged and neutral nanoclusters formed in superfluid helium droplets
Electron diffraction of clusters doped in superfluid helium droplets is an in situ technique for cluster synthesis and atomic structure determination. Both neutral and ionic nanoclusters can be investigated with proper care of the helium background.
Multi-resolution simulation of DNA transport through large synthetic nanostructures
A new combination of coarse-grained modeling and finite element calculations enable rapid and accurate characterization of DNA transport through nanostructures of diverse geometries.
Palladium clusters, free and supported on surfaces, and their applications in hydrogen storage
Palladium clusters enhance the hydrogen storage of nanoporous carbons.
Photoelectron spectroscopy in molecular physical chemistry
Photoelectron spectroscopy has evolved into a powerful tool for physical chemistry and molecular physics. Some recent examples are highlighted in this perspective.
Recent advances in dendrite-free lithium metal anodes for high-performance batteries
This review provides an overview of the significant progresses that occur on lithium metal anodes for lithium metal batteries. Some modification strategies and in situ characterization approaches are discussed.
Perspective on interface engineering for capacitive energy storage polymer nanodielectrics
Polymer nanodielectrics with high breakdown strength (Eb), high energy density (Ue) and low energy loss have great potential to be used as capacitive energy storage materials of high-voltage film capacitors in modern electrical and electronic equipment, such as smart grids, new energy vehicles and pulse powered weapons.
Theoretical study of macrocyclic host molecules: from supramolecular recognition to self-assembly
In this review, we take heteroatom-bridged heteroaromatic calixarene, cucurbituril and cyclodextrin as examples, and summarize the recent progress in the molecular recognition and self-assembly of macrocyclic host molecules by multiscale modelling.
Exploring the materials space in the smallest particle size range: from heterogeneous catalysis to electrocatalysis and photocatalysis
Minireview on ultrasmall subnanometer clusters driving chemical transformations in heterogeneous catalysis, electrocatalysis and photocatalysis.
Violations to the principle of least motion: the shortest path is not always the fastest
The shortest reaction path is not always that of lowest activation energy.
Infrared spectroscopic monitoring of solid-state processes
We put a spotlight on IR spectroscopic investigations in materials science by providing a critical insight into the state of the art, covering both fundamental aspects, examples of its utilisation, and current challenges and perspectives focusing on the solid state.
Designing 3d metal oxides: selecting optimal density functionals for strongly correlated materials
First-row TMOs have remarkable properties that are appealing in materials design for technological applications. Their electronic structure can be modelled with DFT, but this requires careful considerations due to strong correlation effects of 3d orbitals.
Multiscale molecular modelling: from electronic structure to dynamics of nanosystems and beyond
This tutorial review provides an introduction to multiscale modelling of complex chemical, physical and biological processes through case studies, aimed at beginning researchers and more senior colleagues who are changing direction to focus on multiscale aspects of their research.
Mesoporous TiO2 layer suppresses ion accumulation in perovskite solar cells
The TiO2-nanoparticle scaffold suppresses ion accumulation in mesoporous perovskite solar cells by reducing the electrostatic interaction between the conductive substrate and the perovskite active layer.
Design and applications of water irradiation devoid RF pulses for ultra-high field biomolecular NMR spectroscopy
Water devoid RF pulses designed by an evolutionary algorithm and AI improve solvent suppression and increase the NMR spectra sensitivity.
Transition between growth of dense and porous films: theory of dual-layer SEI
The film-growth model predicts a morphology-driven dual-layer structure due to slowing down of electron diffusion through the SEI.
Variation of bending rigidity with material density: bilayer silica with nanoscale holes
Helium atom scattering experiments on a “holey” silica bilayer film reveal that the bending rigidity of the material, extracted from phonon dispersion curves, decreases with decreasing material density.
B96: a complete core–shell structure with high symmetry
A complete core–shell B96 is highly symmetric (Th) and stable, and exhibits a superatomic electronic configuration and spherical aromaticity.
Nucleophilicity of the boron atom in compounds R–B, (R = F, Cl, Br, I, CN, NC, CH3, SiH3, CF3, H): a new look at the inductive effects of the group R
Nucleophilicities NR–B of molecules R–B (R = F, Cl, Br, I, CN, NC, CH3, SiH3, CF3, H) are determined from the equilibrium dissociation energies De of 70 hydrogen-bonded complexes R–B⋯HX (X = F, Cl, Br, I, HCN, HCCH, HCP).
Stepwise dissociation of ion pairs by water molecules: cation-dependent separation mechanisms between carboxylate and alkali-earth metal ions
The first steps of ion dissociation in microhydrated H2-tagged ion pairs (Ca2+, AcO−)(H2O)n=0–8 and (Ba2+, AcO−)(H2O)n=0–5 are revealed by IR photodissociation laser spectroscopy and DFT-D frequency calculations.
A straightforward method to quantify the electron-delocalizing ability of π-conjugated molecules
The inter-fragment delocalization index (IFDI) is introduced as a simple, easy-to-use method for quantifying electronic delocalization in molecular wires and oligomers.
Biphenylene monolayer: a novel nonbenzenoid carbon allotrope with potential application as an anode material for high-performance sodium-ion batteries
Biphenylene monolayer, a novel carbon allotrope of metallic character, is a promising anode material for high-performance sodium-ion batteries.
On the atomic structure of two-dimensional materials with Janus structures
Difference in the lengths of metal–S and metal–Se bonds and contribution from configurational entropy destabilise Janus-structures and make energetically favorable disordered configurations.
A one-dimensional high-order commensurate phase of tilted molecules
We report on the formation of a quasi-1D high-order commensurate (HOC) structure of dihydro-tetraazapentacene (DHTAP) molecules on a Cu(110)–(2 × 1)O surface and its stabilization through internal degrees of freedoms, namely the molecular tilt.
Non-intersecting ring currents in infinitene
The aromaticity of the newly synthesized infinitene is addressed via analysis of the magnetically induced current density and the induced magnetic field.
Poisoning density functional theory with benchmark sets of difficult systems
“Poison sets” introduced in this work specifically target failures of density functional approximations. They thereby offer insights into hard computational chemistry problems via novel benchmarking strategies.
Direct atomic-scale imaging of a screw dislocation core structure in inorganic halide perovskites
Screw dislocation core structures are characterized with helicoid structures at atomic resolution along a viewing direction perpendicular to the dislocation lines and the screw dislocation line locates at a plane containing Cs and Br atoms in orthorhombic CsBrBr3.
Collision-assisted stripping for determination of microsolvation-dependent protonation sites in hydrated clusters by cryogenic ion trap infrared spectroscopy: the case of benzocaineH+(H2O)n
Protonation sites in hydrated clusters can be clearly determined by CAS-IRPD (collision-assisted stripping infrared photodissociation) spectroscopy as shown for the example of hydrated protonated benzocaine.
Is ethaline a deep eutectic solvent?
The ethaline composition lies in the ChCl-saturated region of the phase diagram which explains why ChCl precipitates in this solvent.
Hourglass Weyl and Dirac nodal line phonons, and drumhead-like and torus phonon surface states in orthorhombic-type KCuS
Hourglass Weyl nodal line phonons and Dirac nodal line phonons coexist in the phonon dispersion of a single material KCuS.
Oxidative evolution of Z/E-diaminotetraphenylethylene
Z/E-Diaminotetraphenylethylene molecules suffer primarily from oxidative evolution rather than recognized isomerization.
Quantum anomalous Hall effect in germanene by proximity coupling to a semiconducting ferromagnetic substrate NiI2
A model Ge/NiI2 van der Waals heterostructure for topological field transistor devices is reported.
Investigating the abnormal conductivity behaviour of divalent cations in low dielectric constant tetraglyme-based electrolytes
The solvation structure and ionic conductivity of Ca(TFSI)2/tetraglyme solutions were studied using a combination of experimental and theoretical approaches. A higher fraction of free ions was detected in solutions with higher molar concentrations.
Enhanced elastic scattering of He2 and He3 from solids by multiple-edge diffraction
We report on a method of enhanced elastic and coherent reflection of 4He2 and 4He3 from a micro-structured solid surface under grazing incidence conditions.
Modulating the Schottky barrier of MXenes/2D SiC contacts via functional groups and biaxial strain: a first-principles study
2D MXene Ti3C2T2 (T=F, O, OH) are employed to serve as electrode for 2D SiC through van der Waals interaction. The Schottky barrier height of contacts can be tuned by changing the functional T group of Ti3C2T2 and applying biaxial strain.
H atom scattering from W(110): A benchmark for molecular dynamics with electronic friction.
Molecular dynamics with electronic friction (MDEF) at the level of the local density friction approximation (LDFA) has been applied to describe electronically non-adiabatic energy transfer accompanying H atom collisions with many solid metal surfaces.
Magnetism and interlayer bonding in pores of Bernal-stacked hexagonal boron nitride
High-energy electron beam creates triangular pores in h-BN. We report the interlayer bonding and electronic structure of nested pores in AB-stacked h-BN, important for applications like DNA sequencing.
Magnetic exchange and valence delocalization in a mixed valence [Fe2+Fe3+Te2]+ complex: insights from theory and interpretations of magnetic and spectroscopic data
A mixed valence tellurium bridged Fe(II)–Fe(III) complex was studied using correlated ab initio methods. Spectroscopic and magnetic properties have been rationalized considering coupling between spins and vibrations.
Mutual effects between single-stranded DNA conformation and Na+–Mg2+ ion competition in mixed salt solutions
Based on the Langevin dynamics simulations of the ssDNA-Na+/Mg2+ systems, we reported the quantitative dependence of both the binding fractions of the excess ions and radii of gyration of ssDNA on ion concentrations.
Revisiting the K-edge X-ray absorption fine structure of Si, Ge–Si alloys, and the isoelectronic series: CuBr, ZnSe, GaAs, and Ge
Extended X-ray absorption fine structure (EXAFS) has evolved into an unprecedented local-structure technique that is routinely used to study materials’ problems in the biological, chemical, and physical sciences.
Accurate core excitation and ionization energies from a state-specific coupled-cluster singles and doubles approach
A proper treatment of orbital relaxation and correlation, while addressing spin contamination and the shortcomings of the CVS, allows ΔCCSD to reach errors smaller than 0.5 eV compared to experimental X-ray absorption excitation energies.
Modulating the intersystem crossing mechanism of anthracene carboxyimide-based photosensitizers via structural adjustments and application as a potent photodynamic therapeutic reagent
ISC mechanism and triplet state properties of anthracene carboxyimide (ACI) were successfully tuned. High triplet yield (ΦΔ = 99%) and long-lived triplet state (τT = 122 μs) was accessed in ACI dyad and application as PDT reagent was explored.
About this collection
Welcome to our online rolling collection of the hottest work published in PCCP. Here we feature all of the 2022 articles highlighted as HOT by our Editors and Referees. Congratulations to all those featured!