Themed collection 2021 PCCP HOT Articles
Spectroscopic analysis focusing on ionic liquid/metal electrode and organic semiconductor interfaces in an electrochemical environment
Attenuated total reflectance ultraviolet spectroscopy can facilitate access to ionic liquid/solid substrate interfaces in an electrochemical environment.
Morphological design strategies to tailor out-of-plane charge transport in conjugated polymer systems for device applications
The transport of charge carriers throughout an active conjugated polymer (CP) host, characterized by a heterogeneous morphology of locally varying degrees of order and disorder, profoundly influences the performance of CP-based electronic devices.
Computational elucidations on the role of vibrations in energy transfer processes of photosynthetic complexes
This perspective provides accounts on recent studies regarding the role of vibrations toward energy transfers in photosynthetic complexes. The latest developments in simulation techniques are also reviewed with an outlook to future directions.
Rotational action spectroscopy of trapped molecular ions
Rotational action spectroscopy is an experimental method in which rotational spectra of molecules, typically in the microwave to sub-mm-wave domain of the electromagnetic spectrum (∼1–1000 GHz), are recorded by action spectroscopy.
Rechargeable aqueous zinc–bromine batteries: an overview and future perspectives
We review the past and present investigations on ZBBs, discuss the key problems and technical challenges, and propose perspectives for the future, with the focus on materials and chemistry.
On the fate of high-resolution electron energy loss spectroscopy (HREELS), a versatile probe to detect surface excitations: will the Phoenix rise again?
High-resolution electron energy loss spectroscopy is a powerful tool to investigate surface excitations (vibrations of chemisorbed atoms and molecules, phonons, plasmons). Here, a perspective on the status and the future perspectives of HREELS is presented.
Phonon transport in graphene based materials
Graphene, due to its atomic layer structure, has the highest room temperature thermal conductivity k for all known materials and many excellent thermal properties.
Unravelling the role of charge transfer state during ultrafast intersystem crossing in compact organic chromophores
The role of the intermolecular charge transfer state during ultrafast intersystem crossing in compact chromophores is revealed by spectroscopy and theoretical investigations.
The electron-transfer intermediates of the oxygen evolution reaction (OER) as polarons by in situ spectroscopy
The conversion of diffusive forms of energy (electrical and light) into short, compact chemical bonds by catalytic reactions regularly involves moving a carrier from an environment that favors delocalization to one that favors localization.
High-fidelity first principles nonadiabaticity: diabatization, analytic representation of global diabatic potential energy matrices, and quantum dynamics
This Perspective discusses recent advances in constructing high fidelity diabatic potential energy matrices for nonadiabatic systems and the associated quantum dynamics.
The rise of X-ray spectroscopies for unveiling the functional mechanisms in batteries
Synchrotron-based X-ray spectroscopies have been key tools in the discovery, understanding, and development of battery materials. In this Perspective review, their state-of-the-art is highlighted, with special emphasis on future trends and needs.
Studying 2D materials with advanced Raman spectroscopy: CARS, SRS and TERS
Perspectives on advancing our understanding of two-dimensional materials using coherent anti-Stokes (CARS), stimulated (SRS) and tip-enhanced (TERS) Raman spectroscopy techniques.
Digital-intellectual design of microporous organic polymers
In this perspective, we propose digital-intellectual materials design as the fifth stage of materials design and present its overview of microporous polymers.
Solubilities in aqueous nitrate solutions that appear to reverse the law of mass action
Non-ideal aqueous electrolyte solutions have been studied since the start of the application of thermodynamics to chemistry in the late 19th century.
High-performance lithium–sulfur batteries enabled by regulating Li2S deposition
This perspective highlights the significance of regulating Li2S deposition and the related methods in improving the performance of lithium–sulfur batteries.
Understanding the molecular mechanisms of transcriptional bursting
Microscopic origins of transcriptional bursting phenomena are discussed from the physical–chemical point of view.
2D ferroelectric devices: working principles and research progress
Due to their unique reversible polarization, 2D ferroelectrics are promising for nanodevice applications in ferroelectric field effect transistors, diodes and tunnel junctions.
Single-layer carbon nitride: synthesis, structure, photophysical/photochemical properties, and applications
This Perspective provides a critical summary of the current state of the art in the synthesis and properties of polyheptazine single-layer carbon nitride (SLCN).
Kinetics of photon upconversion by triplet–triplet annihilation: a comprehensive tutorial
Kinetics of triplet–triplet annihilation photon upconversion is organized from the basics for non-experts and experts. From self-consistent analyses of the tangled photophysical events, many important and useful relations are derived and summarized.
Progress in phase-sensitive sum frequency generation spectroscopy
Representative methods of surface-selective phase-sensitive sum frequency generation spectroscopy are reviewed in terms of interferometer implementation for optical heterodyne detection.
Integration of theory, simulation, artificial intelligence and virtual reality: a four-pillar approach for reconciling accuracy and interpretability in computational spectroscopy
A general “four-pillar strategy” (theory, simulation, machine learning and augemented reality/virtual reality) to integrate computational and experimental spectroscopy.
Modern multireference methods and their application in transition metal chemistry
Modern multireference methods open up the possibility to treat complicated transition metal systems on a physically sound basis.
The π-hole revisited
Two views of the computed electrostatic potential on the 0.001 au surface of 2,4,6-trifluoro-1,3,5-triazine. Red is the most positive color range, while blue is the most negative.
Electron spin dynamics in excited state photochemistry: recent development in the study of intersystem crossing and charge transfer in organic compounds
Recent developments of electron spin dynamics in organic molecular systems studied by time-resolved electron paramagnetic spectroscopy are summarized.
Homogeneous nucleation of sheared liquids: advances and insights from simulations and theory
Computational approaches for analyzing the homogeneous nucleation of sheared simple liquids are reviewed. We examine underlying mechanisms and effects of flow. The experimental scope and sheared nucleation of polymers and glasses are also covered.
Phenothiazine functional materials for organic optoelectronic applications
This prospective provides a brief overview of the working principles of various optoelectronic devices and the structure–property relationships in phenothiazine.
Energy storage electrochromic devices in the era of intelligent automation
A catalog summary and capacity comparison of ECESDs.
Weak covalent interactions and anionic charge-sharing polymerisation in cluster environments
How solvation obstructs charge sharing and limits the size of covalently bound core anions in clusters.
Perspective on computational reaction prediction using machine learning methods in heterogeneous catalysis
Machine learning algorithms can facilitate the reaction prediction in heterogeneous catalysis.
Design and perspective of amorphous metal nanoparticles from laser synthesis and processing
Pulsed laser strategies (i.e. pulsed laser ablation and fragmentation in liquid) have been reviewed with a focus on the synthesis and processing of amorphous metal nanoparticles. The possible formation criteria and mechanism have been discussed.
Improved insights in time-resolved photoelectron imaging
We review new light source developments and data analysis considerations relevant to the time-resolved photoelectron imaging technique. Case studies illustrate how these themes may enhance understanding in studies of excited state molecular dynamics.
Ordered mesoporous metal oxides for electrochemical applications: correlation between structure, electrical properties and device performance
In this Perspective, the authors review the interplay between structure and charge-transport properties of mesoporous metal oxides, with an emphasis on applications in electrochemical energy storage, catalysis and gas sensing.
Computational approaches to dissociative chemisorption on metals: towards chemical accuracy
The theoretical description of dissociative chemisorption of isolated molecules on metal surfaces is discussed. Emphasis is put on methods that deliver chemical accuracy for the dissociative chemisorption probability S0, so that Δ ≤ 1 kcal mol−1.
Substance and shadow of formamidinium lead triiodide based solar cells
We shed light on the compositional, surface engineering and crystallization kinetics manipulations for FAPbI3 followed by a proposition for unified testing protocols in order to scale-up the solar cells from the lab to the market.
Ultrafast photoinduced dynamics in Prussian blue analogues
A review on ultrafast photoinduced processes in molecule-based magnets with an emphasis on Prussian blue analogues.
First-principles calculations of hybrid inorganic–organic interfaces: from state-of-the-art to best practice
This work highlights the challenges and problems when modelling inorganic–organic interfaces and provides practical tips and suggestions for efficient calculations.
Grazing incidence fast atom diffraction, similarities and differences with thermal energy atom scattering (TEAS)
In the elastic regime, GIFAD is equivalent to TEAS with an effective energy E⊥ between 1 meV and 1 eV providing a high sensitivity to topology and to attractive forces. The inelastic regime merges to the classical limit and is still in development.
Metal clusters synthesized in helium droplets: structure and dynamics from experiment and theory
In this Perspective we present the state of the art of creating mixed metal clusters in the superfluid droplet environment and their investigation through a successful interplay between experimental characterization and theoretical modelling.
Understanding the structure, bonding and reactions of nanocrystalline semiconductors: a novel high-resolution instrumental method of solid-state synchronous luminescence spectroscopy
Solid-state synchronous luminescence spectroscopy (SS-SLS) is a novel high-resolution method to study the absorption and emission of light, electronic structure, and reactions of nanocrystalline semiconductors.
Microfluidic technologies for the synthesis and manipulation of biomimetic membranous nano-assemblies
A mini-review of microfluidic technologies for the generation and manipulation of biomimetic nano-assemblies, including perspectives for future research directions.
Recent progress in the development of thermal interface materials: a review
Recent progress in the development of thermal interface materials.
Viscosity models for ionic liquids and their mixtures
Review of principles and limitations of viscosity models for ionic liquids and their mixtures focusing on the use of inappropriate mixing rules for molten salts.
Ultrafast processes: coordination chemistry and quantum theory
The correlation between electronic densities and active molecular vibrations drives the spin–vibronic mechanism of ultrafast decays in coordination chemistry.
Thermal enhancement of upconversion emission in nanocrystals: a comprehensive summary
Thermal enhancement of upconversion luminescence in lanthanide-doped nanocrystals are summarized and the enhancement mechanism is discussed in detail with a fresh perspective.
Integration of global ring currents using the Ampère–Maxwell law
We present a method based on Ampère–Maxwell's integral law for calculating strengths of magnetically induced ring currents.
Threshold photoelectron spectroscopy of iminoborane, HBNH
A threshold photoelectron spectrum of HBNH is reported, recorded using synchrotron radiation.
Cas12a target search and cleavage on force-stretched DNA
CRISPR-Cas12a target search and cleavage on force-stretched λ-DNA using optical tweezers.
Unraveling electronic band structure of narrow-bandgap p–n nanojunctions in heterostructured nanowires
Direct comparison of bandgaps of GaSb zinc blende and wurtzite polytypes (0.75 and 0.84 eV, respectively) by means of valence electron energy-loss spectroscopy (VEELS) in a transmission electron microscope (TEM).
Localized orbital locator as a descriptor for quantification and digital presentation of lone pairs: benchmark calculations of 4-substituted pyridines
The parameters of the (3,−3) critical point in the localized orbital locator topology reflect the changes in the size, density and electron energy of the nitrogen lone pair and correlate with the complexation energy.
Low-frequency vibrational spectroscopy: a new tool for revealing crystalline magnetic structures in iron phosphate crystals
In this report, the strong-dependence of low-frequency (terahertz) vibrational dynamics on weak and long-range forces in crystals is leveraged to determine the bulk magnetic configuration of iron phosphate – a promising material for cathodes in lithium ion batteries.
Rigorous analysis of the interaction between proteins and low water-solubility drugs by qNMR-aided NMR titration experiments
We have developed a new NMR spectroscopic method to rigorously quantify the interaction between a low water-solubility drug and its target protein by accurate estimation of precipitation using quantitative NMR (qNMR).
Lifting the discrepancy between experimental results and the theoretical predictions for the catalytic activity of RuO2(110) towards oxygen evolution reaction
The high catalytic activity of RuO2(110) towards the oxygen evolution reaction is explained theoretically by considering an alternate reaction pathway for this catalyst.
Impact of vibronic coupling effects on light-driven charge transfer in pyrene-functionalized middle and large-sized metalloid gold nanoclusters from Ehrenfest dynamics
Ehrenfest dynamics study describing the photoinduced charge transfer in metalloid gold nanoclusters.
Reconciling experimental and theoretical vibrational deactivation in low-energy O + N2 collisions
The large vibrational deactivation, experimentally found in low-energy O + N2 collisions, is quantitatively reproduced only using a vibronic mechanism.
Universal description of steric hindrance in flexible polymer gels
Steric effects on solute diffusion in flexible polymer gels can be described by a very simple mathematical rule.
Small matrix modular path integral: iterative quantum dynamics in space and time
This work presents a small matrix decomposition of the modular path integral for spin arrays or molecular aggregates, which leads to an iterative treatment with respect to the units that comprise the system and the propagation time.
Size dependence of the dissociation process of spherical hydrate particles via microsecond molecular dynamics simulations
The dissociation process of spherical sII mixed methane–propane hydrate particles in liquid hydrocarbon was investigated via microsecond-long molecular dynamics simulations.
Should a hotter paramagnet transform quicker to a ferromagnet? Monte Carlo simulation results for Ising model
A hotter paramagnet relaxes to a ferromagnetic state faster than a colder one, resembling the counter-intutive Mpemba effect in water-ice transition.
Is a transition metal–silicon quadruple bond viable?
Quadruple bonding in heavier main group elements is not known albeit having four valence orbitals accessible for bonding.
Polaron-formation revealed by transient XUV imaginary refractive index changes in different iron compounds
We report different polaron trap depths in hematite and akageneite measured by transient XUV reflection–absorption spectroscopy.
The interplay between spatial and heliconical orientational order in twist-bend nematic materials
In sulfur containing liquid crystal dimers we find that at the transition to the NTB phase the positional correlation length drops. The nanoscale periodicity was also observed in the upper range of a smectic phase that forms below the NTB state.
Revealing scenarios of interzeolite conversion from FAU to AEI through the variation of starting materials
A prior dealumination was proven effective to modify the structure of the initial FAU and consequently facilitate its conversion to the AEI. Based on the obtained results, we proposed a scheme of the interzeolite conversion from FAU to AEI.
Unleashing the shape of L-DOPA at last
Four different conformers have been revealed in the supersonic expansion for the amino acid and supramolecular synthone L-DOPA (see figure), rejecting its previously reported conformational restriction. The role of the N-H···π interactions have been thoroughly described.
Natural reaction orbitals for characterizing electron transfer responsive to nuclear coordinate displacement
Natural reaction orbitals, a new molecular orbital analysis method, enable automated extraction of reactive orbitals and analysis of electron transfer.
Threshold photoelectron spectroscopy of 9-methyladenine: theory and experiment
TPES spectroscopy is used to unveil the complex vibronic structure of 9-methyladenine cations.
Pulsed-ramped-field-ionization zero-kinetic-energy photoelectron spectroscopy: a methodological advance
A new method is proposed to record photoelectron spectra based on the well-established pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopy technique and inspired by the data treatment employed in slow photoelectron spectroscopy.
Interaction of nanoparticles with lipid films: the role of symmetry and shape anisotropy
Topological effects are key in driving nano-bio interface phenomena: the symmetry of the lipid membrane (cubic or lamellar) dictates the interaction mechanism, while nanoparticles shape (sphere or rod) modulates the interaction strength.
Electrolyte buffering species as oxygen donor shuttles in CO electrooxidation
Electrolyte buffering species are shown to act as oxygen donor in the carbon monoxide electrooxidation
Quantitative electronic structure and work-function changes of liquid water induced by solute
Significant differences are observed in liquid-water's lowest electron binding energy with increasing solute concentration in archetypal aqueous solutions. For NaI(aq) and TBAI(aq), the energy changes extend to +0.3 eV and −0.7 eV, respectively.
Concentration-dependent ion correlations impact the electrochemical behavior of calcium battery electrolytes
Emergent calcium battery electrolytes in ethereal solvents exhibit concentration-dependent ion correlations involving significant second-shell interactions. These interactions have a strong influence on both conductivity and metal cycling efficiency.
About this collection
Welcome to our online rolling collection of the hottest work published in PCCP. Here we feature all of the 2021 articles highlighted as HOT by our Editors and Referees. Congratulations to all those featured!