Themed collection 2020 PCCP HOT Articles
Using anion photoelectron spectroscopy of cluster models to gain insights into mechanisms of catalyst-mediated H2 production from water
Anion PE spectroscopy and DFT calculations reveal molecular and electronic structural features of cluster models for catalysis.
The role of electron–nuclear coupling on multi-state photoelectron spectra, scattering processes and phase transitions
This article presents development of first principle based Beyond Born–Oppenheimer theory and its applications in conjunction with Jahn–Teller theory.
Coupled transport of electrons and protons in a bacterial cytochrome c oxidase—DFT calculated properties compared to structures and spectroscopies
DFT calculated structures, vibrational frequencies, and energies provide insights into the reaction/proton pumping cycle of cytochrome c oxidase.
Assessing cluster models of solvation for the description of vibrational circular dichroism spectra: synergy between static and dynamic approaches
Solvation effects are essential for defining the shape of vibrational circular dichroism (VCD) spectra.
Phonon, thermal, and thermo-optical properties of halide perovskites
Halide perovskites possess unusual phonon and thermal properties, which lead to unique thermo-optical responses very different from those of conventional inorganic semiconductors.
Energy conversion based on superhydrophobic surfaces
Different forms of energy conversion based on superhydrophobic surfaces.
Molecular recognition at the air–water interface: nanoarchitectonic design and physicochemical understanding
Significant enhancements of binding constants for molecular recognition are observed at the air–water interface, which would be related to molecular recognition in biomolecular systems.
Emerging trends in the dynamics of polyelectrolyte complexes
Polyelectrolyte complexes (PECs) exhibit varying dynamic responses depending upon the ionic strength, water content, temperature, pH, and molecular weight.
Theory and algorithms for chiroptical properties and spectroscopies of aqueous systems
We review an atomistic, fully polarizable approach to accurately predict the chiroptical properties of molecular systems in aqueous solution, by retaining all relevant physico-chemical interactions.
Recent progress in use and observation of surface hydrogen migration over metal oxides
An overview of catalysis related to hydrogen spillover, surface protonics, analysis techniques for hydrogen migration, and low-temperature catalysis using surface protonics are summarized.
2D materials towards ultrafast photonic applications
Two-dimensional materials are now excelling in yet another arena of ultrafast photonics, including optical modulation through optical limiting/mode-locking, photodetectors, optical communications, integrated miniaturized all-optical devices, etc.
Reorganization energies and spectral densities for electron transfer problems in charge transport materials
Various contributions to the outer reorganization energy of an electron transfer system and their theoretical and computational aspects have been discussed.
Multifaceted aspects of charge transfer
Charge transfer is vital for life on Earth and makes our modern ways of living possible.
Asymmetric reactions induced by electron spin polarization
Spin polarized electrons can control asymmetric electrochemical reactions.
Nanoparticles influence miscibility in LCST polymer blends: from fundamental perspective to current applications
Polymer blending is an effective method that can be used to fabricate new versatile materials with enhanced properties.
Theoretical model for predicting thermoelectric properties of tin chalcogenides
Accelerated prediction of thermoelectric properties by a simple theoretical modelling.
Soft XAS as an in situ technique for the study of heterogeneous catalysts
Perspectives on the use of soft X-ray absorption spectroscopy as a tool to rationally develop new heterogeneous catalysts.
Quantum state and surface-site-resolved studies of methane chemisorption by vibrational spectroscopies
Infrared spectroscopic methods enable quantum-state-specific and surface-site-selective studies of methane chemisorption on stepped platinum surfaces.
Large cluster ions: soft local probes and tools for organic and bio surfaces
Large cluster projectiles boost molecular sensitivity in mass spectrometry and open new avenues for physical characterization and nanofabrication.
Piecewise linearity, freedom from self-interaction, and a Coulomb asymptotic potential: three related yet inequivalent properties of the exact density functional
Three properties of the exact energy functional of DFT are important in general and for spectroscopy in particular, but are not necessarily obeyed by approximate functionals. We explain what they are, why they are important, and how they are related yet inequivalent.
Orientational ordering in heteroepitaxial water ice on metal surfaces
Sum frequency generation spectroscopy uncovers the orientational ordering in crystalline ice films of water grown on Pt(111) and Rh(111).
Morphology control, spectrum modification and extended optical applications of rare earth ion doped phosphors
This review summarizes the morphology control strategy, phase transfer theory, spectrum modulation, and extended optical applications of RE3+-doped phosphors.
Rotational–vibrational resonance states
All molecular systems possess a significant number of rovibrational resonance states accessible via spectroscopic and scattering experiments, which can also be computed and rationalized by a variety of first-principles quantum-chemical techniques.
Hexagonal rare-earth manganites and ferrites: a review of improper ferroelectricity, magnetoelectric coupling, and unusual domain walls
In this review, the multiferroic properties, vortex domain patterns and non-stoichiometric effect in hexagonal rare-earth manganites and ferrites are discussed.
Metal–organic framework-based nanomaterials for photocatalytic hydrogen peroxide production
Metal–organic frameworks act as efficient photocatalysts for visible-light driven hydrogen peroxide production in a single-phase system and two-phase system.
Probing radical–molecule interactions with a second generation energy decomposition analysis of DFT calculations using absolutely localized molecular orbitals
Proper treatment of intermolecular complexes formed by radicals and closed-shell molecules in energy decomposition analysis of DFT calculations.
Single-molecule functionality in electronic components based on orbital resonances
A gateable single-molecule diode and resonant tunneling diode are realized using molecular orbital engineering in multi-site molecules.
Intramolecular vibrational energy redistribution and the quantum ergodicity transition: a phase space perspective
The onset of facile intramolecular vibrational energy flow can be related to features in the connected network of anharmonic resonances in the classical phase space.
Universal crossed beam imaging studies of polyatomic reaction dynamics
Crossed-beam imaging studies of polyatomic reactions show surprising dynamics not anticipated by extrapolation from smaller model systems.
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.
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.
What is “many-body” dispersion and should I worry about it?
“Many-body” dispersion can refer to two distinct phenomena, here termed electronic and atomic many-body effects, both of which cause the dispersion energy to be non-additive.
Designing water splitting catalysts using rules of thumb: advantages, dangers and alternatives
Breaking the OH–OOH scaling relation does not necessarily enhance water splitting electrocatalysis. Seeking “electrocatalytic symmetry” is a suitable alternative.
The challenging playground of astrochemistry: an integrated rotational spectroscopy – quantum chemistry strategy
Astrochemistry: toward the molecular complexity in the interstellar medium.
High throughput sequencing of in vitro selections of mRNA-displayed peptides: data analysis and applications
High-throughput sequencing (HTS) of mRNA display selection of functional peptides.
Probing ultracold chemistry using ion spectrometry
Reactions between KRb molecules at sub-microkelvin temperatures were probed using ion spectrometry.
Approaches to mid-infrared, super-resolution imaging and spectroscopy
Modern microscopy to access super-resolution infrared absorption of materials.
A review of mathematical representations of biomolecular data
Recently, machine learning (ML) has established itself in various worldwide benchmarking competitions in computational biology, including Critical Assessment of Structure Prediction (CASP) and Drug Design Data Resource (D3R) Grand Challenges.
Spin-flip methods in quantum chemistry
This perspective discusses, theory, applications, and recent developments of spin-flip methods in quantum chemistry.
From atoms to aerosols: probing clusters and nanoparticles with synchrotron based mass spectrometry and X-ray spectroscopy
Synchrotron radiation provides insight into spectroscopy and dynamics in clusters and nanoparticles.
Distance dependent energy transfer dynamics from a molecular donor to a zeolitic imidazolate framework acceptor
An ultrathin Al2O3 layer deposited between RuN3 and ZIF-67 by ALD can finely control the energy transfer efficiency between them.
Electronegativity equalization: taming an old problem with new tools
Electronegativity equalization is examined after understanding an atom-in-a-molecule as an open quantum system, characterized by a variable fluctuating number of electrons whose average is set through charge-constrained electronic structure calculations.
Solubilization power of surfactant-free microemulsions
An octanol/ethanol/water surfactant-free microemulsion solvates hydrophobic propane in small octanol/ethanol aggregates similar to traditional micelles.
Light and electric field induced unusual large-scale charge separation in hybrid semiconductor objects
Charge separation can be achieved over very long distances in semiconductors by combining bipolar electrochemistry with UV irradiation.
Rationalising the influence of solvent choice on the porosity of conjugated microporous polymers
A design strategy for high surface area CMPs is to choose a solvent that minimises miscibility of solvent and reactants.
A probabilistic spin annihilation method for quantum chemical calculations on quantum computers
A probabilistic spin annihilation method based on the quantum phase estimation algorithm is presented for quantum chemical calculations on quantum computers.
Synergistic effect of two action sites on a nitrogen-doped carbon catalyst towards acetylene hydrochlorination
In this work, the dynamic reaction pathways of nitrogen-doped carbon catalysts are investigated in acetylene hydrochlorination.
Site-dependent selectivity in oxidation reactions on single Pt nanoparticles
Site-dependent selectivity in oxidation reactions on Pt nanoparticles was identified by conducting IR nanospectroscopy measurements while using allyl-functionalized N-heterocyclic carbenes (allyl-NHCs) as probe molecules.
New insights into the radiolytic stability of metal(IV) phosphonate hybrid adsorbent materials
The dependence of radiolytic stability on both the organic and inorganic components of hybrid materials is explained.
A neutron irradiation-induced displacement damage of indium vacancies in α-In2Se3 nanoflakes
The discovery of layered two-dimensional (2D) ferroelectric materials has promoted the development of miniaturized and highly integrated ferroelectric electronics.
Excimer-origin CPL vs. monomer-origin magnetic CPL in photo-excited chiral binaphthyl-ester-pyrenes: critical role of ester direction
1 exhibited opposite Py excimer-origin CPL in chloroform and PMMA film. 2 exhibited mirror-symmetric Py-monomer-origin MCPL.
In cell Gd3+-based site-directed spin labeling and EPR spectroscopy of eGFP
A newly synthesized Gd3+ chelate complex allows in cell spin labeling and detection of eGFP by EPR spectroscopy.
Structural characterization of molybdenum–dinitrogen complex as key species toward ammonia formation by dispersive XAFS spectroscopy
Dispersive XAFS (DXAFS) was used for the structural characterization of a hardly-isolatable molybdenum–dinitrogen complex bearing a PNP-type pincer ligand.
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.
Spectroscopic characterisation of radical polyinterhalogen molecules
Spectroscopic characterisations of the radical polyinterhalogen molecules IF2 and I2F are reported using anion photoelectron spectroscopy.
Controlling the emission frequency of graphene nanoribbon emitters based on spatially excited topological boundary states
Graphene nanoribbons (GNRs) with atomically precise heterojunction interfaces are exploited as nanoscale light emitting devices with modulable emission frequencies.
Linear free energy relationships for transition metal chemistry: case study of CH activation with copper–oxygen complexes
We propose a computational framework for developing Taft-like linear free energy relationships to characterize steric effects on the catalytic activity of transition metal complexes.
Real-time degradation dynamics of hydrated per- and polyfluoroalkyl substances (PFASs) in the presence of excess electrons
Per- and polyfluoroalkyl substances (PFASs) are harmful man-made chemicals that have contaminated several drinking water resources worldwide. Our work provides the first real-time assessment of PFAS degradation in the presence of excess electrons.
Combining site-directed spin labeling in vivo and in-cell EPR distance determination
Non-canonical amino acid incorporation via amber stop codon suppression and in vivo site-directed spin labeling allow in-cell EPR distance determination in E. coli.
On the development of a gold-standard potential energy surface for the OH− + CH3I reaction
We develop the first accurate full-dimensional ab initio PES for the OH− + CH3I SN2 and proton-transfer reactions treating the failure of CCSD(T) at certain geometries.
The nanoscopic principles of capacitive ion sensing interfaces
Herein we discuss the operational principles of molecular interfaces that specifically recruit ions from an electrolyte solution and report this in a reagentless capacitive manner.
In situ environmental TEM observation of two-stage shrinking of Cu2O islands on Cu(100) during methanol reduction
A distinct two-stage reduction of Cu2O islands under methanol is revealed via combined in situ ETEM, statistical analysis, and DFT calculations.
Basis set dependence of SO stretching frequencies and its consequences for IR and VCD spectra predictions
Using chiral tosylates as model systems we evaluate the effect of diffuse and polarization functions on the quality of predicted VCD and IR spectra. Polarization functions on sulfur are shown to be important to reliable determine ACs using VCD.
Spectrally tunable nanocomposite metamaterials as near-perfect emitters for mid-infrared thermal radiation management
Nanocomposite absorbers possess a simple structure and tailorable absorption in the mid-infrared (MIR) region achieved by manipulating structural parameters.
The structure and hydrogen-bond properties of N-alkyl-N-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide and DMSO mixtures
Mixing ionic liquids (ILs) with cosolvents can extend the practical applications of ILs and overcome the drawbacks of neat ILs. Studies on the structure and hydrogen-bond interaction properties of IL–cosolvent mixtures is essential for chemical applications.
Segregation tendencies of transition-metal dopants in wide band gap semiconductor nanowires
The segregation tendency of an impurity in a semiconductor nanowire can be tuned by adjusting the Fermi level position.
Ion-specific interactions at calcite–brine interfaces: a nano-scale study of the surface charge development and preferential binding of polar hydrocarbons
This research provides an atomic-level insight into the synergic contribution of mono- and divalent ions to interfacial environment of calcite surfaces exposed to electrolyte solutions containing organic compounds.
Dynamic solvent effects in radical–radical coupling reactions: an almost bottleable localised singlet diradical
The lifetime of a localised singlet diradical with bulky substituents was extended using the dynamic solvent effect and reached an almost bottleable timescale of ∼2 s under extremely viscous conditions induced by high pressure.
The diffusion of doxorubicin drug molecules in silica nanoslits is non-Gaussian, intermittent and anticorrelated
The motion of the confined doxorubicin drug molecule exhibits an interesting combination of anomalous diffusion features.
Influence of the Coriolis effect on the properties of scattering resonances in symmetric and asymmetric isotopomers of ozone
This work analyzes rotational–vibrational spectra of scattering resonances in four ozone isotopomers in relation to the symmetry-driven isotope effect.
About this collection
Welcome to our online rolling collection of the hottest work published in PCCP. Here we feature all the 2020 PCCP articles highlighted as HOT by the handling editor or our referees. Congratulations to all the authors whose articles are featured.