Glass polymorphism and liquid–liquid phase transition in aqueous solutions: experiments and computer simulations
Water is an intriguing substance. It shows sharp and reversible transitions between amorphous ices and, possibly, a liquid–liquid phase transition. Here, we discuss how this behavior is altered by the addition of solutes, such as salts and alcohols.
Structure of the aqueous electron
A cavity or excluded-volume structure best explains the experimental properties of the aqueous or “hydrated” electron.
Scanning probe microscopy for real-space observations of local chemical reactions induced by a localized surface plasmon
Scanning probe microscopy techniques providing mechanistic insights into chemical reactions induced by localized surface plasmon on the basis of real-space observations.
Characterization of chemically modified gold and silver clusters in gas phase
This perspective summarizes our recent efforts in the application of gas-phase characterization methods to ligand-protected Au/Ag clusters chemically synthesized with atomic precision.
Ultrafast probes at the interfaces of solar energy conversion materials
Transient reflection, photoreflectance and attenuated total reflection spectroscopy are developed to understand the ultrafast interfacial dynamics of solar conversion materials.
Ionic-surfactants-based thermotropic liquid crystals
Ionic surfactants can be combined with various functional groups through electrostatic interaction, resulting in a series of thermotropic liquid crystals (TLCs).
Photoinduced C–H bond fission in prototypical organic molecules and radicals
We survey and assess current knowledge regarding the primary photochemistry of hydrocarbon molecules and radicals.
Bayesian machine learning for quantum molecular dynamics
This article discusses applications of Bayesian machine learning for quantum molecular dynamics.
Vibrational sum-frequency generation spectroscopy of electrode surfaces: studying the mechanisms of sustainable fuel generation and utilisation
The electrocatalytic oxidation of water coupled to the reduction of carbon dioxide, to make carbon based products, or the reduction of protons to provide hydrogen, offers a sustainable route to generating useful fuels.
2D oxides on metal materials: concepts, status, and perspectives
Two-dimensional oxide-on-metal materials: concepts, methods, and link to technological applications, with 5 subtopics: structural motifs, robustness, catalysis, ternaries, and nanopatterning.
Two-dimensional supramolecular crystal engineering: chirality manipulation
This review summarizes the recent progress in chirality manipulation on 2D supramolecular crystal engineering.
Locality of conical intersections in semiconductor nanomaterials
We review recent efforts to model nonradiative recombination in semiconductor nanoparticles through conical intersections, focusing on the reasons for and consequences of the locality of such intersections.
Opportunities and challenges for electrochemistry in studying the electronic structure of nanocrystals
We review the state-of-the-art of determining the electronic structure of nanocrystals in thin films by electrochemistry and emphasize the benefits of correlating electrochemical with spectroscopic methods to this end.
Time-resolved radiation chemistry: femtosecond photoelectron spectroscopy of electron attachment and photodissociation dynamics in iodide–nucleobase clusters
The pump pulse initiates intracluster charge transfer, creating transient nucleobase anions that model DNA damage pathways induced by low-energy electron attachment.
Electrochemical hydrogenation of non-aromatic carboxylic acid derivatives as a sustainable synthesis process: from catalyst design to device construction
Electrochemical hydrogenation of a carboxylic acid using water as a hydrogen source is an environmentally friendly synthetic process for upgrading bio-based chemicals.
Density-based descriptors and exciton analyses for visualizing and understanding the electronic structure of excited states
Quantum-chemical exciton analysis allows for quantitative, yet facile characterization of excited-state electronic structure and advanced multi-parameter benchmarking.
Modulating the intrinsic reactivity of molecules through non-covalent interactions
Non-covalent interactions as tools for modifying molecular properties.
The canonical behavior of the entropic component of thermodynamic effective molarity. An attempt at unifying covalent and noncovalent cyclizations
The statistically corrected entropic component of effective molarity (EMS*) complies with the “canonical” values expressed by the log plot of EMS* vs. the number n of single bonds in the ring product.
Enhancement of electron accepting ability of para-benzoquinone by a single water molecule
Electron acceptors built upon the para-benzoquinone (pBQ) electro-phore are ubiquitous in nature.
Hydrate nucleation and growth on water droplets acoustically-levitated in high-pressure natural gas
We present the first quantitative measurements of hydrate formation probability, nucleation rate and growth on a water droplet suspended within a high pressure natural gas by acoustic levitation.
Large volume liquid state scalar Overhauser dynamic nuclear polarization at high magnetic field
Dynamic Nuclear Polarization (DNP) can increase the sensitivity of Nuclear Magnetic Resonance (NMR), but it is challenging in the liquid state at high magnetic fields.
Pyridine–acetaldehyde, a molecular balance to explore the n→π* interaction
Weak n→π* and C–H⋯O interactions determine the structure of pyridine–acetaldehyde adduct. The n→π* distance oscillates with the methyl group internal rotation which acts as a sort of molecular balance to explore the n→π* interaction energy.
How flexible is the disulfide linker? A combined rotational–computational investigation of diallyl disulfide
The symmetrically substituted diallyl disulfide adopts an asymmetric conformation in the gas phase, as observed in the rotational spectrum.
Unique reactivity of B in B[Ge9Y3]3 (Y = H, CH3, BO, CN): formation of a Lewis base
Boron compounds usually exhibit Lewis acidity at the boron center due to the presence of vacant p-orbitals. But using Zintl-ion based groups (Ge9Y3, Y = H, CH3, BO, CN), we can alter Lewis acid nature of B to a Lewis base.
Why is the cubic structure preferred in newly formed ice?
The structure of liquid water promotes the formation of ice in which the content of the cubic structure is higher than the content of the hexagonal structure.
Controlled deuterium labelling of imidazolium ionic liquids to probe the fine structure of the electrical double layer using neutron reflectometry
The electrical double layer structure formed in an ionic liquid electrolyte was determined by combining the neutron reflectivity and deuterium labelling techniques.
Triplet dynamic nuclear polarization of nanocrystals dispersed in water at room temperature
Room-temperature triplet dynamic nuclear polarization (triplet-DNP) of nanocrystals dispersed in water is achieved for the first time.
New two-dimensional carbon nitride allotrope with 1 : 1 stoichiometry featuring spine-like structures: a structural and electronic DFT-D study
In this communication the prediction of a two-dimensional carbon nitride allotrope (CN) featuring a 1 : 1 stoichiometry is considered.
Unusual temperature-sensitive excimer fluorescence from discrete π–π dimer stacking of anthracene in a crystal
An unusual blue shift in excimer fluorescence with increasing temperature was observed from a crystal with a discrete π–π anthracene dimer.
Threshold photoelectron spectrum of the CH2OO Criegee intermediate
We present the photoelectron spectroscopy of the simplest Criegee intermediate, CH2OO, close to the first ionization energy.
Valuable structure-size relationships for tadpole-shaped single-chain nanoparticles with long and short flexible tails unveiled
Tadpole-shaped single-chain nanoparticles (TSCNPs) are useful soft building blocks for nanotechnology composed of a flexible polymer chain tethered to an intramolecularly folded single-chain nanoparticle.
Enhancing electrocatalysis for hydrogen production over CoP catalyst by strain: a density functional theory study
The facet-dependent strain effects on the hydrogen evolution reaction catalyzed by CoP were studied using density functional theory methods.
Detailed electronic structure of a high-spin cobalt(II) complex determined from NMR and THz-EPR spectroscopy
Here we report a combined use of THz-EPR and paramagnetic NMR spectroscopy for obtaining a detailed electronic structure of a high-spin cobalt(II) complex.
Endohedral metal-nitride cluster ordering in metallofullerene–NiII(OEP) complexes and crystals: a theoretical study
The ordering of endohedral clusterfullerenes Sc3N@C80 and YSc2N@C80 co-crystallized with Ni(OEP) and isolated complexes with Ni(OEP) have been investigated theoretically.
Structural and magnetic studies of KOsO4, a 5d1 quantum magnet oxide
The quantum magnet KOsO4 has been characterized by a combination of X-ray and neutron diffraction techniques. This represents the first structural and magnetic characterization of a simple Os7+, S = 1/2 oxide system.
Surface-mediated spin dynamics probed by optical-pump–probe scanning tunneling microscopy
In current materials science and technologies, surface effects on carrier and spin dynamics in functional materials and devices are of great importance.
Cu(II)-nanoparticle-derived structures under CO2 reduction conditions: a matter of shape
We investigate the structural evolution of Cu(OH)2 nanoparticle-derived electrodes under CO2 electroreduction conditions and its effect on their electrocatalytic performance.
Parahydrogen-induced polarization with a metal-free P–P biradicaloid
The activation of parahydrogen by a metal-free P–P biradicaloid leads to 1H and 31P nuclear spin hyperpolarization.
The application of the surface energy based solubility parameter theory for the rational design of polymer-functionalized MWCNTs
Solubility parameter theories can be used to model the degree of polymer functionalization of MWCNTs in different solvent media.
Reaction of chloride anion with atomic oxygen in aqueous solutions: can cold plasma help in chemistry research?
The reaction between atomic oxygen and chloride anion in aqueous solutions exposed to cold plasma was investigated experimentally and computationally.
High-resolution rotational Raman spectroscopy of benzene
A time-domain laser experiment resolved spectra for benzene with single-MHz resolution, a 100-fold improvement on literature data.
Fullerene and endometallofullerene Kagome lattices with symmetry-forced spin frustration
Salts of fullerene C60˙− (1) and endometallofullerene Sc3N@Ih-C80˙− (2) radical anions with the Bu3MeP+ cation were obtained. These radical anions form Kagome lattices with equilateral fullerene triangles. The strong antiferromagnetic coupling of spins in 1 and 2 without magnetic ordering down to 1.5–1.9 K indicates strong spin frustration.
Rate constants for the N(2D) + C2H2 reaction over the 50–296 K temperature range
The reactions of metastable atomic nitrogen N(2D) are important processes in the gas-phase chemistry of several planetary atmospheres.
Combined co-solvent and pressure effect on kinetics of a peptide hydrolysis: an activity-based approach
An activity-based approach to predict combined influence of pressure and co-solvent on enzymatic reaction kinetics is presented.
The ionization energy of the vinyl radical: a Mexican standoff with a happy ending
Theoretical approaches and experimental spectra are confirmed as the origin transition is shown to be forbidden in vinyl photoionization.
Nanocavity effects of various zeolite frameworks on n-pentane cracking to light olefins: combination studies of DFT calculations and experiments
Better control of light olefin product selectivity (ethylene and propylene) on various zeolite frameworks (H-FER, H-ZSM-5 and H-FAU) obtained from n-pentane catalytic cracking has attracted considerable attention from both scientific and petrochemical industrial viewpoints.
Deconvolution of BIL-SFG and DL-SFG spectroscopic signals reveals order/disorder of water at the elusive aqueous silica interface
Through the prism of the rather controversial and elusive silica/water interface, ab initio DFT-based molecular dynamics simulations of the structure and non-linear SFG spectroscopy of the interface are analysed.
Revealing the thermodynamics of individual catalytic steps based on temperature-dependent single-particle nanocatalysis
Due to the intrinsic heterogeneity of nanocatalysis, many underlying catalytic details on nanocatalysts are hidden in ensemble-averaged measurements.
β12-Borophene becomes a semiconductor and semimetal via a perpendicular electric field and dilute charged impurity
In this paper, the possible electronic phase transitions of β12-borophene crystal are examined using a five-band tight-binding calculation.
Investigation of glycerol hydrogen-bonding networks in choline chloride/glycerol eutectic-forming liquids using neutron diffraction
Neutron scattering reveals the persistent three-dimensional hydrogen-bonding network between glycerol molecules in the 1 : 2 choline chloride/glycerol eutectic.
Beyond the Coulson–Fischer point: characterizing single excitation CI and TDDFT for excited states in single bond dissociations
HF/DFT orbitals spin-polarize when single bonds are stretched past the Coulson–Fischer point. We report unphysical features in the excited state potential energy surfaces predicted by CIS/TDDFT in this regime, and characterize their origin.
Efficient thermal- and photocatalysts made of Au nanoparticles on MgAl-layered double hydroxides for energy and environmental applications
We compared the effect of the surfactant PVP on the catalyst and found that Au/MgAl-LDHs had better catalytic activity than (PVP@Au)/MgAl-LDHs.
Photo induced chemical modification of surface ligands for aggregation and luminescence modulation of copper nanoclusters in the presence of oxygen
Photooxidation of ligands stabilizing copper nanoclusters for modulation of luminescence.
A type-II C2N/α-Te van der Waals heterojunction with improved optical properties by external perturbation
The C2N/α-Te vdW heterojunction possessed a unique type-II band alignment, tunable band gap, improved optical absorption strength, and broad spectrum width (ultraviolet to near-infrared).
NbB12−: a new member of half-sandwich type doped boron clusters with high stability
The global minimum structure of a NbB12− cluster of half-sandwich type.
Synthesis of a photo-responsive single-walled nanoscroll and its photo-reactivity in a nano-layered microenvironment
Novel photo-responsive single-walled nanoscroll (SWNS) of niobate has been synthesized with quantitative estimation of the yield by the intercalation of cationic polyfluorinated surfactant molecules having azobenzene chromophore.
CO2 adsorption on hydroxylated In2O3(110)
Co-adsorption of H2 modifies CO2 activation on In2O3(110).
NMR shifts in aluminosilicate glasses via machine learning
Machine learning (ML) approaches are investigated for the prediction of nuclear magnetic resonance (NMR) shifts in aluminosilicate glasses, for which NMR has proven to be a cutting-edge method over the last decade.
Growth and stability of Pt nanoclusters from 1 to 50 atoms on h-BN/Rh(111)
We investigated growth and temperature stability of Pt nanoclusters from 1 to 50 atoms on h-BN/Rh(111) using high-resolution XPS and STM.
Impact of effective polarisability models on the near-field interaction of dissolved greenhouse gases at ice and air interfaces
The microscopic behaviour of neutral and dissolved particles near the boundary interface has been investigated. Depending on the applied excess polarisability model the results change dramatically from attraction to repulsion.
Two-dimensional infrared spectroscopy from the gas to liquid phase: density dependent J-scrambling, vibrational relaxation, and the onset of liquid character
Ultrafast 2DIR reveals rotational relaxation rates, critical slowing effects, and co-existence of free rotor and liquid populations in supercritical fluids.
A DNP-hyperpolarized solid-state water NMR MASER: observation and qualitative analysis
Observation and theoretical analysis of an NMR MASER of hyperpolarized 1H nuclei by dynamic nuclear polarization (DNP) at 1.2 K and in a magnetic field of 6.7 T are presented in this study.
Ultrafast polaron-pair dynamics in a poly(3-hexylthiophene-2,5-diyl) device influenced by a static electric field: insights into electric-field-related charge loss
Photogenerated polaron-pair ultrafast dynamics in poly(3-hexylthiophene)-based devices are found to be influenced by external electric fields via delayed field-induced singlet exciton dissociation, yielding a bimolecular decay contribution.
Mechanistic insight into photocrosslinking reaction between triplet state 4-thiopyrimidine and thymine
Multiple nonadiabatic pathways greatly facilitate the proceeding of photocrosslinking reactions between 4-thiopyrimidine and thymine.
A theoretical investigation on boron–ligand cooperation to activate molecular hydrogen by a frustrated Lewis pair and subsequent reduction of carbon dioxide
Activation of molecular hydrogen by a B/N frustrated Lewis pair.
Phase transition and electronic properties of skutterudite-type IrP3 under high pressure
We present an extensive global structural optimization to identify the crystal structures of IrP3 using the developed CALYPSO method under both ambient and high-pressure conditions.
Cm3+/Eu3+ induced structural, mechanistic and functional implications for calmodulin
Trivalent lanthanide and actinide can strongly bind to calmodulin (CaM). The global structure of Ln/An-bound CaM were found to be similar to Ca-CaM but the local environment around Ln/An is distorted giving less structural rigidity to Ln/An-CaM.
Ab initio spectroscopy of water under electric fields
IR and Raman spectra of bulk liquid water under intense electric fields reveal the contraction of both spectra and the onset of a novel high-frequency librational mode band. Moreover, the water structure evolves toward “ice-like” arrangements.
Periodically-arrayed ferroelectric nanostructures induced by dislocation structures in strontium titanate
A new engineering method of ferroelectric nanostructures: ferroelectric nanostructures induced and controlled by dislocation arrangements in SrTiO3.
Dependency of f states in fluorite-type XO2 (X = Ce, Th, U) on the stability and electronic state of doped transition metals
Transition metals (TMs) exhibit different quantum-mechanical oxidation state (OSqm) population when doped into fluorite-type CeO2, ThO2 and UO2.
About this collection
Welcome to our online rolling collection of the hottest work published in PCCP. Here we feature all the 2019 PCCP articles highlighted as HOT by the handling editor or our referees. Congratulations to all the authors whose articles are featured.