Themed collection 2024 PCCP HOT Articles

In this feature article, we use hydrophobic ferrite (Fe₃O₄) nanocrystal shells filled with Au nanocrystals self-assembled into 3D superlattices and dispersed in water.

We describe a first-principles vibrational and rotational mode-specific reaction dynamics approach and its applications for several neutral and anionic systems with positive and negative barriers.

This review focuses on the general strategies for strengthening charge separation and transfer in g-C₃N₄, involving structural modulation, heterojunction construction and cocatalyst loading, and also analyzes their respective characteristics.

The traditional synergy between theory and experiment has been made vulnerable by advances in each realm that require highly specialized expertise. Lessons and recommendations are drawn from reviews of several cases.

We review the progress in low-energy electron collisions with molecular systems relevant to developing new chemo-radiotherapies and provide an experimentalist's perspective of the field.

A detailed chemical understanding of H₂ interactions with binding sites in the nanoporous crystalline structure of metal–organic frameworks (MOFs) can lay a sound basis for the design of new sorbent materials.

Using multiscale models in computational simulations, the collective motion of an array of molecular machines is regulated under external fields.

In pursuing a clean and environmentally friendly future, a magnetic refrigerator based on the magnetocaloric effect has been proposed to replace conventional refrigeration characterized by inefficient energy use and greenhouse gas emissions.

Molecular machines are evolved through changing their field of activity while maintaining their basic functions. Finally, their active field even includes the interface of living organisms.

The formation and properties of smart (stimuli-responsive) membranes are reviewed, with a special focus on temperature and pH triggering of gating to water, ions, polymers, nanoparticles, or other molecules of interest.

We designed and synthesized indanone derivatives with ESIPT, correlated to H-bond strength. Compound 4 shows mechanically induced ESIPT for the first time, with –CF₃–HN– interactions crucial for non-centrosymmetric crystal packing.

Study of the degenerate exchange involving two xenon atoms and a cryptophane via ab initio molecular dynamics reveals a faster reaction rate than for the more simple dissociative mechanism and a self-organization of the cage.

High-throughput ab initio calculations and data-mining reveal Hund's rule to prevail across the chemical space of small organic molecules with systematically varying compositions and structures.

CO-stripping experiments are employed as a highly structure-sensitive and in situ strategy to explore plasmon-enhanced electrooxidation reactions on Pt–Au heterodimers.

An accurate method is proposed to deal with such nonadiabatic transitions as those energetically inaccessible, namely, classically forbidden transitions.

The adsorption behavior of water on the Co(0001) surface at 100 K was studied. Ordered (√3 × √3)R30° D₂O bilayer D-up and D-down configurations were identified, along with their transitions to amorphous ice structures.

Accurate calculated infrared signatures support experimental interpretation. A tailored computational protocol is presented enabling the efficient calculation of anharmonic infrared signatures, as demonstrated for CO and OH stretching vibrations.

A pure spin-current device based on a h-BN/graphene/h-BN van der Waals vertical heterostructure under light irradiation from the top view (a) and the front view (b).

Neutron total scattering reveals that the phase transition in TlTcO₄ is driven by disordering of the Tl⁺ 6s² lone pairs.

A theoretical model has been proposed to study the structure and dynamics of aqueous vanadyl sulfate (VOSO₄) solution used in the conventional flow (CF) through cell design operating under varying thermodynamic conditions.

Two sensitivity analysis techniques are applied to rate coefficients in a kinetic model of a dark molecular cloud, revealing that aromatic species such as cyanonaphthalene are sensitive to early hydrocarbon growth and ring-formation mechanisms.

Here we investigate how structural changes stabilise (or destabilise) indolcarbazole-based diradical systems, demonstrating that they are very useful motifs for dynamic covalent chemistry.

Comprehensive DFT analysis of Diels–Alder reactions between cyclopentadiene and metallofullerenes Sc, Y, and La@C₈₂ and La@C₇₂, considering concerted and stepwise mechanisms.

FASTCAR is a tool allowing an easy exploration of the conformation degrees of freedom along molecular reaction paths, by the automatic pruning of conformers ensembles from CREST via RSMD and frequency evaluations, followed by full DFT optimisations.

The oxidation of the major SEI component Li₂O via the oxidative subsequent SEI formation process is suppressed under the influence of LiNO₃ additive, favoring a dendrite-less surface in the dilute LiTFSI/TEGDME electrolyte.

To aid the interstellar search for OPAHs and gain insights into their microsolvation, we investigated xanthene and its hydrated clusters with up to four water molecules using IR-UV ion dip and broadband rotational spectroscopy.

Femtosecond transient absorption and photophysical studies reveal the photoinduced dynamics in short-wavelength infrared polymethine dyes for bioimaging applications.

The topological surface states change (ΔE_TSS) of MgB₂ with the adsorbates of H is apparently stronger than the adsorbates of OH.

Accurate predictions of the heat of water adsorption and the protonation state requires passing from density functional theory (PBE+D) to wavefunction methods (MP2).

Imidazole's gas-phase oxidation by OH radicals leads to the formation of two major closed-shell products, 4H-imidazol-4-ol and N,N′-diformylformamidine.

Full potential energy curves, electronic configurations, spectroscopic parameters, dipole moments, and energetics of ground and excited electronic states of TaB and WB were studied using MRCI, MRCI+Q, CCSD(T), and DFT levels of theory.

The X–H algorithm is used to reveal the main accepting modes for the IC process. Replacing the H atom in acceptor bonds with appropriate substituents may reduce the IC rate constant and increase the fluorescence quantum yield of porphyrin nanorings.

The absorption spectrum of the hydrogen dimer, (H₂)₂, is detected at room temperature while from its bond dissociation energy of only about 3 cm⁻¹ (∼4.5 K), such a detection was unexpected.

H + CH⁺ reactive collisions are found to be not very efficient at the low temperatures that characterised the interstellar medium.

Extension of the DFT-D3 and -D4 London dispersion corrections to francium, radium, and the full actinides series, with minimal modifications to the existing parameterization strategy.

Liquid-jet photoemission spectroscopy directly probes specific molecular structure of solutes.

A novel S-scheme Zn²⁺ doped C₄N₃ (Zn–C₄N₃)/BiOBr heterostructure with good stability is constructed to efficiently suppress fast recombination of photogenerated electron–hole pairs for efficient photodegradation of tetracycline (TC).

Time-dependent blue shift of action spectra in storage rings are used to determine the radiative cooling rate of naphthalene dimer cations, (C₁₀H₈)₂⁺. DFTB-EXCI and Monte-Carlo models are successful in reproducing infrared cooling temporal evolution.

A combined Raman spectroscopic and quantum chemical investigation provides thermodynamic and structural information of UO₂F⁺, UO₂F₂(aq), UO₂F₃⁻, UO₂F₄²⁻, and UO₂F₅³⁻ in aqueous solution.

Cu and Ru-incorporated ceria catalysts showed low-temperature redox performances in which all three metal species were involved and showed high ammoxidation activity of benzyl alcohol.

Generic frozen solution embedding enables the ab initio prediction of condensed-phase spin-dynamics under realistic conditions for molecules without crystal structures, giving insight into the impact of intramolecular bridging on magnetic relaxation.

A surface tension model is presented applicable to multi-component solutions containing water, salts, organic, and amphiphilic substances in a mixture.

Unprecedented superconductivity is discovered in technetium borides that stay dynamically stable at moderate or even ambient pressure.

DFT calculations show that Ca₂N is the most favourable electrene to insert to eliminate Schottky and tunnelling barriers across Au/MoS₂ or Cu/MoS₂ interfaces.

We propose an LPMI method to calculate the mismatch index heterogeneous ice nucleation. This new method is more physically sound as it considers both the lattice parameters and Miller index.

We present the measurement and analysis of the 2OH stretching band of methanol between 7165 cm⁻¹ and 7230 cm⁻¹ cooled down to 26 ± 12 K in a buffer gas cooling experiment.

Conical intersections (CIs) are often involved in nonadiabatic chemical reactions. We propose a diabatization method, which can effectively handle the significant fluctuations in derivative-couplings caused by CI seams.

Data mining algorithms and Spearman correlation analysis are coupled to DFT calculations in the search for descriptors that drive the stability of NiPd clusters. A unique kind of core–shell segregation is revealed.

This work provides a new understanding of both Lifshitz transition and reversal for p-n carrier sign of 2H-TaS₂.

After the loading of BC, the photoexcited electrons of TiO₂ migrate to BC surface, which is conducive to improving the adsorption-photocatalytic performance for the reduction of Cr(VI) under sunlight irradiation.

U isotope fractionation coefficients were calculated using relativistic electron correlation methods. B3LYP calculations for U(VI)–U(VI) systems agree with experiments, while describing open-shell U(IV) states remains challenging for all the methods.

This study illustrates that the spring-like hydrogen bond acts as a switcher of the PLC–NLC conversion along the crystal b-axis due to its high compressibility at low pressure and incompressibility at high pressure.

The conformational flexibility of ethyl groups manifests in their methyl rotor tunnelling behaviour observed with ESEEM spectroscopy at low temperatures resulting in lower rotation barriers for ethyl groups than for methyl groups in nitroxides.

Chemical ordering is studied in the core and facets of simulated Ni–Pt nanoalloys, with chemical ordering frustrations. Pt surface segregation is enhanced with temperature, and more pronounced in the icosahedral shape compared to truncated octahedral nanoparticles.

An improved version of ORCA's automated generator environment is presented, which is capable of producing well-performing code for highly complex methods, such as multireference coupled-cluster and analytic nuclear gradients for correlation methods.

Production of a singlet state oxywater species and its transition to hydrogen peroxide using quantum mechanical calculations.

Photoinduced NO linkage isomers: total charges on NO are not correlated to the frequency of the NO stretching vibration. Local force constants reveal a significant change in coupling of Ru–N/O and N–O stretching vibrations.

The detergent combination of H₂O₂/NH₃ is predicted to have the highest detoxification efficiency toward A-234, where the timely-formed hydrogen-bond network between the detergent combination and A-234 improves the decontamination efficiency.

Investigating the effects of compositional and structural changes of interfacial SiO_x and TiO₂ films on the surface passivation and its correlation with the charge transfer (CT) across the TiO₂–Si interface.

In asymmetric supercapacitors, transition metal selenates are promising electrodes, but their capacity is limited by a single redox center.

Fukui function for nucleophilic attack on H₂CO in a parallel magnetic field showing a significantly reduced Bürgi–Dunitz angle.

This study reports on the temperature dependence of the surface morphology of amorphous solid water (ASW) and the variation in the local contact potential difference depending on its surface morphology.

Defects are ubiquitous in the atomically thin limit. Machine learning models, including XGBoost and DenseNet, predict mechanical behavior of defective 2D-TMDCs (stress–strain response), aiding in understanding structure–property relations.

In this paper, we propose a new two-step strategy for computing ro-vibrational energy levels and wavefunctions of a triatomic molecule and apply it to CO₂.

A theoretical model is proposed that allows the estimation of the quantum yield of phosphorescence of dye molecules in the vicinity of plasmonic nanoparticles.

Assesses the performance of DFT for atomization energies using a big-data set of 122 000 small drug-like molecules relative to CCSD(T) reference values. B3LYP emerges as the best performer (MAD = 4.1 kcal mol⁻¹) followed by M06-L (MAD = 6.2 kcal mol⁻¹).

The chromium doped nitrogen clusters are studied by mass spectrometry technique and DFT calculations.

Investigation of solvation effects emphasizes the importance of including explicit and implicit solvent for accurate DFT predictions on ion exchange.

We study the supramolecular interaction between ubiquitin and lanthanide complexes by paramagnetic NMR and molecular dynamics. Our observations shed new light on the dynamic interaction processes between these complexes and the surface of the protein.

In this work, we utilized accurate electronic structure theory to study the structure, stability, bonding, electronic properties, collision cross-section, and electrical mobilities of AgO_kH_m^± clusters, where k and m range from 1 to 4.