Themed collection 2024 PCCP HOT Articles

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.

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.

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.

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.

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.

In this work, we develop a novel capacitive humidity sensor based on Al–Si acceptor–donor co-doped SnO₂ for real-time monitoring of ambient humidity and human respiration.

π–π coupling between neighbouring aromatic molecules with rigid structure can be enhanced by the bias voltage, clarifying that the regulating effect, regardless of the structural flexibility, originates from the changes of the molecular dipole moment.

In the hydrogenation of LA to GVL catalyzed by RuCl₃ in aqueous solution, CO₂ promotes the Ru–OH bond cleavage in [RuOH]²⁺ owing to its Lewis acidity.

A low level of water in fuel gas enhances the adsorption of NH₃ and potentially the reaction rate of SCR of NO_x. A high level of water decreases the Lewis acidity and the adsorption of NH₃, and hinders the removal rate of NO_x.

Hydration water dynamics, structure, and thermodynamics are crucially important to understand and predict water-mediated properties at molecular interfaces.

What is the mechanism of photodissociation of the PyH–NH₃ complex into the radicals Py and NH₄ – impulsive hydrogen transfer, electron coupled proton transfer, or fragmentation after thermalization in the excited state? A molecular beam study.

This study showed that the combination of weak hydrogen bonding and strong electrostatic contributions in hydrated PRL and LID could play an important role in inducing the anti-plasticizing effect of water on those drugs.

HER activities and hydrogen adsorption energies on the surface sites of AuPt alloys are almost neighbor independent. The d-band properties show little impact on the adsorption strengths at the element-specific surface sites.

Protonated ions of fucose-containing oligosaccharides needs a mobile proton to undergo internal glycan rearrangement. Immobilizing a proton in a strong hydrogen bond inhibits the rearrangement.

Constructing Z-scheme heterojunctions incorporating an exquisite hollow structure is an effective performance regulation strategy for the realization of high quantum efficiency and a strong redox ability over photocatalysts.

The addition of ligand O affects the charge distribution of the metal centers in V_nO⁺ (n = 1−9) cluster cations, resulting in a significant increase in the cluster reactivity. The agostic interaction determines the size-dependent reactivity of V_nO⁺ cluster cations. This study provides a novel approach for improving the reactivity of early 3d transition metals.

BaTiO₃–TiO₂ hollow spheres were synthesized for efficient MWDT in cancer treatment, enabling precise tumor elimination with minimal damage to healthy tissues by enhancing production of ROSs upon microwave triggering.

We investigate, for a range of laser-pulse parameters, the efficacy of phase-only pulse shaping for the dissociation of HeH⁺. The numerical results show that pulse shaping is most effective at low pulse energies and broad spectral bandwidths.

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

A systematic study of Ag⁺-ion conducting behaviour in AgBr-doped AgI/mesoporous alumina (MPA) composites was conducted. The highest conductivity was found when the AgBr content was 10 mol% (1.6 × 10⁻³ S cm⁻¹ at 25 °C).

In this article, we analyze polarization-dependent effects in vibrational absorption spectra of 2D finite-size adsorbate islands on dielectric substrates. Using a multi-scale approach, we predict the transition from finite-size islands to a monolayer.

The second-order nonlinear optical (NLO) responses of a donor–acceptor stenhouse adduct (DASA) are investigated by using a computational approach combining molecular dynamics simulations and density functional theory (DFT) calculations.

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.

Simultaneous Bi to Pb substitution and Cu vacancies enhance power factor, increasing zT. Lattice thermal conductivity, crucial for zT_max, is greatly influenced by synthesis method.

Arachno-type geometries have been validated for Sn₁₄TM (with TM = Cr, Mn, Fe) by cryogenic electric beam deflection. Variable temperature Stern–Gerlach experiments reveal that Sn₁₄Cr is a singlet, Sn₁₄Mn a doublet and Sn₁₄Fe most probably a triplet.

This work presents the influence of molecular self-assembly of dibrominated hexaphenylbenzene (Br₂-HPB) on the on-surface polymerization reactions on Au(111) substrate.

The scarcity of superhard materials with magnetism or a narrow band gap, and their potential applications in various fields, makes it desirable to design such materials.

The active hydrogen on the anion allows [P₄₄₄₂][Hy] to be a potential CO₂-responsive molecular switch, in contrast to its role on the cation. [P₄₄₄₂]₂[Hy] without active hydrogen on the anion shows good CO₂ capture and conversion.

Benchmark of LC-TD-DFTB to investigate the excited state properties of a non-fullerene electron acceptor. The tight-binding method is highly dependent on the long-range parameter but reproduced LC-TD-DFT results and experimental absorption spectra.

Tunneling splittings in vibrationally excited states of the water trimer are calculated considering the flips of free OH bonds and five bifurcation mechanisms that break and reform hydrogen bonds in the trimer ring.

We report the experimental observation and spectroscopic characterization, and structure and bonding analyses of copper–borozene complexes.

To scrutinise the impact of electric fields on the structure and vibrations of biomolecules in the presence of water, we study the sequential solvation of lithium diglycine up to three water molecules with cryogenic infrared action spectroscopy.

Mechanochemical reactivity suggests an interesting parallel between equimolar Al–Ni powder mixtures and multilayers.

The all-solid Z-type heterostructure photoanode achieved a photocurrent density of 5.30 mA cm⁻² and a charge separation efficiency rising up to 85% at 1.23 V vs. RHE. These can be majorly attributed to the acceleration of the hydrolysis kinetics.

Electronic spectra are measured for cryogenically cooled HC_2n+1H⁺ chains containing between 5 and 13 carbon atoms.

The gas-phase infrared spectra of neutral carbon clusters are measured in a wide spectral range.

TMAO effectively immobilizes surrounding water molecules through forming complexes. Hyper-Raman spectroscopy enables us to observe that collective motions of water are much more restricted, revealed by the librational modes of water.