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.

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.

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.

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.

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.

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.

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.

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.

Through calculations of the energy transfer rate using structures from a thermal ensemble, we show that the standard Förster resonance energy transfer theory is capable of describing energy transfer in orthogonally arranged systems.

The development of density functional approximations stands at a crossroads: while machine-learned functionals show potential to surpass their human-designed counterparts, their extrapolation to unseen chemistry lags behind.

The electric-field-driven dynamics of the emerging polar and chiral nematics, dubbed helielectric nematics, have been experimentally and numerically confirmed.

This study illustrated the potential use of a lighter element-based transition metal dichalcogenide (TMD)-like material as a viable candidate for the detection of NO and NO₂ gases with applications in future nanoelectronics.

QM/MM calculations revealed dominant binding modes, keto–enol tautomerization and decarboxylation of oxaloacetate in the active site of macrophomate synthase. The water-assisted tautomerization was calculated to be easier than decarboxylation.

In this work, we report on the effects observed in MAPbI₃ polycrystalline films and solar cells under moderate gamma-ray doses of 3–21 kGy.

Multistep thermal dehydration behavior of inorganic hydrates is regulated by the thermodynamic phase relationship between hydrates and the physico-geometrical kinetic constraints of the component reactions.

A novel high finesse cavity allowing THz CRDS has enabled accurate quantification of CF₄. Yielding spectral parameters with unprecedented precision, these finding are critical to monitor and understand CF₄'s contribution to global radiative forcing.

In the dynamically stepwise reaction pathway C–H insertion versus Cope selectivity is highly influenced by whether or not vibrational synchronization occurs in the nonstatistical entropic intermediate.

The application or removal of CO₂ can simultaneously trigger the switching of two different amines, but only if limitations on basicity and concentration are met.

Simultaneous investigations of first-order transition evolution on different length scales in Langmuir monolayers have revealed that the interfacial line tension plays a significant role for the hierarchy and heterogeneity of monolayer growth.

This study presents a thorough reinvestigation of the B₁₅^+/0/− isomers, first employing coupled-cluster theory CCSD(T) calculations to validate the performance of different DFT functionals.

Well-defined and densely packed tripodal self-assembled monolayers on oxide substrates were formed using a combination of triptycene framework and phosphonic acid anchoring groups. Functional character of these films was demonstrated.

Continued evolution of the SARS-CoV-2 Omicron lineage has led to subvariants, and the mAbs with the potential for immune escape.

The hydroquinone reducing agent is regenerated during the mechanochemical reduction of gold salt to form metal nanoparticles, and it remains active in the chemical reduction process even when used in sub-stoichiometric conditions.

Photoinduced bending of needle crystals caused by photochemical transformation can be used as an extremely sensitive method for studying the kinetics of the transformation.

Quantum-chemical calculations combined with molecular-dynamics simulations reveal mechanisms for improving the quantum yields by which aromatic compounds form their non-aromatic Dewar isomers, with potential implications in solar-energy storage.

We have quantum chemically investigated how microsolvation affects the various E2 and S_N2 pathways, their mutual competition, and the α-effect of the model reaction system HOO⁻(H₂O)_n + CH₃CH₂Cl, at the CCSD(T) level.

A combination of infrared multiple-photon dissociation (IRMPD) action spectroscopy and quantum chemical calculations was employed to investigate the [M,C,2H]⁺ (M = Ru and Rh) species.

The initial decomposition pathways of α-FOX-7 in the condensed phase (crystal) were investigated via density functional theory.

Excited-state proton transfer of a photoacid HPTS becomes solvent-independent in small methanol- and water-in-oil reverse micelles. We attribute anomalous proton transfers from the bulk solutions to the limited solvation dynamics inside the micelles.

Liquid–liquid phase separation (LLPS) plays a pivotal role in the organization and functionality of living cells.

Large Rashba effect and nontrivial topological properties of the Janus mono layers, resulting from inversion symmetry breaking, band-inversion and band anticrossing effects.

The rate coefficient for two deuterium substituted isotopologues of reaction CH₃ + HBr → CH₄ + Br has been determined using the quasiclassical trajectory (QCT) method.

Trimethylamine-N-oxide enhances or suppresses phase separation in aqueous two-phase systems depending on the composition and concentration of phase forming components.

This study investigates if automatically sampling the electron band structure can predict the ease of separating chemically bonded layers by analyzing the relationship between conductivity effective mass and exfoliation energy.

The intricate conformational landscape of a flexible, long-chain fluoroalcohol was explored using rotational spectroscopy and theoretical calculations, revealing synergistic interplay between London dispersion interactions and hydrogen bonds.

Ab initio electron-propagator calculations continue to be useful companions to experimental investigations of electronic structure in molecular anions.

A similarity score of vibrational spectra is proposed to reveal the structures of two conformers of a pentapeptide, acetyl-SIVSF-N-methylamide. One of the conformers is found to be 25 kJ mol⁻¹ less stable than the most stable one.

The photophysical properties of circularly polarized thermally activated delayed fluorescence (CP-TADF) molecules are regulated by adjusting the type of donors.

Simulated indentation experiments reveal how the incident angle and speed affect connective neck formation, material transfer, and structural disruption; important parameters for the mechanochemical cocrystallisation of theophylline and citric acid.

A combination of IR multiple-photon dissociation (IRMPD) action spectroscopy and quantum chemical calculations was employed to investigate the [M,C,2H]⁺ (M = Fe and Co) species.

Dissociation of CO₂ occurs on vicinal Cu surfaces at temperatures between 80 K and 90 K. This is mainly caused by an oxygen-exchange reaction between CO₂ and CO promoted by a small amount of coadsorbed oxygen.

We report the results of the SAMPL9 host–guest blind challenge for predicting binding free energies.

AuTiO_x nanoparticles with a core–shell structure on TiO₂ show improved stability for CO oxidation compared to pure Au nanoparticles.

Understanding the selectivity mechanisms of AKR1B1/10 inhibition through the multiple computational strategies based on selective inhibitor lidorestat and HAHE.

3D Ni–Co-LDH NTA/NGS electrode enhances Li–S battery performance with superior cyclability, rate efficiency, and areal capacity. Defect engineering boosts adsorption and catalysis for improved battery performance.

The hydrogen bonds and π-stacking interactions cling together syringyl and guaiacyl subunits, promoting the formation of stable water-bridged dimeric complexes in S–G and S-lignins.

Mechanisms underlying co-recovery of energy critical metals and carbon mineralization by harnessing organic ligands are uncovered by investigating the influence of chemical and mineral heterogeneity and the morphological transformations of minerals.

Electron induced dissociation of condensed benzene (C₆H₆) in thin films on a Pt substrate is investigated by the electron stimulated desorption of anions and cations. Desorption yields and effective dipolar dissociation cross-sections are obtained.

The role of intersystem crossing (ISC) in the dynamics and kinetics of gas-phase ion–molecule reactions is investigated by a mix of experimental and theoretical methods. We found that ISC can act as a bottleneck even for highly efficient reactions.