Themed collection PCCP 25th Anniversary Issue

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

Quantum-centric high performance computing (QCHPC), which combines the strengths of quantum computing and high performance computing, is anticipated to significantly enhance computational capabilities for solving challenging problems in quantum chemistry.

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.

Most commonly acknowledged as the least reactive element group in the periodic table, noble gases can form complexes under nearly ambient conditions. This Perspective spans their theoretical prediction and bonding categories.

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.

We show how NRT analysis can be modified to unify Pauling-type resonance-theoretic description of electronic interactions from the localized Lewis-structural “molecular” limit to the extreme delocalized limit of supramolecular “soft-matter” aggregation.

Diabatic and adiabatic energy surfaces for rotation-induced electron detachment.

Atomistic discrete interaction models can bridge the size gap between quantum and classical continuum models in addressing nanoparticle plasmonics and give insights into the discrete nature of ultrafine nanoparticles.

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.

Ternary oil–water–surfactant systems can give rise to an O/W microemulsion in equilibrium with excess oil, a W/O microemulsion in equilibrium with excess water, or a bicontinuous microemulsion in equilibrium with excess oil and water.

Understanding the mechanisms underlying the emergence of giant spin splitting (GSS) is fundamental in the pursuit of more robust strategies for designing materials with desired spin splitting.

Some of our recent developments and applications of algorithmic graph theory for extracting the physical and chemical properties of materials from molecular dynamics simulations are presented.

A high-resolution rotational spectroscopy study of the rotational conformers and nuclear spin isomerism of carbonyl diisothiocyanate, a reactive compound that is composed of bosons exclusively.

The simulation of chemical reactions is an anticipated application of quantum computers.

A TD-DFT benchmark study on exciplexes reveals how dispersion-corrected double-hybrids, including the (ω)B2(GP-)PLYP-D3(BJ) functionals, are the most robust approaches. However, the study also shows that there is potential for future improvements.

The behavior of the dynamical electron correlation energy is remarkably complex at short internuclear distances: ΔE_DEC(ΔR) = E_DEC(ΔR) − E_DEC(R = ∞) with ΔR = R − R_e.

Quantum chemical calculations of the anions OAeF⁻ (Ae = Be–Ba) have been carried out using ab initio methods at the CCSD(T)/def2-TZVPP level and density functional theory employing BP86 with various basis sets.

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

This theoretical study demonstrates that molecular plasmons in naphthalene can be effectively modulated through intermolecular interactions and strong light–matter coupling, with synergistic effects observed when these methods are combined.

Enhancements to the Deep Potential network integrate message-passing, achieving high accuracy with significant speed advantages. Applied to solvated electron in bulk water, confirming the cavity model and determining structural properties.

The kinetics and thermodynamics of the electrochemical reactions of redox mediators for lithium–air batteries depend on ionic association strength with Li⁺ ions and on specific pathways, potentially affecting the energetic efficiency of devices.

Electric double-layer capacitance plots on Au(111) are studied to better understand the role of water, cations, and anions, coupled with in situ scanning tunnelling microscopy under electrochemical conditions (ECSTM) to track the mobile surface.

The bonding structures of CO₃Li₃⁺ and CS₃Li₃⁺ are studied by means of oriented quasi-atomic orbitals (QUAOs) to assess the possibility of these molecules being planar hexacoordinated carbon (phC) systems.

The bonding structures of infinitene, the Chemical and Engineering News 2021 Molecule of the Year, is studied by means of oriented quasi-atomic orbitals (QUAOs) to assess the degree of aromaticity within the molecule.

Thermodynamic free energy barrier offered by mycolic acid monolayer for tuberculosis drugs.

The excited state processes of a bacteriophytochrome are studied using high-level multireference methods.

Cycloheptratriene-1-carbonitrile represents a natural next step in the complexity of detected CN-substituted molecules in space. We provide a comprehensive rotational spectroscopy analysis to facilitate its detection in the interstellar medium.

Comparison of the kinetic isotope effect using QM, RPMD and QCT with experimental data.

High level calculations at the MRCI+Q and CCSD(T) levels were used to predict the spectroscopic properties and bond dissociation energy of NiO. A range of DFT functionals were tested and most did not provide good agreement.

Chemical modifications of triangular boron–carbon–nitride (BCN) molecules that remove the central boron atom, but conserve electronic conjugation along the molecular rim, retain the singlet–triplet inversion in these systems.

Using full-dimensional quantum scattering calculations we show strong alignment effects in rotational quenching of HD in cold collisions with D₂.

Molecular transport is an important aspect in metal–organic frameworks (MOFs) as it affects many of their applications, such as adsorption/separation, drug delivery and catalysis.

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.

Our manuscript presents a convenient method for estimating the strength of argentophilic (Ag⋯Ag) and aurophilic (Au⋯Au) interactions using QTAIM parameters.

An algorithmic method of spectral unmixing was devised to extract FRET values of spectrally overlapping dye pairs for single-molecule spectroscopy.

Accurate simulations of transient X-ray photoelectron spectra (XPS) provide unique opportunities to bridge the gap between theory and experiment in understanding the photoactivated dynamics in molecules and materials.

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.

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

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.

An exploration of group two ansa-metallocenes for solvent effects, interannular bridges, and quantitative bond strength through local mode analysis.

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 electronically excited states of dopamine and dopamine-o-quinone adsorbed on graphene-type nanostructures present different charge transfer behaviours, first shows molecule-to-surface, while for the second, surface-to-molecule character.

Hybrid DFT predicts that Fe-doping of NiOOH changes the OER activity from insensitive to highly sensitive to crystal facet.

We present a benchmark set of dimerization energies of “inorganic benzenes” composed of all non-carbon p-block elements of main groups III to VI up to polonium representing a challenge to contemporary quantum chemical methods.

Memristors display hysteresis effects in the form of self-crossing looping current–voltage curves. We show intrinsic dynamic inductor-like (conduction inductance) and capacitance-like (conduction capacitance) behaviours.

Online mass spectrometry of lithium oxygen batteries during linear voltage sweep charge after discharge revealed that LiOH and Li₂CO₃ are generated during discharge in addition to two types of Li₂O₂ which are oxidized in low and high charge voltages.

Ultrafast UV photophysics of adenine and its derivatives are interrogated by XUV-TRPES with a gas-dynamic flat liquid jet.

Phenalenyl growth reactions were studied theoretically. Application of the computed rate constants to all π radicals revealed that the PAH growth proceeds via alternating and sterically diverse acetylene and methyl HACA additions.

Strong correlations identified between barrier heights/widths for concerted proton transfer in cyclic hydrogen bonded clusters and properties of minima (dissociation energies/frequency shifts).

From left to right and top to bottom, the five Ge₂H₂⁺ structures are shown: trans, monobridged, butterfly, germylidene, and linear.

The impact of ionic liquids (ILs) on polar reactions is well recognised, however the impact of ILs on non-polar reactions is less well understood or explored.

Most QM-cluster models of enzymes are constructed based on X-ray crystal structures, which limits comparison to in vivo structure and mechanism. This work introduces an MD to QM-cluster model workflow.

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 reaction of nitrogen, boron, phosphorus and aluminium doped nanographenes (NGs) with CO₂ in the absence/presence of Na⁺ is studied. The Al₃P₃-NG system is the most suitable one for the activation/sequestration of up to three CO₂ molecules.

We explore the simulation of conical intersections (CIs) on quantum devices, setting the groundwork for potential applications in nonadiabatic quantum dynamics within molecular systems.

We find kinetic energy operator (KEO) models based on n-mode expansions to be flexible, systematically improvable and accurate KEO representations in vibrationally correlated calculations in curvilinear coordinate systems.

Electronic structure calculations suggest that reverse intersystem crossing in B and N-doped triangulenes can occur via both direct (spin–orbit coupling) and mediated (spin–vibronic coupling) mechanisms.

Long-lived doubly charged dimers and trimers of krypton and xenon are formed by sequential ionization of doped helium nanodroplets.

Substitution of the transiently chiral cis-1,2-cyclohexanediol (cis-CD) by a phenyl results in (S,S)-(+)-1-phenylcyclohexane-cis-1,2-diol (cis-PCD) and modifies the hydrogen bond pattern in its dimer. The heterochiral preference observed in cis-CD changes for homochiral in cis-PCD.

Sodium chloride clusters show rich structural diversity. Magic cluster sizes like the (NaCl)₄Na⁺ cluster are not always energetically favoured. Their high abundance in mass spectra is explained by their kinetic stability against dissociation.

The OH stretching overtone region of micro-solvated hydronium ions was explored by NIR spectroscopy and anharmonic vibrational simulations.

Impact of the adopted DFT functional on the activation of CO₂ on a set of single-atom catalysts.

C₈₀ and Sc₃N@I_h–C₈₀ can be used as building blocks to assemble stable 2D lattices. These materials possess desired physical properties, including unique electronic band structures, appreciable carrier mobility, strong optical absorption, and anisotropic optical behavior.

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

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.

Due to its sensitivity to the local electronic structure, nuclear spin-induced circular dichroism can be used to gain insight into properties of excited states. New computational tools for its calculation are presented.

This study reports on the high yield of new particle formation (NPF) from the reaction of an alkanolamine commonly used in carbon capture and storage technology, monoethanolamine, with strong atmospherically relevant acid, methanesulfonic acid.

Modeling the interfacial selective first hyperpolarizability at methanol–air interfaces was successfully achieved using the sequential molecular dynamics and quantum chemistry approach.

Targeted modifications of the 1 : 2 Choline-and-geranate (CAGE) structure promote the formation of room-temperature ionic liquid crystals.

Changes in free energy, enthalpy, and entropy for transfer of a solute from the gas phase into solution are computed using Monte Carlo simulations in direct and van't Hoff approaches.