Themed collection PCCP 25th Anniversary Issue

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.

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.

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

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.

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.

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.

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.

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.

Formation of cluster-based materials requires a fundamental understanding of the resulting cluster aggregation processes.

Contrary to prior assumptions, the global minimum structure of B₅H₅ is not quasi-planar but rather an asymmetrical three-dimensional form.

The axial–equatorial equilibrium in mono-substituted cyclohexanes, governed by the interplay of London dispersion and steric repulsion, is a textbook example that many density functional approximations cannot easily handle.

DS-DN incorporated DNA bound to Taq.

Dynamical conformational change of DS–DN incorporated DNA forming both WCF and nWCF conformers with SYN and ANTI orientations.

State-of-the-art quasi-Newton unitary optimizer with trust-region (QUOTR) is nearly as efficient as the reference method for simple cases and is more robust for complex cases such as proteins with zero HOMO–LUMO gap in semilocal Kohn–Sham DFT.

The limited activation of O₂ on Cu₅ clusters supported on CHA zeolite favors the selective oxidation of methane to methanol.

The calculated energy inversion of the first excited states of a heptazine phenylthiolate molecule is consistent with the intense blue fluorescence in the solid state and in toluene solution.

Conformations of organic radical–solvent complexes are vibrationally assigned by comparison to related closed-shell complexes.

Computation of accurate geometrical structures and spectroscopic properties of large flexible molecules in the gas-phase is tackled at an affordable cost using a general exploration/exploitation strategy.

Through simply incorporating phenyl rings into experimental molecules, two new TADF emitters are designed. The luminescence color of TADF emitters is modulated from green to blue emission, and k_r and k_RISC are also enhanced.

Joint photoelectron spectroscopy and first-principles theory investigations indicate that the Pb-doped PbB₂(BO)_n⁻ clusters (n = 0−2) undergo a transformation from σ + π doubly aromatic triangle PbB₂⁻ to PbB₄(BO)₂^−/0 complexes with a B≡B triple bond.

The TiO₂/Ti₂AlNb interface bonding interactions and the effects of alloying elements were investigated via first principles calculations. Sc, Zr, and Hf are beneficial for inhibiting oxide spalling.

The work describes the in-depth experimental and computational investigation of a novel series of enantiomerically pure, circularly polarized emitters based on tris-carbonyl Re(I) complexes.

n-Cyanoindole fluorescent probes hydrogen bonded with one or two water molecules can form cyclic or non-cyclic structures. These structures can lead to excited state proton or hydrogen transfer to the solvent molecules.

Nonadiabatic quantum dynamics sheds light on the non-monotonic energy dependence of the branching fractions of N₂.

1D potential along the ring puckering coordinate of cyclobutyl radical represents a double minimum well with a shallow barrier. The equilibrium structure is predicted to be a puckered geometry while the transition state reflects a planar geometry.

Mechanism of ionic dissociation of HCl in the smallest water clusters was proposed on the basis of direct ab initio MD calculations.

The CC2 electronic-structure method is applied to dipole-bound, quadrupole-bound, and correlation-bound anions.

The intramolecular H-bonding networks in protonated and deprotonated 3-hydroxyglutaric acid feature intriguing correlated proton dynamics and distinct diffuse vibrational signatures.

A relativistic coupled-cluster study of RaOH pertinent to its spectroscopic detection and laser cooling is reported.