The foreword to this special issue of the Journal dedicated to Professor Graham Chandler provides an account of his distinguished career in theoretical chemistry and also describes his many scientific achievements.

This study investigated the motivations and attitudes of two student cohorts enrolled in an introductory chemistry unit, which Emeritus Professor Graham Chandler helped to create. An interview with Graham describes the origins of this unit. Therefore, this study has particular interest in this special issue celebrating Graham’s career in chemistry.

Ingenol-3-angelate is a potent anticancer compound. This work uses double-hybrid density functional theory to investigate the reaction mechanisms (uncatalysed and water-catalysed) for acyl rearrangements in this compound. These rearrangements may affect the potency of the drug and its shelf-life. We find that a water catalyst leads to a significant reduction in the reaction barrier heights for the acyl migrations.

Electronic effects, not sterics, dominate the site selectivity of ruthenium coordination compounds.

The bonding situation and resonance in the nitrate anion NO₃⁻ in comparison with the related species nitric acid HNO₃, FNO₃, and KNO₃ are investigated with a set of modern bonding descriptors from experiment and theory. Usefulness and limitations of the simple Lewis model are revealed by quantitatively assessing the weights of the Lewis structures as well as the non-Lewis contributions.

The S66 benchmark for non-covalent interactions has been re-evaluated using explicitly correlated methods with basis sets near the one-particle basis set limit. We were able to establish convergence to the basis set limit on all components. The best compromises between accuracy and computational cost are graphically represented above.

In this paper, we explore the influence of ring size and composition on thermal and photochemical eliminative cyclization reactions.

A ‘consistent-conformation-pathway’ approach to the study of hydrogen-abstraction reactions of small peptide models provides information that may be more relevant to larger peptides and proteins than the information obtained by the more commonly used ‘minimum-energy-structure pathway’ approach.

Gas phase complexes formed between halide anions and the nitric oxide molecule are investigated via ab initio calculations, mass spectrometry, and photoelectron spectroscopy. Experimental electron binding energies are provided, along with predicted geometries and binding energies for the clusters.

Our DFT study reveals mechanistic details of nickel-catalyzed three-component coupling for transforming CO₂ into a homoallylic alcohol. Our results point towards several key factors for an efficient reaction, and reaffirm the utility of computational modelling in the design of advanced reactions.

The structural diversity in polymorphs of the flexible molecule ROY challenges computational attempts to predict or rationalize their relative stability. This work explores the reliability of CE-B3LYP estimates of relative lattice energies combined with conformational energy differences.

This is the first report on the bromination of acridine since 1954. The bromination of acridine made in concentrated sulfuric acid and also acetic acid afforded only two species containing one bromine, with 4-bromoacridine the major product in sulfuric acid and 2-bromoacridine the major product in acetic acid. Knowing the substitutional patterns for electrophilic substitution in aza-aromatic compounds is important fundamental information.

Ruthenium half-sandwich complexes are central in a wide range of diverse applications in the field of organometallic chemistry. As such, exploration of their preparation and reactivity is crucial for development of their chemistry. We present alternative synthetic methods for Cp*Ru(dppm)Cl, Cp*Ru(dppe)Cl, Cp*Ru(dppf)Cl, [Cp*Ru(COD)(MeCN)]⁺, and [Cp*Ru(bpy)(MeCN)]⁺ starting from the easily accessible [Cp*Ru(η⁶-C₁₀H₈)]⁺.

Formulae for the static electronic polarizability and hyperpolarizability are derived in terms of moments of the ground-state electron density matrix and then tested against coupled-perturbed Hartree-Fock results for a set of 40 donor-π-acceptor systems. For the polarizability, the correlation is reasonable; by constrast, the results for the hyperpolarizabilities are poor, not even within one or two orders of magnitude.

A simple, multigram-scale preparation of 1,4-bis(trimethylsilyl)buta-1,3-diyne that minimises risks associated with the preparation of this useful compound is reported.

The reaction mechanism involved in the exothermic carbon isotope-exchange reaction ¹³C¹²CS + H → ¹²C¹³CS + H was determined by means of highly accurate ab initio calculations.