Concluding remarks: Reaction mechanisms in catalysis: perspectives and prospects

We consider the current status of our understanding of reaction mechanisms in catalysis in the light of the papers presented in this Discussion. We identify some of the challenges in both theoretical and experimental studies, which we illustrate by considering three key reactions

A COMPARISON OF DEFECT ENERGIES IN MGO USING MOTT-LITTLETON AND QUANTUM-MECHANICAL PROCEDURES

The authors compare the predictions of Mott-Littleton calculations, based on empirical interatomic potentials, with predictions based on self-consistent solutions of the Schrodinger equation for embedded clusters. Simple vacancy and substitutional defects in MgO are modelled using both the classical Mott-Littleton and quantum mechanical methods. Particular attention is paid to the size of the quantum mechanical cluster, the different ways that polarisation is taken into account and the choice of basis set. Results are presented for closed-shell systems only, namely V"Mg and Vo vacancies and for Li'Mg, Na'Mg, AlMg, Fo and Clo substitutional impurities. They find a respectable level of agreement between the quite distinct approaches. This both validates the classical calculations and indicates useful generalisations combining the two approache

A tribute to the scientific career of Neville Greaves: the Daresbury years

We present a personal account of both the developments in technique and instrumentation led by Neville Greaves and the scientific applications which they enabled. We focus on the pioneering period at the Synchrotron Radiation Source, Daresbury in the 1980s and 90s. We discuss and illustrate the lasting impact of these key developments on chemistry, materials and catalytic scienc

GEOMETRY AND CHARGE-DISTRIBUTION OF H-CENTERS IN THE FLUORITE STRUCTURE

The analysis of experimental optical and spin-resonance data for the H centre gives a consistent picture of the local geometry and one-electron wavefunctions. One of the two ions in the F2- molecular ion remains very close to the perfect lattice site the other is at a distance close to that found in other F2- centres. This analysis is confirmed by atomistic calculations using the HADES code. The results are used to give a preliminary analysis of the self-trapped exciton data

Prediction of Rate Constants for Catalytic Reactions with Chemical Accuracy

Ex machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources

Computational and materials structural science

The themes of materials and computation continue to grow and diversify in IUCrJ, but with a continuing emphasis on unravelling the structural science of complex functional materials and on developing further understanding of structure–property relations. The recent articles in the journal highlight both developments in technique and approach, as well as the exploration of new classes of system and of problems

An experimental and computational IR and hybrid DFT-D3 study of the conformations of l-lactic and acrylic acid: new insight into the dehydration mechanism of lactic acid to acrylic acid

We have studied using hybrid Density Functional Theory (DFT) with an aug-cc-pVTZ basis set and D3 dispersion corrections the intra-molecular hydrogen bond of L-lactic acid and L-lactic-acid analogs with the hydroxyl group on the alpha carbon atom substituted by α-XH (where X = S, Se, Te) as well as the conformations of acrylic acid. The results show that there are three types of intramolecular hydrogen bonds that can form only when α-OH is present, whereas other less electronegative functional groups such as –SH, –SeH and –TeH do not exhibit the formation of an intramolecular H-bond. We show that the intra-molecular H-bond formed between the alpha-OH hydrogen and the COOH carbonyl oxygen would enhance the rate of nucleophilic substitution of alpha-OH at the K+ sites in the previously suggested dehydration mechanism of L-lactic to acrylic acids. We find that a temperature range between 190 and 210 °C would be optimum to maximise the rate of nucleophilic substitution of the alpha-OH group at the potassium sites during the dehydration mechanism of L-lactic acid to acrylic acid. Additionally, our hybrid-DFT simulation of the infrared spectrum of the various conformers shows that the lowest energy conformer can be identified by a single vibrational band at 3734 cm−1 whereas for the other conformers, this vibrational band is split with Δν that ranges between 6 cm−1 and 176 cm−1. We also find that the various conformers of acrylic acid can be identified by a double peak for the C[double bond, length as m-dash]O and O–H vibrations, which have Δν′ and Δν′′ values of 24 and 42 cm−1, respectively. This computational study is useful for spectroscopic experimental efforts that try to identify the various conformers of L-lactic acid and acrylic acid and to gain mechanistic insight into the dehydration mechanism over K substituted NaY zeolites

Efficient and accurate approach to modeling the microstructure and defect properties of LaCoO3

Complex perovskite oxides are promising materials for cathode layers in solid oxide fuel cells. Such materials have intricate electronic, magnetic, and crystalline structures that prove challenging to model accurately. We analyze a wide range of standard density functional theory approaches to modeling a highly promising system, the perovskite LaCoO3, focusing on optimizing the Hubbard U parameter to treat the self-interaction of the B-site cation's d states, in order to determine the most appropriate method to study defect formation and the effect of spin on local structure. By calculating structural and electronic properties for different magnetic states we determine that U=4 eV for Co in LaCoO3 agrees best with available experiments. We demonstrate that the generalized gradient approximation (PBEsol+U) is most appropriate for studying structure versus spin state, while the local density approximation (LDA+U) is most appropriate for determining accurate energetics for defect properties

Microscopic origin of the optical processes in blue sapphire

Al2O3 changes from transparent to a range of intense colours depending on the chemical impurities present. In blue sapphire, Fe and Ti are incorporated; however, the chemical process that gives rise to the colour has long been debated. Atomistic modelling identifies charge transfer from Ti(III) to Fe(III) as being responsible for the characteristic blue appearance

QM/MM study of the stability of dimethyl ether in zeolites H-ZSM-5 and H-Y

The methanol-to-hydrocarbons (MTH) process transforms C1 carbon sources to higher hydrocarbons, but details of the mechanism that leads to the formation of the first carbon–carbon bond remain unclear. Here, we present a computational investigation of how a crucial intermediate, dimethyl ether (DME), interacts with different zeolite catalysts (H-ZSM-5, H-Y) to gain insight into the initial stages in the MTH process. We use QM/MM computational simulations to model the conversion of methanol to DME in H-ZSM-5, which is a well characterised and important reaction intermediate. We analyse and compare the stability of DME on several acid sites in H-ZSM-5 and H-Y, and show that the more acidic and open “intersection sites” in the H-ZSM-5 framework are able to bond strongest with DME, with complete deprotonation of the acid site occurring. The conversion of methanol to DME in H-ZSM-5 is calculated as requiring a higher activation energy than framework methoxylation, which indicates that a stepwise (indirect) mechanism, through a methoxy intermediate, is the most likely route to DME formation during the initiation of the MTH process