Development and application of a possible mechanism for the generation of cis-pinic acid from the ozonolysis of α- and β-pinene
- M. Jenkin, D. Shallcross, J. Harvey
The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol
- J. Müller, Zhen Liu, V. S. Nguyen, T. Stavrakou, J. Harvey, J. Peeters
- ChemistryNature Communications
- 17 October 2016
The molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory and it is shown that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall meethanol yield of ∼30%, consistent with the theoretical estimates given their uncertainties.
High-accuracy computation of reaction barriers in enzymes.
- F. Claeyssens, J. Harvey, H. Werner
- ChemistryAngewandte Chemie
- 20 October 2006
Good agreement is obtained between the computed and the experimentally determined activation barriers for two quite different enzymatic reactions, a Claisen rearrangement in chorismate mutase and an electrophilic aromatic substitution in parahydroxybenzoate hydroxylase.
Mechanism of the Morita-Baylis-Hillman reaction: a computational investigation.
- R. Robiette, V. Aggarwal, J. Harvey
- ChemistryJournal of the American Chemical Society
- 28 November 2007
The mechanism of the MBH reaction is addressed, focusing on the reaction between methyl acrylate and benzaldehyde, catalyzed by a tertiary amine, and it is predicted that deprotonation of the alpha-position is the rate-determining step and occurs through a cyclic transition state.
Inclusion of Dispersion Effects Significantly Improves Accuracy of Calculated Reaction Barriers for Cytochrome P450 Catalyzed Reactions
- R. Lonsdale, J. Harvey, A. Mulholland
- 26 October 2010
Prediction of cytochrome P450 reactivity is of great importance to the development of new medicinal compounds. Density functional theory (DFT) has proven itself as a useful tool in the…
High precision NOEs as a probe for low level conformers--a second conformation of strychnine.
- C. Butts, Catharine R Jones, J. Harvey
- Physics, ChemistryChemical Communications
- 10 January 2011
A second conformer of strychnine, with a very low population (2.5%), has been identified experimentally, and confirmed by computation, demonstrating the ability of NOE measurements to discriminate…
Understanding the kinetics of spin-forbidden chemical reactions.
- J. Harvey
- Chemistry, PhysicsPhysical Chemistry, Chemical Physics - PCCP
- 2 January 2007
It is shown that in cases where the surface-hopping probability is low, the kinetics of spin-forbidden reactions will be characterised by unusually unfavourable entropies of activation, which can be expected to compete poorly with spin-allowed reactions at high temperatures (or energies).
On the accuracy of density functional theory in transition metal chemistry
- J. Harvey
- 3 August 2006
Density Functional Theory has become very widely used to study the electronic structure and related properties of transition metal complexes. Despite the many successes obtained using modern…
Taking Ockham's razor to enzyme dynamics and catalysis.
- D. Glowacki, J. Harvey, A. Mulholland
- Physics, BiologyNature Chemistry
- 1 March 2012
The role of protein dynamics in enzyme catalysis is a matter of intense current debate. Enzyme-catalysed reactions that involve significant quantum tunnelling can give rise to experimental kinetic…
Spin-forbidden ligand binding to the ferrous-heme group: ab initio and DFT studies.
- N. Strickland, J. Harvey
- ChemistryJournal of Physical Chemistry B
- 10 January 2007
The potential energy surfaces (PESs) and associated energy barriers that characterize the spin-forbidden recombination reactions of the gas-phase ferrous deoxy-heme group with CO, NO, and H2O ligands…