Tests of an adaptive QM/MM calculation on free energy profiles of chemical reactions in solution.

We present reaction free energy calculations using the adaptive buffered force mixing quantum mechanics/molecular mechanics (bf-QM/MM) method. The bf-QM/MM method combines nonadaptive electrostatic embedding QM/MM calculations with extended and reduced QM regions to calculate accurate forces on all atoms, which can be used in free energy calculation methods that require only the forces and not the energy. We calculate the free energy profiles of two reactions in aqueous solution: the nucleophilic substitution reaction of methyl chloride with a chloride anion and the deprotonation reaction of the tyrosine side chain. We validate the bf-QM/MM method against a full QM simulation, and show that it correctly reproduces both geometrical properties and free energy profiles of the QM model, while the electrostatic embedding QM/MM method using a static QM region comprising only the solute is unable to do so. The bf-QM/MM method is not explicitly dependent on the details of the QM and MM methods, so long as it is possible to compute QM forces in a small region and MM forces in the rest of the system, as in a conventional QM/MM calculation. It is simple, with only a few parameters needed to control the QM calculation sizes, and allows (but does not require) a varying and adapting QM region which is necessary for simulating solutions.

Calculation of metallic and insulating phases of V2O3 by hybrid density functionals.

The electronic structure of vanadium sesquioxide V2O3 in its different phases has been calculated using the screened exchange hybrid density functional. The hybrid functional accurately reproduces the experimental electronic properties of all three phases, the paramagnetic metal (PM) phase, the anti-ferromagnetic insulating phase, and the Cr-doped paramagnetic insulating (PI) phase. We find that a fully relaxed supercell model of the Cr-doped PI phase based on the corundum structure has a monoclinic-like local strain around the substitutional Cr atoms. This is found to drive the PI-PM transition, consistent with a Peierls-Mott transition. The PI phase has a calculated band gap of 0.15 eV, in good agreement with experiment.

Novel fluid grid and voidage calculation techniques for a discrete element model of a 3D cylindrical fluidized bed

A discrete element model (DEM) combined with computational fluid dynamics (CFD) was developed to model particle and fluid behaviour in 3D cylindrical fluidized beds. Novel techniques were developed to (1) keep fluid cells, defined in cylindrical coordinates, at a constant volume in order to ensure the conditions for validity of the volume-averaged fluid equations were satisfied and (2) smoothly and accurately measure voidage in arbitrarily shaped fluid cells. The new technique for calculating voidage was more stable than traditional techniques, also examined in the paper, whilst remaining computationally-effective. The model was validated by quantitative comparison with experimental results from the magnetic resonance imaging of a fluidised bed analysed to give time-averaged particle velocities. Comparisons were also made between theoretical determinations of slug rise velocity in a tall bed. It was concluded that the DEM-CFD model is able to investigate aspects of the underlying physics of fluidisation not readily investigated by experiment. © 2014 The Authors.