On the microscopic mechanism of carbon gasification: A theoretical study

In this paper we report the results of ab initio calculations on the energetics and kinetics of oxygen-driven carbon gasification reactions using a small model cluster, with full characterisation of the stationary points on the reaction paths. We show that previously unconsidered pathways present significantly reduced barriers to reaction and must be considered as alternative viable paths. At least two electronic spin states of the model cluster must be considered for a complete description. (C) 2004 Elsevier Ltd. All rights reserved.

Quantum nondemolition measurement of Fock states of mesoscopic mechanical oscillators

We investigate a scheme that makes a quantum nondemolition (QND) measurement of the excitation level of a mesoscopic mechanical oscillator by utilizing the anharmonic coupling between two beam bending modes. The nonlinear coupling between the two modes shifts the resonant frequency of the readout oscillator in proportion to the excitation level of the system oscillator. This frequency shift may be detected as a phase shift of the readout oscillation when driven on resonance. We derive an equation for the reduced density matrix of the system oscillator, and use this to study the conditions under which discrete jumps in the excitation level occur. The appearance of jumps in the actual quantity measured is also studied using the method of quantum trajectories. We consider the feasibility of the scheme for experimentally accessible parameters.

Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

The ‘leading coordinate’ approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information.