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Gaining insights into the working principles of photocatalysts on an atomic scale is a challenging task. The obviously high complexity of the reaction mechanism involving photo-excited electrons and holes is one reason. Another complicating aspect is that the electromagnetic field, driving photocatalysis, is not homogeneous on a nanoscale level for particle based catalysts as it is influenced by the particle’s shape and size.
We present a simple model, inspired by the CO2 reduction on titania anatase, which addresses the impact of these heterogeneities on the photocatalytic kinetics by combining kinetic Monte Carlo with electromagnetic wave simulations. We find that average activity and especially efficiency might differ significantly between different particles. Moreover, we find sizable variation of the catalytic activity on a single facet of a nanocrystal. Besides this quantitative heterogeneity, the coverage situation in general changes laterally on this facet and we observe a concomitant change of the rate-determining steps.
This heterogeneity on all levels of photocatalytic activity is masked in experimental studies, where only the spatially averaged activity can be addressed. Microkinetic models based on experimental findings might therefore not represent the true micro- scopic behavior, and mechanistic conclusion drawn from these need to be handled with care.
We present a Newton-like method to solve inverse problems and to quantify parameter uncertainties. We apply the method to parameter reconstruction in optical scatterometry, where we take into account a priori information and measurement uncertainties using a Bayesian approach. Further, we discuss the influence of numerical accuracy on the reconstruction result.
The introduction of the near-field quantity of optical chirality has emerged in various numerical and few experimental studies of local chirality enhancement due to its relation to the excitation rate of chiral molecules. This time-even pseudoscalar has been dismissed as being a higher-order version of helicity. Nevertheless, we revisit the derivation of the underlying conservation law and define optical chirality in media similar to. We identify the mechanism of chirality conversion by either inhomogeneous or anisotropic space to complement the conservation of optical chirality.
The conservation law of optical chirality in arbitrary space enables the extension of the concept of polarization to the near-field where no distiniguished propagation direction of light is present. We show that the connection of electromagnetic energy and optical chirality provide the ability to define a circular polarization basis in time-harmonic near-field analysis.
In order to illustrate our theory, we present electromagnetic field simulations of simple as well as more complex nanostructures. Results using the well-known far-field polarization concept are readily reproduced and extended from the point of view of chirality conversion.