Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling

X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the Restricted Active Space Self-Consistent Field method including spin-orbit coupling is used to cope with this challenge and to calculate valence and core photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the $\text{[Fe(H}_2\text{O)}_6\text{]}^{2+}$ complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments

Transport Properties of Highly Aligned Polymer Light-Emitting-Diodes

We investigate hole transport in polymer light-emitting-diodes in which the emissive layer is made of liquid-crystalline polymer chains aligned perpendicular to the direction of transport. Calculations of the current as a function of time via a random-walk model show excellent qualitative agreement with experiments conducted on electroluminescent polyfluorene demonstrating non-dispersive hole transport. The current exhibits a constant plateau as the charge carriers move with a time-independent drift velocity, followed by a long tail when they reach the collecting electrode. Variation of the parameters within the model allows the investigation of the transition from non-dispersive to dispersive transport in highly aligned polymers. It turns out that large inter-chain hopping is required for non-dispersive hole transport and that structural disorder obstructs the propagation of holes through the polymer film.Comment: 4 pages, 5 figure

Including a Cold Pool Representation in a Convection Parameterization and Simulating Its Impacts on the Spatial and Temporal Variability of the Precipitation in the NASA GEOS GCM

We developed and implemented a simple representation of a cold pool in the Grell-Freitas (GF) convection parameterization. The cold pool parameterization is based on the observation that convective-scale downdrafts produce a local deficit of the moist static energy (MSE). This information is advected and becoming downwind available to trigger and intensify new convection. The cold pool is dissipated by a simple exponential decay using a lifetime of a few hours, or by interacting with the underneath surface by exchanging latent and sensible heat fluxes. Preliminary results show some improvement of the simulation of the diurnal cycle of the precipitation over the land, mainly during the nighttime

Design, Synthesis and Catalytic Activity of (Cyclopentadienone)iron Complexes Containing a Stereogenic Plane and a Stereogenic Axis

Herein, we report the synthesis and characterization of several chiral (cyclopentadienone)iron complexes (CICs) featuring either two (R)-BINOL-derived stereoaxes or a combination of one (R)-BINOL-derived stereoaxis and a stereogenic plane. The stereoplane-containing CICs were obtained as epimer mixtures, which were separated by flash column chromatography and assigned an absolute configuration based on XRD analysis, NMR and order of elution. The library was tested in the asymmetric hydrogenation of ketones showing good catalytic activity and a moderate stereoselectivity which, notably, is mostly imparted by the stereogenic plane. Indeed, the two epimers of each CIC possessing a stereoplane show opposite and equally strong stereochemical preference.Winning plane: chiral (cyclopentadienone)iron complexes (CICs) featuring a combination of an (R)-BINOL-derived stereoaxis and a stereogenic plane were synthesized in diastereoisomerically pure form, characterized and tested in the asymmetric hydrogenation of ketones. The new CICs showed good catalytic activity and, remarkably, the stereoplane epimers displayed similar and opposite stereochemical preference

Monolithic solder-on nanoporous Si-Cu contacts for stretchable silicone composite sensors

We report a method of creating solderable, mechanically robust, electrical contacts to interface (soft) silicone-based strain sensors with conventional (hard) solid-state electronics using a nanoporous Si-Cu composite. The Si-based solder-on electrical contact consists of a copper-plated nanoporous Si top surface formed through metal-assisted chemical etching and electroplating, and a smooth Si bottom surface which can be covalently bonded onto silicone-based strain sensors through plasma bonding. We investigated the mechanical and electrical properties of the contacts proposed under relevant ranges of mechanical stress for applications in physiological monitoring and rehabilitation. We also produced a series of proof-of-concept devices, including a wearable respiration monitor, leg band for exercise monitoring and Squeeze-ball for monitoring rehabilitation of patients with hand injuries or neurological disorders, to demonstrate the mechanical robustness and versatility of the technology developed, in real-world applications