Polarizable Density Embedding for Large Biomolecular Systems

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, Copyright © 2020 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jctc.0c00763.We present an efficient and robust fragment-based quantum–classical embedding model capable of accurately capturing effects from complex environments such as proteins and nucleic acids. This is realized by combining the molecular fractionation with conjugate caps (MFCC) procedure with the polarizable density embedding (PDE) model at the level of Fock matrix construction. The PDE contributions to the Fock matrix of the core region are constructed using the local molecular basis of the individual fragments rather than the supermolecular basis of the entire system. Thereby, we avoid complications associated with the application of the MFCC procedure on environment quantities such as electronic densities and molecular-orbital energies. Moreover, the computational cost associated with solving self-consistent field (SCF) equations of the core region remains unchanged from that of purely classical polarized embedding models. We analyze the performance of the resulting model in terms of the reproduction of the electrostatic potential of an insulin monomer protein and further in the context of solving problems related to electron spill-out. Finally, we showcase the model for the calculation of one- and two-photon properties of the Nile red molecule in a protein environment. Based on our analyses, we find that the combination of the MFCC approach with the PDE model is an efficient, yet accurate approach for calculating molecular properties of molecules embedded in structured biomolecular environments

Formation of desert rose structures in vacuum plasma sprayed electrodes for alkaline electrolysis

The EU FCH-JU RESelyser project is concerned with the development of high pressure, high efficiency and low cost alkaline water electrolysers that can be operated variably and intermittently to meet the demands for integration into energy networks relying on fluctuating renewable energy. The project utilizes NiAlMo alloy electrodes produced at the German Aerospace Center (DLR) by vacuum plasma spraying (VPS). VPS results in a heterogeneous microstructure consisting of a multitude of intermetallic phase sub domains and pores. Prior to electrolysis operation the electrodes are activated by leaching of Al and some Al containing intermetallic phases leaving micrometer pores and nanometer dendritic pores increasing the surface area available for the electrolysis reactions. The vacuum plasma sprayed electrodes were analyzed by high resolution SEM and TEM before and after electrolysis operation and after storage in water. Analyses of cross sections and electrode surfaces revealed desert rose like nano flake structures on the surface and in the pores on several electrodes. The formation of the desert rose structure appeared to be related to the electrolysis operation as well as the duration of storage in distilled water. The size of the faceted flakes varied from tens of nm to a couple of µm where the thickness varied from a few nm to ~50 nm. The desert rose structure was confirmed by TEM to consist primarily of NiO and Al2NiO4 like phases (similar lattice parameters). The possible implications for the application and performance of the electrodes are discussed