<p>The mapping of an electronic state on a real-space support lattice may offer advantages over a basis set ansatz in cases where there are linear dependences due to basis set overcompleteness or when strong internal or external fields are present. Such discretization methods are also of interest because they allow for the convenient numerical integration of matrix elements of local operators. We ...

We discuss the characteristic factors that determine the electrochemical potentials in a metal-organic framework used as cathode for Li-ion batteries via density functional theory-based simulations. Our focus is on MIL-101(Fe) cathode material. Our study gives insight into the role of local atomic environment and structural deformations in generating electrochemical potential.

Electron and nuclear magnetic resonance spectroscopies are indispensable and powerful methods for investigating the molecular and electronic structures of open-shell systems. We demonstrate that the NMR and EPR parameters are extremely sensitive quantitative probes for the electronic spin density around heavy-metal atoms and the metal–ligand bonding. Using relativistic density-functional theory, we ...

The electronic circular dichroism (ECD) properties of the green fluorescent protein and other fluorescent proteins have been calculated with density functional theory. The influence of different embedding models on the ECD signal of the chromophore has been investigated by modeling the protein environment by the polarizable continuum model (QM/PCM), by the polarizable embedding model (PE-QM/MM), by ...

The e ect of surfaces and interfaces on the structure and properties of molecules is of a great interest in a number of biological and technological applications. Nevertheless, such an investigation is extremely challenging from an experimental point of view, due to the bidimensionality of the environment. In recent years, we have developed a framework to study molecules at surfaces ...

Using multiwavelets, we have obtained total energies and corresponding atomization energies for the GGA-PBE and hybrid-PBE0 density functionals for a test set of 211 molecules with an unprecedented and guaranteed μHartree accuracy. These quasi-exact references allow us to quantify the accuracy of standard all-electron basis sets that are believed to be highly accurate for molecules, such as Gaussian-type ...

CO₂ is a promising and sustainable carbon feedstock for organic synthesis. New catalytic protocols for efficient incorporation of CO₂into organic molecules are continuously being reported. However, little progress has been made in the enantioselective conversion of CO₂to form enantioenriched molecules. In order to allow CO₂to become a versatile carbon ...

Production of psychrophilic enzymes in the commonly used mesophilic expression systems is hampered by low intrinsic stability of the recombinant enzymes at the optimal host growth temperatures. Unless strategies for low-temperature expression are advanced, research on psychrophilic enzymes may end up being biased toward those that can be stably produced in commonly used mesophilic host systems. Two ...

The role played by entropy for the enormous rate enhancement achieved by enzymes has been debated for many decades. There are, for example, several confirmed cases where the activation free energy is reduced by around 10 kcal/mol due to entropic effects, corresponding to a rate enhancement of ∼107 compared to the uncatalyzed reaction. However, despite substantial efforts from both the experimental ...

The cellular methyl donor S-adenosylmethionine (SAM) and other endo/exogenous agents methylate DNA bases non-enzymatically into products interfering with replication and transcription. An important product is 3-methyladenine (m³A), which in <i>Escherichia coli</i> is removed by m³A-DNA glycosylase I (Tag) and II (AlkA). The <i>tag</i> gene is constitutively expressed, while ...