5 research outputs found
Implicit self-consistent electrolyte model in plane-wave density-functional theory
The ab-initio computational treatment of electrochemical systems requires an
appropriate treatment of the solid/liquid interfaces. A fully quantum
mechanical treatment of the interface is computationally demanding due to the
large number of degrees of freedom involved. In this work, we describe a
computationally efficient model where the electrode part of the interface is
described at the density-functional theory (DFT) level, and the electrolyte
part is represented through an implicit solvation model based on the
Poisson-Boltzmann equation. We describe the implementation of the linearized
Poisson-Boltzmann equation into the Vienna Ab-initio Simulation Package (VASP),
a widely used DFT code, followed by validation and benchmarking of the method.
To demonstrate the utility of the implicit electrolyte model, we apply it to
study the surface energy of Cu crystal facets in an aqueous electrolyte as a
function of applied electric potential. We show that the applied potential
enables the control of the shape of nanocrystals from an octahedral to a
truncated octahedral morphology with increasing potential
Emergence of Coupled Rotor Dynamics in MetalâOrganic Frameworks via Tuned Steric Interactions
International audienceThe organic components in metalâorganic frameworks (MOFs) are unique: they are embedded in a crystalline lattice, yet, as they are separated from each other by tunable free space, a large variety of dynamic behavior can emerge. These rotational dynamics of the organic linkers are especially important due to their influence over properties such as gas adsorption and kinetics of guest release. To fully exploit linker rotation, such as in the form of molecular machines, it is necessary to engineer correlated linker dynamics to achieve their cooperative functional motion. Here, we show that for MIL-53, a topology with closely spaced rotors, the phenylene functionalization allows researchers to tune the rotors' steric environment, shifting linker rotation from completely static to rapid motions at frequencies above 100 MHz. For steric interactions that start to inhibit independent rotor motion, we identify for the first time the emergence of coupled rotation modes in linker dynamics. These findings pave the way for function-specific engineering of gear-like cooperative motion in MOFs
Emergence of Cooperative Rotor Dynamics in Metalâorganic Frameworks via Tuned Steric Interactions
The organic components in metal-organic frameworks (MOFs) enjoy a unique situation: they are embedded in a crystalline lattice, yet, as they are separated from each other by tunable free space, a large variety of dynamic behavior can emerge. These rotational dynamics of the organic linkers are especially important due to their influence over properties such as gas adsorption and kinetics of guest release. In order to fully exploit linker rotation, it is necessary to engineer correlated linker dynamics to achieve their cooperative functional motion. Here, we show that for MIL-53, a topology with closely spaced rotors, the phenylene functionalization allows to tune the rotorsâ steric environment, shifting linker rotation from completely static to rapid motions at frequencies above 100 MHz. For steric interactions that start to inhibit independent rotor motion, we identify for the first time the emergence of correlated rotation modes in linker dynamics. These findings pave the way for function-specific engineering of gearlike cooperative motion in MOFs