Notes

Healthcare workers thinking to COVID-19 vaccine as well as the relation to professional and personal existence.
We present an embedding approach to treat local electron correlation effects in periodic environments. In a single consistent framework, our plane wave based scheme embeds a local high-level correlation calculation [here, Coupled Cluster (CC) theory], employing localized orbitals, into a low-level correlation calculation [here, the direct Random Phase Approximation (RPA)]. This choice allows for an accurate and efficient treatment of long-range dispersion effects. Accelerated convergence with respect to the local fragment size can be observed if the low-level and high-level long-range dispersions are quantitatively similar, as is the case for CC in RPA. To demonstrate the capabilities of the introduced embedding approach, we calculate adsorption energies of molecules on a surface and in a chabazite crystal cage, as well as the formation energy of a lattice impurity in a solid at the level of highly accurate many-electron perturbation theories. The absorption energy of a methane molecule in a zeolite chabazite is converged with an error well below 20 meV at the CC level. As our largest periodic benchmark system, we apply our scheme to the adsorption of a water molecule on titania in a supercell containing more than 1000 electrons.Using large deviation theory and principles of stochastic optimal control, we show that rare molecular dynamics trajectories conditioned on assembling a specific target structure encode a set of interactions and external forces that lead to enhanced stability of that structure. Such a relationship can be formulated into a variational principle, for which we have developed an associated optimization algorithm and have used it to determine optimal forces for targeted self-assembly within nonequilibrium steady-states. We illustrate this perspective on inverse design in a model of colloidal cluster assembly within linear shear flow. We find that colloidal clusters can be assembled with high yield using specific short-range interactions of tunable complexity. Shear decreases the yields of rigid clusters, while small values of shear increase the yields of nonrigid clusters. The enhancement or suppression of the yield due to shear is rationalized with a generalized linear response theory. By studying 21 unique clusters made of six, seven, or eight particles, we uncover basic design principles for targeted assembly out of equilibrium.Excited Costrained Density Functional Theory (XCDFT) [Ramos and Pavanello, J. Chem. Phys. selleck inhibitor 148, 144103 (2018)] is a variational excited state method that extends ground state DFT to the computation of low-lying excited states. It borrows much of the machinery of Constrained DFT (CDFT) with a crucial difference the constraint imposes a population of one electron in the Hilbert space spanned by the virtuals of a reference ground state. In this work, we present theory and implementation for evaluating nonadiabatic coupling vectors (NACVs) between the first excited state computed with XCDFT and the ground state. Our NACVs are computed analytically using density functional perturbation theory with a formalism that is general enough that could be applied to CDFT diabatic states. We showcase the new method with pilot NACV calculations for the conical intersection in H3, the avoided crossing in selenoacrolein, and the NACV magnitudes in azobenzene. Despite complications from the nonorthogonality of the wavefunctions, XCDFT's energy surfaces and NACVs reproduce benchmark values and respect known sum rules within a reasonable degree. This shows that XCDFT is a viable method for nonadiabatic dynamics simulations.We investigate the polymorphism of complexes formed by the hydration of a functionalized azobenzene molecule by low-temperature scanning tunneling microscopy. Under conditions at which the water-less azobenzene molecules remain as monomers on Au(111), co-adsorption of water leads to water-azobenzene complexes. These complexes prefer to adopt linear arrangements of the azobenzene mediated by its functionalized end groups. Such structures may serve as model systems for investigating the influence of a solvent on a surface reaction.The exact time-dependent potential energy surface driving the nuclear dynamics was recently shown to be a useful tool to understand and interpret the coupling of nuclei, electrons, and photons in cavity settings. Here, we provide a detailed analysis of its structure for exactly solvable systems that model two phenomena cavity-induced suppression of proton-coupled electron-transfer and its dependence on the initial state, and cavity-induced electronic excitation. We demonstrate the inadequacy of simply using a weighted average of polaritonic surfaces to determine the dynamics. Such a weighted average misses a crucial term that redistributes energy between the nuclear and the polaritonic systems, and this term can in fact become a predominant term in determining the nuclear dynamics when several polaritonic surfaces are involved. Evolving an ensemble of classical trajectories on the exact potential energy surface reproduces the nuclear wavepacket quite accurately, while evolving on the weighted polaritonic surface fails after a short period of time. The implications and prospects for application of mixed quantum-classical methods based on this surface are discussed.Cellular membranes consist of a large variety of lipids and proteins, with a composition that generally differs between the two leaflets of the same bilayer. One consequence of this asymmetry is thought to be the emergence of differential stress, i.e., a mismatch in the lateral tension of the two leaflets. This can affect a membrane's mechanical properties; for instance, it can increase the bending rigidity once the differential stress exceeds a critical threshold. Using coarse-grained molecular dynamics simulations based on the MARTINI model, we show that this effect arises due to the formation of more highly ordered domains in the compressed leaflet. The threshold asymmetry increases with temperature, indicating that the transition to a stiffened regime might be restricted to a limited temperature range above the gel transition. We also show that stiffening occurs more readily for larger membranes with smaller typical curvatures, suggesting that the stiffening transition is easier to observe experimentally than in the small-scale systems accessible to simulation.
Website: https://www.selleckchem.com/products/pamapimod-r-1503-ro4402257.html