Unlocking Unexpected Charge Transfer Pathways in Interconnected Nanostructures.

Accurate control of charge transfer pathways is critical to unlocking the full potential of charge transfer plasmons (CTPs) and exploring their diverse applications. We show that the intentional manipulation of junctions in Al nanocrosses on graphene induces asymmetry, unlocking unexpected charge transfer pathways and facilitating the generation of coupled resonators. The junction asymmetry, which is induced by nanotrench formation facilitated by focused electron beam irradiation, provides a versatile means to achieve precise and controlled interconnect manipulation.

Nearly linear orbital molecules on a pyrochlore lattice.

The interplay of spin-orbit coupling with other relevant parameters gives rise to the rich phase competition in complex ruthenates featuring octahedrally coordinated Ru. While locally, spin-orbit coupling stabilizes a nonmagnetic = 0 state, intersite interactions resolve one of two distinct phases at low temperatures: an excitonic magnet stabilized by the magnetic exchange of upper-lying = 1 states or Ru molecular orbital dimers driven by direct orbital overlap. Pyrochlore ruthenates RuO ( = rare earth, Y) are candidate excitonic magnets with geometrical frustration.

A Constraint-Based Orbital-Optimized Excited State Method (COOX).

In this work, we present a novel method to directly calculate targeted electronic excited states within a self-consistent field calculation based on constrained density functional theory (cDFT). The constraint is constructed from the static occupied-occupied and virtual-virtual parts of the excited state difference density from (simplified) linear-response time-dependent density functional theory calculations (LR-TDDFT). Our new method shows a stable convergence behavior, provides an accurate excited state density adhering to the Aufbau principle, and can be solved within a restricted SCF for singlet excitations to avoid spin contamination.

How big is big data?

Big data has ushered in a new wave of predictive power using machine-learning models. In this work, we assess what big means in the context of typical materials-science machine-learning problems. This concerns not only data volume, but also data quality and veracity as much as infrastructure issues.

Accurate determination of excitation energy: An equation-of-motion approach over a bi-exponential coupled cluster theory.

The calculation of molecular excited states is critically important to decipher a plethora of molecular properties. In this paper, we develop an equation of motion formalism on top of a bi-exponentially parameterized ground state wavefunction toward the determination of excited states. While the ground state bi-exponential parameterization ensures an accurate description of the wavefunction through the inclusion of high-rank correlation effects, the excited state is parameterized by a novel linear response operator with an effective excitation rank beyond two.

Bibliometric analysis of publications that cited the CIOMS 2016 "International ethical guidelines for health-related research involving humans".

The CIOMS book "International Ethical Guidelines for Health-related Research Involving Humans", published in 2016 (IEG2016), provides information to assist research ethics committee members and research practitioners with pragmatically implementing ethical considerations while planning and conducting their research. To identify which aspects of research IEG2016 has had the greatest impact since its publication, we analyzed metadata from 942 papers that cited IEG2016 (English language title only) from Web of Science (WoS, Clarivate). Using VOSviewer, we mapped the co-occurrence of keywords to derive the network of all keywords that co-occurred at least five times in the set of citing papers.

Impact of Synthesis Method on the Structure and Function of High Entropy Oxides.

The term sample dependence describes the troublesome tendency of nominally equivalent samples to exhibit different physical properties. High entropy oxides (HEOs) are a class of materials where sample dependence has the potential to be particularly profound due to their inherent chemical complexity. In this work, we prepare a spinel HEO of identical nominal composition by five distinct methods, spanning a range of thermodynamic and kinetic conditions: solid state, high pressure, hydrothermal, molten salt, and combustion syntheses.

Low-Scaling, Efficient and Memory Optimized Computation of Nuclear Magnetic Resonance Shieldings within the Random Phase Approximation Using Cholesky-Decomposed Densities and an Attenuated Coulomb Metric.

An efficient method for the computation of nuclear magnetic resonance (NMR) shielding tensors within the random phase approximation (RPA) is presented based on our recently introduced resolution-of-the-identity (RI) atomic orbital RPA NMR method [Drontschenko, V. 2023, 19, 7542-7554] utilizing Cholesky decomposed density type matrices and employing an attenuated Coulomb RI metric. The introduced sparsity is efficiently exploited using sparse matrix algebra.

Decoupling of Light and Dark Reactions in a 2D Niobium Tungstate for Light-Induced Charge Storage and On-Demand Hydrogen Evolution.

The direct coupling of light harvesting and charge storage in a single material opens new avenues to light storing devices. Here we demonstrate the decoupling of light and dark reactions in the two-dimensional layered niobium tungstate (TBA)(NbWO) for on-demand hydrogen evolution and solar battery energy storage. Light illumination drives Li/H photointercalation into the (TBA)(NbWO) photoanode, leading to small polaron formation assisted by structural distortions on the WO sublattice, along with a light-induced decrease in material resistance over 2 orders of magnitude compared to the dark.

Multiferroicity in plastically deformed SrTiO.

Quantum materials have a fascinating tendency to manifest novel and unexpected electronic states upon proper manipulation. Ideally, such manipulation should induce strong and irreversible changes and lead to new relevant length scales. Plastic deformation introduces large numbers of dislocations into a material, which can organize into extended structures and give rise to qualitatively new physics as a result of the huge localized strains.

Simulation of the non-adiabatic dynamics of an enone-Lewis acid complex in an explicit solvent.

Unlocking the full potential of Lewis acid catalysis for photochemical transformations requires a comprehensive understanding of the ultrafast dynamics of substrate-Lewis acid complexes. In a previous article [Peschel , 2021, , 10155], time-resolved spectroscopy supported by static calculations revealed that the Lewis acid remains attached during the relaxation of the model complex cyclohexenone-BF. In contrast to the experimental observation, surface-hopping dynamics in the gas phase predicted ultrafast heterolytic dissociation.

Celebrating Ten Years of Covalent Organic Frameworks for Solar Energy Conversion: Past, Present and Future.

Accelerated anthropogenic emission of greenhouse gases due to increasing energy demands has created a negative impact on our planet. Therefore, the replacement of fossil by renewable energy resources has become of paramount interest, both societally and scientifically. It is within this setting that organic photocatalysts have emerged as a new generation of earth-abundant catalysts for the conversion of solar radiation into chemical energy.

Permutation symmetry in spin-adapted many-body wave functions.

In the domain of exchange-coupled polynuclear transition-metal (PNTM) clusters, local emergent symmetries exist which can be exploited to greatly increase the sparsity of the configuration interaction (CI) eigensolutions of such systems. Sparsity of the CI secular problem is revealed by exploring the site permutation space within spin-adapted many-body bases, and highly compressed wave functions may arise by finding optimal site orderings. However, the factorial cost of searching through the permutation space remains a bottleneck for clusters with a large number of metal centers.

3D DNA origami pincers that multitask on giant unilamellar vesicles.

Proteins self-assemble to function in living cells. They may execute essential tasks in the form of monomers, complexes, or supramolecular cages via oligomerization, achieving a sophisticated balance between structural topology and functional dynamics. The modularity and programmability make DNA origami unique in mimicking these key features.

Selective excitation of vibrations in a single molecule.

The capability to excite, probe, and manipulate vibrational modes is essential for understanding and controlling chemical reactions at the molecular level. Recent advancements in tip-enhanced Raman spectroscopies have enabled the probing of vibrational fingerprints in a single molecule with Ångström-scale spatial resolution. However, achieving controllable excitation of specific vibrational modes in individual molecules remains challenging.

Polyaptamer-Driven Crystallization of Alendronate for Synergistic Osteoporosis Treatment through Osteoclastic Inhibition and Osteogenic Promotion.

Osteoclastic inhibition using antiresorptive bisphosphonates and osteogenic promotion using antisclerostin agents represent two distinct osteoporosis treatments in clinical practice, each individual treatment suffers from unsatisfactory therapeutic efficacy due to its indirect intervention in osteoclasis and promotion of osteogenesis simultaneously. Although this issue is anticipated to be resolved by drug synergism, a tempting carrier-free dual-medication nanoassembly remains elusive. Herein, we prepare such a nanoassembly made of antiresorptive alendronate (ALN) crystal and antisclerostin polyaptamer (Apt) via a nucleic acid-driven crystallization method.

Energy landscapes-Past, present, and future: A perspective.

Energy landscapes and the closely related cost function landscapes have been recognized in science, mathematics, and various other fields such as economics as being highly useful paradigms and tools for the description and analysis of the properties of many systems, ranging from glasses, proteins, and abstract global optimization problems to business models. A multitude of algorithms for the exploration and exploitation of such landscapes have been developed over the past five decades in the various fields of applications, where many re-inventions but also much cross-fertilization have occurred. Twenty-five years ago, trying to increase the fruitful interactions between workers in different fields led to the creation of workshops and small conferences dedicated to the study of energy landscapes in general instead of only focusing on specific applications.

Spin-Orbit-Lattice Entangled State in A_{2}MgReO_{6} (A=Ca, Sr, Ba) Revealed by Resonant Inelastic X-Ray Scattering.

The 5d^{1} ordered double perovskites present an exotic playground for studying novel multipolar physics due to large spin-orbit coupling. We present Re L_{3} edge resonant inelastic x-ray scattering (RIXS) results that reveal the presence of the dynamic Jahn-Teller effect in the A_{2}MgReO_{6} (A=Ca, Sr, Ba) family of 5d^{1} double perovskites. The spin-orbit excitations in these materials show a strongly asymmetric line shape and exhibit substantial temperature dependence, indicating that they are dressed with lattice vibrations.

Plasmon-Enhanced Light Absorption Below the Bandgap of Semiconducting SnS Microcubes for Highly Efficient Solar Water Evaporation.

Semiconducting materials show high potential for solar energy harvesting due to their suitable bandgaps, which allow the efficient utilization of light energy larger than their bandgaps. However, the photon energy smaller than their bandgap is almost unused, which significantly limits their efficient applications. Herein, plasmonic Pd/SnS microcubes with abundant Pd nanoparticles attached to the SnS nanosheets are fabricated by an in situ photoreduction method.

Orbital optimisation in xTC transcorrelated methods.

We present a combination of the bi-orthogonal orbital optimisation framework with the recently introduced xTC version of transcorrelation. This allows us to implement non-iterative perturbation based methods on top of the transcorrelated Hamiltonian. Additionally, the orbital optimisation influences results of other truncated methods, such as the distinguishable cluster with singles and doubles.

Dependence of lactose adsorption on the exposed crystal facets of metals: a comparative study of gold, silver and copper.

In this theoretical work, we investigated the adsorption of a lactose molecule on metal-based surfaces, with a focus on the influence of the nature of the metal and of the type of exposed crystal facet on the adsorbed structures and energetics. More precisely, we considered three flat crystallographic facets of three face-centered cubic metals (gold, silver, and copper). For the global exploration of the energy landscape, we employed a multi-stage procedure where high-throughput searches, using a stochastic method that performs global optimization by iterating local searches, are followed by a refinement of the most probable adsorption conformations of the molecule at the level.