Tuning Electronic and Structural Properties of Lead-Free Metal Halide Perovskites: A Comparative Study of 2D Ruddlesden-Popper and 3D Compositions.

In recent decades, two-dimensional (2D) perovskites have emerged as promising semiconductors for next-generation photovoltaics, showing notable advancements in solar energy conversion. Herein, we explore the impact of alternative inorganic lattice BX-based compositions (B=Ge or Sn, X=Br or I) on the energy gap and stability. Our investigation encompasses BA2Man-1BnX3n+1 2D Ruddlesden-Popper perovskites (for n=1-5 layers) and 3D bulk (MA)BX3 systems, employing first-principles calculations with spin-orbit coupling (SOC), DFT-1/2 quasiparticle, and D3 dispersion corrections. The study unveils how atoms with smaller ionic radii induce anisotropic internal and external distortions within the inorganic and organic lattices. Introducing the spacers in the low-layer regime reduces local distortions but widens band gaps. Our calculation protocol provides deeper insights into the physics and chemistry underlying 2D perovskite materials, paving the way for optimizing environmentally friendly alternatives that can efficiently replace with sustainable materials.

Unveiling oxygen vacancy impact on lizardite thermo and mechanical properties.

Here, we performed a systematic DFT study assisted by the workflow framework SimStack for the mechanical and thermodynamic properties of the clay mineral lizardite in pristine and six different types of O vacancies configurations. In most cases, the defect caused a structural phase transition in the lizardite from the trigonal (pristine) to the triclinic phase. The results show that oxygen vacancies in lizardite significantly reduce the lattice thermal conductivity, accompanied by an elastic moduli reduction and an anisotropy index increase. Through the P-V relation, an increase in compressibility was evidenced for vacancy configurations. Except for the vacancy with the same crystalline structure as pristine lizardite, the sound velocities of the other vacancy configurations produce a decrease in these velocities, and it is essential to highlight high values for the Grüneisen parameter. We emphasize the great relevance of the punctual-defects introduction, such as O vacancies, in lizardite, since this microstructural design is responsible for the decrease of the lattice thermal conductivity in comparison with the pristine system by decreasing the heat transfer ability, turning lizardite into a promising candidate for thermoelectric materials.

Revealing the impact of organic spacers and cavity cations on quasi-2D perovskites via computational simulations.

Two-dimensional hybrid lead iodide perovskites based on methylammonium (MA) cation and butylammonium (BA) organic spacer-such as [Formula: see text]-are one of the most explored 2D hybrid perovskites in recent years. Correlating the atomistic profile of these systems with their optoelectronic properties is a challenge for theoretical approaches. Here, we employed first-principles calculations via density functional theory to show how the cation partially canceled dipole moments through the [Formula: see text] terminal impact the structural/electronic properties of the [Formula: see text] sublattices. Even though it is known that at high temperatures, the organic cation assumes a spherical-like configuration due to the rotation of the cations inside the cage, our results discuss the correct relative orientation according to the dipole moments for ab initio simulations at 0 K, correlating well structural and electronic properties with experiments. Based on the combination of relativistic quasiparticle correction and spin-orbit coupling, we found that the MA horizontal-like configuration concerning the inorganic sublattice surface leads to the best relationship between calculated and experimental gap energy throughout n = 1, 2, 3, 4, and 5 number of layers. Conversely, the dipole moments cancellation (as in BA-MA aligned-like configuration) promotes the closing of the gap energies through an electron depletion mechanism. We found that the anisotropy [Formula: see text] isotropy optical absorption conversion (as a bulk convergence) is achieved only for the MA horizontal-like configuration, which suggests that this configuration contribution is the majority in a scenario under temperature effects.

How cation nature controls the bandgap and bulk Rashba splitting of halide perovskites.

Because of instability issues presented by metal halide perovskites based on methylammonium (MA), its replacement to Cs has emerged as an alternative to improve the materials' durability. However, the impact of this replacement on electronic properties, especially gap energy and bulk Rashba splitting remains unclear since electrostatic interactions from organic cations can play a crucial role. Through first-principles calculations, we investigated how organic/inorganic cations impact the electronic properties of MAPbI 3 and CsPbI 3 perovskites. Although at high temperatures the organic cation can assume spherical-like configurations due to its rotation into the cages, our results provide a complete electronic mechanism to show, from a chemical perspective based on ab initio calculations at 0 K , how the MA dipoles suppression can reduce the MAPbI 3 gap energy by promoting a degeneracy breaking in the electronic states from the PbI 3 framework, while the dipole moment reinforcement is crucial to align theory ↔ experiment, increasing the bulk Rashba splitting through higher Pb off-centering motifs. The lack of permanent dipole moment in Cs results in CsPbI 3 polymorphs with a pronounced Pb on-centering-like feature, which causes suppression in their respective bulk Rashba effect.

Determination of specific and non-specific protein-protein interactions for beta-lactoglobulin by analytical ultracentrifugation and membrane osmometry experiments.

Protein-protein interactions are essential for the understanding of biological processes. Specific protein aggregation is an important aspect for many biological systems. In particular, electrostatic interactions play the key role for protein-protein interactions, as many amino acids have pH-dependent charge states. Moreover, protein dissociation is directly related to the solution pH, ionic strength, temperature and protein concentration. The subtle interplay between different specific and non-specific interactions is demonstrated for beta-lactoglobulin (BLG) with a focus on low salt concentrations, thus mimicking technically relevant processing conditions. BLG is a well-characterized model system, proven to attain its monomer-dimer equilibrium strongly dependent upon the pH of the solution. In this manuscript, we present a unique combination of analytical ultracentrifugation and membrane osmometry experiments, which quantifies specific and non-specific interactions, i.e. in terms of the dimer dissociation constants and the second osmotic virial coefficient, at pH 3 and 7 and sodium chloride concentrations of 10 mM and 100 mM. This provides direct insight to protein-protein interactions for a system with a concentration-dependent monomer-dimer equilibrium. Moreover, using a coarse-grained extended DLVO model in combination with molecular dynamics simulations, we quantify non-specific monomer-monomer, monomer-dimer and dimer-dimer interactions as well as the binding free energy of BLG dimerization from theoretical calculations. The experimentally determined interactions are shown to be mainly governed by electrostatic interactions and further agree with free energy calculations. Our experimental protocol aims to determine non-specific and specific interactions for a dynamically interacting system and provides an understanding of protein-protein interactions for BLG at low salt concentrations.

Predicting phosphorus availability from chemically diverse conventional and recycling fertilizers.

Fertilizers produced from heterogeneous, phosphorus-rich biowastes are becoming increasingly relevant. Treatment and processing (combustion, pyrolysis, anaerobic digestion, etc.) increase the diversity of their physico-chemical composition even further. We investigated several approaches to characterize P availability from a set of 13 contrasting fertilizers. We tested them directly using standard fertilizer extractions, as well as a continuous, sink-based P extraction (iron bag) method. We also performed Olsen, CAL and diffusive gradients in thin films (DGT) tests on fertilized soil. Standard extractions correlated only weakly, whereas the iron bag method correlated highly (0.73

Neural evidence that suspense narrows attentional focus.

The scope of visual attention changes dynamically over time. Although previous research has reported conditions that suppress peripheral visual processing, no prior work has investigated how attention changes in response to the variable emotional content of audiovisual narratives. We used fMRI to test for the suppression of spatially peripheral stimuli and enhancement of narrative-relevant central stimuli at moments when suspense increased in narrative film excerpts. Participants viewed films presented at fixation, while flashing checkerboards appeared in the periphery. Analyses revealed that increasing narrative suspense caused reduced activity in peripheral visual processing regions in the anterior calcarine sulcus and in default mode network nodes. Concurrently, activity increased in central visual processing regions and in frontal and parietal regions recruited for attention and dynamic visual processing. These results provide evidence, using naturalistic stimuli, of dynamic spatial tuning of attention in early visual processing areas due to narrative context.

SIMONA 1.0: an efficient and versatile framework for stochastic simulations of molecular and nanoscale systems.

Molecular simulation methods have increasingly contributed to our understanding of molecular and nanoscale systems. However, the family of Monte Carlo techniques has taken a backseat to molecular dynamics based methods, which is also reflected in the number of available simulation packages. Here, we report the development of a generic, versatile simulation package for stochastic simulations and demonstrate its application to protein conformational change, protein-protein association, small-molecule protein docking, and simulation of the growth of nanoscale clusters of organic molecules. Simulation of molecular and nanoscale systems (SIMONA) is easy to use for standard simulations via a graphical user interface and highly parallel both via MPI and the use of graphical processors. It is also extendable to many additional simulations types. Being freely available to academic users, we hope it will enable a large community of researchers in the life- and materials-sciences to use and extend SIMONA in the future. SIMONA is available for download under http://int.kit.edu/nanosim/simona.

In silico discovery of a compound with nanomolar affinity to antithrombin causing partial activation and increased heparin affinity.

The medical and socioeconomic relevance of thromboembolic disorders promotes an ongoing effort to develop new anticoagulants. Heparin is widely used as activator of antithrombin but incurs side effects. We screened a large database in silico to find alternative molecules and predicted d-myo-inositol 3,4,5,6-tetrakisphosphate (TMI) to strongly interact with antithrombin. Isothermal titration calorimetry confirmed a TMI affinity of 45 nM, higher than the heparin affinity (273 nM). Functional studies, fluorescence analysis, and citrullination experiments revealed that TMI induced a partial activation of antithrombin that facilitated the interaction with heparin and low affinity heparins. TMI improved antithrombin inhibitory function of plasma from homozygous patients with antithrombin deficiency with a heparin binding defect and also in a model with endothelial cells. Our in silico screen identified a new, non-polysaccharide scaffold able to interact with the heparin binding domain of antithrombin. The functional consequences of this interaction were experimentally characterized and suggest potential anticoagulant therapeutic applications.

Conformational dependence of DNA ballistic conductivity.

With the atomistic Kubo-Verges method we calculate the ballistic conductance of various conformers of DNA (A,B,Z), as well as intermediate and composite conformations, using experimental structures and model complexes. For duplexes with 6 and 15 base pairs, we find that the valence band conductivity near the Fermi edge varies dramatically between the different conformations, most notably for the B-to-Z transition. The latter conductivity differences are largely unchanged both in the presence and in the absence of trimethylthiol linkers between DNA and gold electrodes in vacuo, but become much less drastic when explicit molecular dynamics and water-counterion surrounding of B- and Z-DNA are taken into account. Based on atomistic structural models, we argue that changes in the electrostatic energy in the presence of an applied external electric field can induce conformational switching that may be exploited in novel DNA-based memory devices of high packing density.

Measurement of the CP asymmetry in b-->sgamma using a sum of exclusive final states.

We perform a measurement of the CP asymmetry in b-->sgamma decays using a sample of 383 x 10(6) B[over] B events collected by the BABAR detector at the SLAC PEP-II asymmetric B factory. We reconstruct 16 flavor-specific B decay modes containing a high-energy photon and a hadronic system X_(s) containing an s quark. We measure the CP asymmetry to be -0.011+/-0.030(stat)+/-0.014(syst) for a hadronic system mass between 0.6 and 2.8 GeV/c(2).

Study of B meson decays with excited eta and eta' mesons.

Using 383 x 10(6) BBover pairs from the BABAR data sample, we report results for branching fractions of six charged B-meson decay modes, where a charged kaon recoils against a charmless resonance decaying to KKover* or etapipi final states with mass in the range (1.2-1.8) GeV/c2. We observe a significant enhancement at the low KKover* invariant mass which is interpreted as B+-->eta(1475)K+, find evidence for the decay B+-->eta(1295)K+, and place upper limits on the decays B+-->eta(1405)K+, B+-->f1(1285)K+, B+-->f1(1420)K+, and B+-->phi(1680)K+.

Evidence for CP violation in B0-->J/psipi0 decays.

We present measurements of the branching fraction and time-dependent CP asymmetries in B0-->J/psipi0 decays based on 466 x 10(6) Upsilon(4S)-->BB over events collected with the BABAR detector at the SLAC PEP-II asymmetric-energy B factory. We measure the CP asymmetry parameters S= -1.23+/-0.21(stat)+/-0.04(syst) and C= -0.20+/-0.19(stat)+/-0.03(syst), where the measured value of (S, C) is 4.0 standard deviations from (0, 0) including systematic uncertainties. The branching fraction is determined to be B(B0-->J/psipi0)=[1.69+/-0.14(stat)+/-0.07(syst)]x10(-5).

Observation of Y(3940) --> J/psiomega in B --> J/psiomegaK at BABAR.

We present a study of the decays B;{0,+}-->J/psiomegaK;{0,+} using 383x10;{6} BB[over ] events obtained with the BABAR detector at PEP-II. We observe Y(3940)-->J/psiomega, with mass 3914.6_{-3.4};{+3.8}(stat)+/-2.0(syst) MeV/c;{2}, and width 34_{-8};{+12}(stat)+/-5(syst) MeV. The ratio of B0 and B+ decay to YK is 0.27_{-0.23};{+0.28}(stat)-0.01+0.04(syst), and the relevant B0 and B+ branching fractions are reported.

Measurement of the decay B(-) ---> D(*0)e(-)nu[overline](e).

Using 226 x 10(6) BB[overline] events recorded on the Upsilon(4S) resonance with the BABAR detector at the SLAC e(+)e(-) PEP-II storage rings, we reconstruct B(-) ---> D(*0)e(-)nu[overline](e) decays using the decay chain D(*0) --> D(0)pi(0) and D(0)-->K(-)pi(+). From the dependence of their differential rate on w, the dot product of the four velocities of B(-) and D(*0), and using the form factor description by Caprini et al. with the parameters F(1) and rhoA(1)(2), we obtain the results rhoA(1)(2) = 1.16+/-0.06+/-0.08, F(1)|V(cb)|=(35.9+/-0.6+/-1.4) x 10(-3), and B(B(-) --> D(*0)e(-)nu[overline](e))=(5.56+/-0.08+/-0.41)%.

Search for CPT and lorentz violation in B0-B[over ]0 oscillations with dilepton events.

We report results of a search for CPT and Lorentz violation in B(0)-B[over ](0) oscillations using inclusive dilepton events from 232 x 10(6) Upsilon(4S)-->BB[over ] decays recorded by the BABAR detector at the PEP-II B Factory at SLAC. We find 2.8sigma significance, compatible with no signal, for variations in the complex CPT violation parameter z at the Earth's sidereal frequency and extract values for the quantities Deltaa(micro) in the general Lorentz-violating standard-model extension. The spectral powers for variations in z over the frequency range 0.26 yr(-1) to 2.1 solar day(-1) are also compatible with no signal.

Measurement of the branching fractions of exclusive _B-->D(*)(pi)l-_nu l decays in events with a fully reconstructed B meson.

We report a measurement of the branching fractions for _B-->D(*)(pi)l- _nu(l) decays based on 341.1 fb(-1) of data collected at the Upsilon(4S) resonance with the BABAR detector at the SLAC PEP-II e+ e- storage rings. Events are tagged by fully reconstructing one of the B mesons in a hadronic decay mode. We obtain B(B- -->D(0)l-_nu(l)=(2.33+/-0.09(stat)+/-0.09(syst)%, B(B- -->D(*0)l-_nu(l)=(5.83+/-0.15(stat) +/-0.30(syst) %, B(_B(0)-->D+l-_nu(l)=(2.21+/-0.11(stat) +/-0.12(syst)%, B(_B(0)-->D(*)l-_nu(l)=(5.49+/-0.16(stat)+/-0.25(syst)%, B(B- -->D+pi-l-_nu(l)=(0.42+/-0.06(stat)+/-0.03(syst)%, B(B- -->D(*)+pi-l-_nu(l)=(0.59+/-0.05(stat)+/-0.04(syst)%, B(_B(0)-->D(0)pi+l-_nu(l)=(0.43+/-0.08(stat)+/-0.03(syst)%, and B(_B(0)-->D(*0)pi+l-_nu(l)=(0.48+/-0.08(stat)+/-0.04(syst)%.

Observation of tree-level B decays with ss production from gluon radiation.

We report on our search for decays proceeding via a tree-level b-->c quark transition in which a gluon radiates into an ss[over ] pair. We present observations of the decays B;{-}-->D_{s};{+}K;{-}pi;{-} and B[over ];{0}-->D_{s};{+}K_{S};{0}pi;{-} and evidence for B;{-}-->D_{s};{+}K;{-}K;{-} and set upper limits on the branching fractions for B[over ];{0}-->D_{s};{+}K_{S};{0}pi;{-} and B;{-}-->D_{s};{+}K;{-}K;{-} using 383x10;{6} Upsilon(4S)-->BB[over ] events collected by the BABAR detector at SLAC. We present evidence that the invariant mass distributions of D_{s};{+}K;{-} pairs from B;{-}-->D_{s};{+}K;{-}pi;{-} decays are inconsistent with the phase-space model, suggesting the presence of charm resonances lying below the D_{s};{+}K;{-} threshold.

Measurements of partial branching fractions for B-->Xulnu and determination of |Vub|.

We present partial branching fractions for inclusive charmless semileptonic B decays B[over ]-->X_{u}lnu[over ], and the determination of the Cabibbo-Kobayashi-Maskawa matrix element |V_{ub}|. The analysis is based on a sample of 383 x 10;{6} Upsilon(4S) decays into BB[over ] pairs collected with the BABAR detector at the SLAC PEP-II e;{+}e;{-} storage rings. We select events using the invariant mass M_{X} of the hadronic system, the invariant mass squared, q;{2}, of the lepton and neutrino pair, the kinematic variable P+, or one of their combinations. We then determine partial branching fractions in limited regions of phase space: DeltaB=(1.18+/-0.09_{stat}+/-0.07_{syst}+/-0.01_{theor})x10;{-3} (M_{X}<1.55 GeV/c;{2}), DeltaB=(0.95+/-0.10_{stat}+/-0.08_{syst}+/-0.01_{theor})x10;{-3} (P+<0.66 GeV/c), and DeltaB=(0.81+/-0.08_{stat}+/-0.07_{syst}+/-0.02_{theor})x10;{-3} (M_{X}<1.7 GeV/c;{2}, q;{2}>8 GeV;{2}/c;{4}). Corresponding values of |V_{ub}| are extracted using several theoretical calculations.

Receptor flexibility for large-scale in silico ligand screens: chances and challenges.

An important contribution to today's computer-aided drug design is the automated screening of large compound databases against structurally resolved protein receptors targets. The introduction of ligand flexibility has, by now, become a standardized procedure. In contrast, a general approach to treat target degrees of freedom is still to be found, a consequence of the extreme increase of computational complexity, which comes along with the relaxation of protein degrees of freedom. In this chapter, we discuss in some detail both benefits and present limitations of target flexibility for high-throughput in silico database screens. Among the benefits are an improved diversity of binding modes, which allows one to identify a wider class of drug candidates. The limitations are related to a diminishing docking accuracy and an increased number of false hits. Using the thymidine kinase receptor and ten known inhibitors as an example, we describe in detail how target flexibility was implemented and how it affected the screening performance.