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- ItemShort-Range Cooperative Slow-down of Water Solvation Dynamics Around SO42--Mg2+ Ion Pairs(Washington, DC : American Chemical Society, 2022) Kundu, Achintya; Mamatkulov, Shavkat I.; Brünig, Florian N.; Bonthuis, Douwe Jan; Netz, Roland R.; Elsaesser, Thomas; Fingerhut, Benjamin P.The presence of ions affects the structure and dynamics of water on a multitude of length and time scales. In this context, pairs of Mg2+ and SO42- ions in water constitute a prototypical system for which conflicting pictures of hydration geometries and dynamics have been reported. Key issues are the molecular pair and solvation shell geometries, the spatial range of electric interactions, and their impact on solvation dynamics. Here, we introduce asymmetric SO42- stretching vibrations as new and most specific local probes of solvation dynamics that allow to access ion hydration dynamics at the dilute concentration (0.2 M) of a native electrolyte environment. Highly sensitive heterodyne 2D-IR spectroscopy in the fingerprint region of the SO42- ions around 1100 cm-1 reveals a specific slow-down of solvation dynamics for hydrated MgSO4 and for Na2SO4 in the presence of Mg2+ ions, which manifests as a retardation of spectral diffusion compared to aqueous Na2SO4 solutions in the absence of Mg2+ ions. Extensive molecular dynamics and density functional theory QM/MM simulations provide a microscopic view of the observed ultrafast dephasing and hydration dynamics. They suggest a molecular picture where the slow-down of hydration dynamics arises from the structural peculiarities of solvent-shared SO42--Mg2+ ion pairs.
- ItemTransient spin injection efficiencies at ferromagnet/metal interfaces(Weinheim : Wiley-VCH, 2022-10-19) Elliott, Peter; Eschenlohr, Andrea; Chen, Jinghao; Shallcross, Sam; Bovensiepen, Uwe; Dewhurst, John Kay; Sharma, SangeetaSpin injection across interfaces driven by ultrashort optical pulses on femtosecond timescales constitutes a new way to design spintronics applications. Targeted utilization of this phenomenon requires knowledge of the efficiency of non-equilibrium spin injection. From a quantitative comparison of ab initio time-dependent density functional theory and interface-sensitive, time-resolved non-linear optical experiment, the spin injection efficiency (SIE) at the Co/Cu(001) interface is determined, and its microscopic origin, i.e., the influence of spin-orbit coupling and the interface electronic structure, is discussed. Moreover, we theoretically predict that the SIE at ferromagnetic–metal interfaces can be optimized through laser pulse and materials parameters, namely the fluence, pulse duration, and substrate material.
- ItemZwitterionic Dendrimersomes: A Closer Xenobiotic Mimic of Cell Membranes(Weinheim : Wiley-VCH, 2022-10-31) Joseph, Anton; Wagner, Anna M.; Garay-Sarmiento, Manuela; Aleksanyan, Mina; Haraszti, Tamás; Söder, Dominik; Georgiev, Vasil N.; Dimova, Rumiana; Percec, Virgil; Rodriguez-Emmenegger, CesarBuilding functional mimics of cell membranes is an important task toward the development of synthetic cells. So far, lipid and amphiphilic block copolymers are the most widely used amphiphiles with the bilayers by the former lacking stability while membranes by the latter are typically characterized by very slow dynamics. Herein, a new type of Janus dendrimer containing a zwitterionic phosphocholine hydrophilic headgroup (JDPC) and a 3,5-substituted dihydrobenzoate-based hydrophobic dendron is introduced. JDPC self-assembles in water into zwitterionic dendrimersomes (z-DSs) that faithfully recapitulate the cell membrane in thickness, flexibility, and fluidity, while being resilient to harsh conditions and displaying faster pore closing dynamics in the event of membrane rupture. This enables the fabrication of hybrid DSs with components of natural membranes, including pore-forming peptides, structure-directing lipids, and glycans to create raft-like domains or onion vesicles. Moreover, z-DSs can be used to create active synthetic cells with life-like features that mimic vesicle fusion and motility as well as environmental sensing. Despite their fully synthetic nature, z-DSs are minimal cell mimics that can integrate and interact with living matter with the programmability to imitate life-like features and beyond.
- ItemSonopharmacology: controlling pharmacotherapy and diagnosis by ultrasound-induced polymer mechanochemistry(Cambridge : RSC, 2022) Yildiz, Deniz; Göstl, Robert; Herrmann, AndreasActive pharmaceutical ingredients are the most consequential and widely employed treatment in medicine although they suffer from many systematic limitations, particularly off-target activity and toxicity. To mitigate these effects, stimuli-responsive controlled delivery and release strategies for drugs are being developed. Fueled by the field of polymer mechanochemistry, recently new molecular technologies enabled the emergence of force as an unprecedented stimulus for this purpose by using ultrasound. In this research area, termed sonopharmacology, mechanophores bearing drug molecules are incorporated within biocompatible macromolecular scaffolds as preprogrammed, latent moieties. This review presents the novelties in controlling drug activation, monitoring, and release by ultrasound, while discussing the limitations and challenges for future developments.
- ItemGain and lasing from CdSe/CdS nanoplatelet stripe waveguides(Amsterdam : Elsevier, 2022) Belitsch, Martin; Dirin, Dmitry N.; Kovalenko, Maksym V.; Pichler, Kevin; Rotter, Stefan; Ghalgaoui, Ahmed; Ditlbacher, Harald; Hohenau, Andreas; Krenn, Joachim R.Colloidal semiconducting nanocrystals are efficient, stable and spectrally tunable emitters, but achievable optical gain is often limited by fast nonradiative processes. These processes are strongly suppressed in slab-shaped nanocrystals (nanoplatelets), due to relaxed exciton Coulomb interaction. Here, we show that CdSe/CdS nanoplatelets can be engineered into (sub)microscopic stripe waveguides that achieve lasing without further components for feedback, i.e., just relying on the stripe end reflection. We find a remarkably high gain factor for the CdSe/CdS nanoplatelets of 1630 cm−1. In addition, by comparison with numerical simulations we assign a distinct emission peak broadening above laser threshold to emission pulse shortening. Our results illustrate the feasibility of geometrically simple monolithic microscale nanoplatelet lasers as an attractive option for a variety of photonic applications.
- ItemNanostructured In3SbTe2 antennas enable switching from sharp dielectric to broad plasmonic resonances(Berlin : de Gruyter, 2022) Heßler, Andreas; Wahl, Sophia; Kristensen, Philip Trøst; Wuttig, Matthias; Busch, Kurt; Taubner, ThomasPhase-change materials (PCMs) allow for non-volatile resonance tuning of nanophotonic components. Upon switching, they offer a large dielectric contrast between their amorphous and crystalline phases. The recently introduced “plasmonic PCM” In3SbTe2 (IST) additionally features in its crystalline phase a sign change of its permittivity over a broad infrared spectral range. While optical resonance switching in unpatterned IST thin films has been investigated before, nanostructured IST antennas have not been studied, yet. Here, we present numerical and experimental investigations of nanostructured IST rod and disk antennas. By crystallizing the IST with microsecond laser pulses, we switched individual antennas from narrow dielectric to broad plasmonic resonances. For the rod antennas, we demonstrated a resonance shift of up to 1.2 µm (twice the resonance width), allowing on/off switching of plasmonic resonances with a contrast ratio of 2.7. With the disk antennas, we realized an increase of the resonance width by more than 800% from 0.24 µm to 1.98 µm while keeping the resonance wavelength constant. Further, we demonstrated intermediate switching states by tuning the crystallization depth within the resonators. Our work empowers future design concepts for nanophotonic applications like active spectral filters, tunable absorbers, and switchable flat optics.
- ItemA general approach for all-visible-light switching of diarylethenes through triplet sensitization using semiconducting nanocrystals(London [u.a.] : RSC, 2022) Hou, Lili; Larsson, Wera; Hecht, Stefan; Andréasson, Joakim; Albinsson, BoCoupling semiconducting nanocrystals (NCs) with organic molecules provides an efficient route to generate and transfer triplet excitons. These excitons can be used to power photochemical transformations such as photoisomerization reactions using low energy radiation. Thus, it is desirable to develop a general approach that can efficiently be used to control photoswitches using all-visible-light aiming at future applications in life- and materials sciences. Here, we demonstrate a simple ‘cocktail’ strategy that can achieve all-visible-light switchable diarylethenes (DAEs) through triplet energy transfer from the hybrid of CdS NCs and phenanthrene-3-carboxylic acid, with high photoisomerization efficiency and improved fatigue resistance. The size-tunable excitation energies of CdS NCs make it possible to precisely match the clear spectral window of the relevant DAE photoswitch. We demonstrate reversible all-visible-light photoisomerization of a series of DAE derivatives both in the liquid and solid state, even in the presence of oxygen. Our general strategy is promising for fabrication of all-visible-light activated optoelectronic devices as well as memories, and should in principle be adaptable to photopharmacology.
- ItemHigh power, high repetition rate laser-based sources for attosecond science(Bristol : IOP Publishing, 2022) Furch, F.J.; Witting, T.; Osolodkov, M.; Schell, F.; Schulz, C.P.; Vrakking, M.J.Within the last two decades attosecond science has been established as a novel research field providing insights into the ultrafast electron dynamics that follows a photoexcitation or photoionization process. Enabled by technological advances in ultrafast laser amplifiers, attosecond science has been in turn, a powerful engine driving the development of novel sources of intense ultrafast laser pulses. This article focuses on the development of high repetition rate laser-based sources delivering high energy pulses with a duration of only a few optical cycles, for applications in attosecond science. In particular, a high power, high repetition rate optical parametric chirped pulse amplification system is described, which was developed to drive an attosecond pump-probe beamline targeting photoionization experiments with electron-ion coincidence detection at high acquisition rates.
- ItemGeneral Time-Dependent Configuration-Interaction Singles II: The Atomic Case(Woodbury, NY : Inst., 2022-10-10) Carlström, Stefanos; Bertolino, Mattias; Dahlström, Jan Marcus; Patchkovskii, SergueiWe present a specialization of the grid-based implementation of the time-dependent configuration-interaction singles described in the preceding paper [S. Carlström et al., preceding paper, Phys. Rev. A 106, 043104 (2022)]. to the case of spherical symmetry. We describe the intricate time propagator in detail and conclude with a few example calculations. Among these, of note are high-resolution photoelectron spectra in the vicinity of the Fano resonances in photoionization of neon and spin-polarized photoelectrons from xenon, in agreement with recent experiments.
- ItemGeneral Time-Dependent Configuration-Interaction Singles I: The Molecular Case(Woodbury, NY : Inst., 2022-10-10) Carlström, Stefanos; Spanner, Michael; Patchkovskii, SergueiWe present a grid-based implementation of the time-dependent configuration-interaction singles method suitable for computing the strong-field ionization of small gas-phase molecules. After outlining the general equations of motion used in our treatment of this method, we present example calculations of strong-field ionization of He, LiH, H2O, and C2H4 that demonstrate the utility of our implementation. The following paper [S. Carlström et al., following paper, Phys. Rev. A 106, 042806 (2022)] specializes to the case of spherical symmetry, which is applied to various atoms.