Vibrational Dichroism of Chiral Valley Phonons.

Valley degrees of freedom in transition metal dichalcogenides thoroughly influence electron-phonon coupling and its nonequilibrium dynamics. We conducted a first-principles study of the quantum kinetics of chiral phonons following valley-selective carrier excitation with circularly polarized light. Our numerical investigations treat the ultrafast dynamics of electrons and phonons on equal footing within a parameter-free ab initio framework. We report the emergence of valley-polarized phonon populations in monolayer MoS2 that can be selectively excited at either the K or K' valleys depending on the light helicity. The resulting vibrational state is characterized by a distinctive chirality, which lifts time-reversal symmetry of the lattice on transient time scales. We show that chiral valley phonons can further lead to fingerprints of vibrational dichroism detectable by ultrafast diffuse scattering and persist beyond 10 ps. The valley polarization of nonequilibrium phonon populations could be exploited as an information carrier, thereby extending the paradigm of valleytronics to the domain of vibrational excitations.

Direct View of Phonon Dynamics in Atomically Thin MoS2.

Transition-metal dichalcogenide monolayers and heterostructures are highly tunable material systems that provide excellent models for physical phenomena at the two-dimensional (2D) limit. While most studies to date have focused on electrons and electron-hole pairs, phonons also play essential roles. Here, we apply ultrafast electron diffraction and diffuse scattering to directly quantify, with time and momentum resolution, electron-phonon coupling (EPC) in monolayer molybdenum disulfide and phonon transport from the monolayer to a silicon nitride substrate. Optically generated hot carriers result in a profoundly anisotropic distribution of phonons in the monolayer within ∼5 ps. A quantitative comparison with ab initio ultrafast dynamics simulations reveals the essential role of dielectric screening in weakening EPC. Thermal transport from the monolayer to the substrate occurs with the phonon system far from equilibrium. While screening in 2D is known to strongly affect equilibrium properties, our findings extend this understanding to the dynamic regime.

Accessing the Anisotropic Nonthermal Phonon Populations in Black Phosphorus.

We combine ultrafast electron diffuse scattering experiments and first-principles calculations of the coupled electron-phonon dynamics to provide a detailed momentum-resolved picture of lattice thermalization in black phosphorus. The measurements reveal the emergence of highly anisotropic nonthermal phonon populations persisting for several picoseconds after exciting the electrons with a light pulse. Ultrafast dynamics simulations based on the time-dependent Boltzmann formalism are supplemented by calculations of the structure factor, defining an approach to reproduce the experimental signatures of nonequilibrium structural dynamics. The combination of experiments and theory enables us to identify highly anisotropic electron-phonon scattering processes as the primary driving force of the nonequilibrium lattice dynamics in black phosphorus. Our approach paves the way toward unravelling and controlling microscopic energy flows in two-dimensional materials and van der Waals heterostructures, and may be extended to other nonequilibrium phenomena involving coupled electron-phonon dynamics such as superconductivity, phase transitions, or polaron physics.

Efficient First-Principles Methodology for the Calculation of the All-Phonon Inelastic Scattering in Solids.

Inelastic scattering experiments are key methods for mapping the full dispersion of fundamental excitations of solids in the ground as well as nonequilibrium states. A quantitative analysis of inelastic scattering in terms of phonon excitations requires identifying the role of multiphonon processes. Here, we develop an efficient first-principles methodology for calculating the all-phonon quantum mechanical structure factor of solids. We demonstrate our method by obtaining excellent agreement between measurements and calculations of the diffuse scattering patterns of black phosphorus, showing that multiphonon processes play a substantial role. The present approach constitutes a step towards the interpretation of static and time-resolved electron, x-ray, and neutron inelastic scattering data.

Ultrafast Hot Phonon Dynamics in MgB_{2} Driven by Anisotropic Electron-Phonon Coupling.

The zone-center E_{2g} modes play a crucial role in MgB_{2}, controlling the scattering mechanisms in the normal state as well the superconducting pairing. Here, we demonstrate via first-principles quantum-field theory calculations that, due to the anisotropic electron-phonon interaction, a hot-phonon regime where the E_{2g} phonons can achieve significantly larger effective populations than other modes, is triggered in MgB_{2} by the interaction with an ultrashort laser pulse. Spectral signatures of this scenario in ultrafast pump-probe Raman spectroscopy are discussed in detail, revealing also a fundamental role of nonadiabatic processes in the optical features of the E_{2g} mode.

Nonadiabatic Kohn Anomaly in Heavily Boron-Doped Diamond.

We report evidence of a nonadiabatic Kohn anomaly in boron-doped diamond, using a joint theoretical and experimental analysis of the phonon dispersion relations. We demonstrate that standard calculations of phonons using density-functional perturbation theory are unable to reproduce the dispersion relations of the high-energy phonons measured by high-resolution inelastic x-ray scattering. On the contrary, by taking into account nonadiabatic effects within a many-body field-theoretic framework, we obtain excellent agreement with our experimental data. This result indicates a breakdown of the Born-Oppenheimer approximation in the phonon dispersion relations of boron-doped diamond.

Band structures of plasmonic polarons.

Using state-of-the-art many-body calculations based on the "GW plus cumulant" approach, we show that electron-plasmon interactions lead to the emergence of plasmonic polaron bands in the band structures of common semiconductors. Using silicon and group IV transition-metal dichalcogenide monolayers (AX_{2} with A=Mo,W and X=S, Se) as prototypical examples, we demonstrate that these new bands are a general feature of systems characterized by well-defined plasmon resonances. We find that the energy versus momentum dispersion relations of these plasmonic structures closely follow the standard valence bands, although they appear broadened and blueshifted by the plasmon energy. Based on our results, we identify general criteria for observing plasmonic polaron bands in the angle-resolved photoelectron spectra of solids.

Bond breaking and bond formation: how electron correlation is captured in many-body perturbation theory and density-functional theory.

For the paradigmatic case of H(2) dissociation, we compare state-of-the-art many-body perturbation theory in the GW approximation and density-functional theory in the exact-exchange plus random-phase approximation (RPA) for the correlation energy. For an unbiased comparison and to prevent spurious starting point effects, both approaches are iterated to full self-consistency (i.e., sc-RPA and sc-GW). The exchange-correlation diagrams in both approaches are topologically identical, but in sc-RPA they are evaluated with noninteracting and in sc-GW with interacting Green functions. This has a profound consequence for the dissociation region, where sc-RPA is superior to sc-GW. We argue that for a given diagrammatic expansion, sc-RPA outperforms sc-GW when it comes to bond breaking. We attribute this to the difference in the correlation energy rather than the treatment of the kinetic energy.

An Overview of In Vitro Assays of 64Cu-, 68Ga-, 125I-, and 99mTc-Labelled Radiopharmaceuticals Using Radiometric Counters in the Era of Radiotheranostics.

Radionuclides are unstable isotopes that mainly emit alpha (α), beta (ß) or gamma (γ) radiation through radiation decay. Therefore, they are used in the biomedical field to label biomolecules or drugs for diagnostic imaging applications, such as positron emission tomography (PET) and/or single-photon emission computed tomography (SPECT). A growing field of research is the development of new radiopharmaceuticals for use in cancer treatments. Preclinical studies are the gold standard for translational research. Specifically, in vitro radiopharmaceutical studies are based on the use of radiopharmaceuticals directly on cells. To date, radiometric ß- and γ-counters are the only tools able to assess a preclinical in vitro assay with the aim of estimating uptake, retention, and release parameters, including time- and dose-dependent cytotoxicity and kinetic parameters. This review has been designed for researchers, such as biologists and biotechnologists, who would like to approach the radiobiology field and conduct in vitro assays for cellular radioactivity evaluations using radiometric counters. To demonstrate the importance of in vitro radiopharmaceutical assays using radiometric counters with a view to radiogenomics, many studies based on 64Cu-, 68Ga-, 125I-, and 99mTc-labeled radiopharmaceuticals have been revised and summarized in this manuscript.

Chirality of Valley Excitons in Monolayer Transition-Metal Dichalcogenides.

By enabling control of valley degrees of freedom in transition-metal dichalcogenides, valley-selective circular dichroism has become a key concept in valleytronics. Herein, we show that valley excitons, bound electron-hole pairs formed at the K or K̅ valleys upon absorption of circularly polarized light, are chiral quasiparticles characterized by a finite orbital angular momentum (OAM). We further formulate an ab initio many-body theory of valley-selective circular dichroism and valley excitons based on the Bethe-Salpeter equation. Besides governing the interaction with circularly polarized light, the OAM confers upon excitons a finite magnetization that manifests itself through an excitonic Zeeman splitting upon interaction with external magnetic fields. The good agreement between our ab initio calculations and recent experimental measurements of the exciton Zeeman shifts corroborates this picture, indicating that valley excitons can carry angular momentum even in their singlet state.

Nonequilibrium Lattice Dynamics in Monolayer MoS2.

The coupled nonequilibrium dynamics of electrons and phonons in monolayer MoS2 is investigated by combining first-principles calculations of the electron-phonon and phonon-phonon interactions with the time-dependent Boltzmann equation. Strict phase-space constraints in the electron-phonon scattering are found to influence profoundly the decay path of excited electrons and holes, restricting the emission of phonons to crystal momenta close to a few high-symmetry points in the Brillouin zone. As a result of momentum selectivity in the phonon emission, the nonequilibrium lattice dynamics is characterized by the emergence of a highly anisotropic population of phonons in reciprocal space, which persists for up to 10 ps until thermal equilibrium is restored by phonon-phonon scattering. Achieving control of the nonequilibrium dynamics of the lattice may provide unexplored opportunities to selectively enhance the phonon population of two-dimensional crystals and, thereby, transiently tailor electron-phonon interactions over subpicosecond time scales.

A Wearable Pendant Sensor to Monitor Compliance with Range of Motion Lymphatic Health Exercise.

Lymphedema is a chronic and debilitating condition affecting 1 in 1000 Americans and there is no known cure for it. The optimal lymph flow (TOLF) is an effective preventive exercise program designed to reduce the risks of lymphedema. This paper proposes a portable and wearable medical device to monitor compliance with the TOLF therapy. Specifically, the wearable pendant sensor (WPS), a low-fidelity prototype of the proposed design, is developed and tested in comparison with a markerless optical motion capture system (Kinect) for measurement accuracy during shoulder abduction-adduction and flexion-extension exercises. It is shown that the Kendall's Tau between the measurements obtained from the WPS and Kinect devices yields a correlation coefficient ρ = 0.807 for abduction-adduction exercise and ρ = 0.783 for flexion-extension exercise with a significance level of p < 0.001, indicating a strong correlation and high statistical significance. Following careful clinical assessment and validation, preliminary engineering design of this paper can be transformed into an Internet of Things (IoT)-based medical device to facilitate telemonitoring of TOLF therapy. Deployment of such an IoT-based device in patient homes can permit remote assessment of motor function to enhance treatment adherence.Clinical Relevance-This paper documents a WPS with potential to render an IoT-based medical device for monitoring adherence to TOLF exercise program to prevent the risk of post-operative lymphedema.

Massive mitral annular calcification mimicking intracardiac mass: Multimodality approach to diagnosis.

The correct differential diagnosis of cardiac masses can be challenging and often carries important clinical implications. We present the case of a 78-year-old man with a cardiac mass of unclear etiology diagnosed on echocardiography. Using a multimodality approach with cardiac magnetic resonance and computed tomography, it was possible to define the real nature of the mass as composed of 2 voluminous calcifications of the mitral annulus.

Origin of the crossover from polarons to Fermi liquids in transition metal oxides.

Transition metal oxides host a wealth of exotic phenomena ranging from charge, orbital and magnetic order to nontrivial topological phases and superconductivity. In order to translate these unique materials properties into device functionalities these materials must be doped; however, the nature of carriers and their conduction mechanism at the atomic scale remain unclear. Recent angle-resolved photoelectron spectroscopy investigations provided insight into these questions, revealing that the carriers of prototypical metal oxides undergo a transition from a polaronic liquid to a Fermi liquid regime with increasing doping. Here, by performing ab initio many-body calculations of angle-resolved photoemission spectra of titanium dioxide, we show that this transition originates from non-adiabatic polar electron-phonon coupling, and occurs when the frequency of plasma oscillations exceeds that of longitudinal-optical phonons. This finding suggests that a universal mechanism may underlie polaron formation in transition metal oxides, and provides a pathway for engineering emergent properties in quantum matter.

Benchmark of GW Approaches for the GW100 Test Set.

For the recent GW100 test set of molecular ionization energies, we present a comprehensive assessment of different GW methodologies: fully self-consistent GW (scGW), quasiparticle self-consistent GW (qsGW), partially self-consistent GW0 (scGW0), perturbative GW (G0W0), and optimized G0W0 based on the minimization of the deviation from the straight-line error (DSLE-min GW). We compare our GW calculations to coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] reference data for GW100. We find scGW and qsGW ionization energies in excellent agreement with CCSD(T), with discrepancies typically smaller than 0.3 eV (scGW) and 0.2 eV (qsGW), respectively. For scGW0 and G0W0 the deviation from CCSD(T) is strongly dependent on the starting point. We further relate the discrepancy between the GW ionization energies and CCSD(T) to the deviation from straight line error (DSLE). In DSLE-minimized GW calculations, the DSLE is significantly reduced, yielding a systematic improvement in the description of the ionization energies.

GW100: Benchmarking G0W0 for Molecular Systems.

We present the GW100 set. GW100 is a benchmark set of the ionization potentials and electron affinities of 100 molecules computed with the GW method using three independent GW codes and different GW methodologies. The quasi-particle energies of the highest-occupied molecular orbitals (HOMO) and lowest-unoccupied molecular orbitals (LUMO) are calculated for the GW100 set at the G0W0@PBE level using the software packages TURBOMOLE, FHI-aims, and BerkeleyGW. The use of these three codes allows for a quantitative comparison of the type of basis set (plane wave or local orbital) and handling of unoccupied states, the treatment of core and valence electrons (all electron or pseudopotentials), the treatment of the frequency dependence of the self-energy (full frequency or more approximate plasmon-pole models), and the algorithm for solving the quasi-particle equation. Primary results include reference values for future benchmarks, best practices for convergence within a particular approach, and average error bars for the most common approximations.