Excitonic Insulators and Superfluidity in Two-Dimensional Bilayers without External Fields.

We explore a new platform for realizing excitonic insulators, namely van der Waals (vdW) bilayers comprising two-dimensional Janus materials. In previous studies, type II heterobilayers have been brought to the excitonic insulating regime by tuning the band alignment using external gates. In contrast, the Janus bilayers presented here represent intrinsic excitonic insulators. We first conduct ab initio calculations to obtain the quasiparticle band structures, screened Coulomb interaction, and interlayer exciton binding energies of the bilayers. These ab initio-derived quantities are then used to construct a BCS-like Hamiltonian of the exciton condensate. By solving the mean-field gap equation, we identify 16 vdW Janus bilayers with insulating ground states and superfluid properties. Our calculations expose a new class of advanced materials that are likely to exhibit novel excitonic phases at low temperatures and highlight the subtle competition between interlayer hybridization, spin-orbit coupling, and dielectric screening that governs their properties.

Controlled generation of luminescent centers in hexagonal boron nitride by irradiation engineering.

Luminescent centers in the two-dimensional material hexagonal boron nitride have the potential to enable quantum applications at room temperature. To be used for applications, it is crucial to generate these centers in a controlled manner and to identify their microscopic nature. Here, we present a method inspired by irradiation engineering with oxygen atoms. We systematically explore the influence of the kinetic energy and the irradiation fluence on the generation of luminescent centers. We find modifications of their density for both parameters, while a fivefold enhancement is observed with increasing fluence. Molecular dynamics simulations clarify the generation mechanism of these centers and their microscopic nature. We infer that VNCB and [Formula: see text] are the most likely centers formed. Ab initio calculations of their optical properties show excellent agreement with our experiments. Our methodology generates quantum emitters in a controlled manner and provides insights into their microscopic nature.

Grid-Based Projector Augmented Wave (GPAW) Implementation of Quantum Mechanics/Molecular Mechanics (QM/MM) Electrostatic Embedding and Application to a Solvated Diplatinum Complex.

A multiscale density functional theory-quantum mechanics/molecular mechanics (DFT-QM/MM) scheme is presented, based on an efficient electrostatic coupling between the electronic density obtained from a grid-based projector augmented wave (GPAW) implementation of density functional theory and a classical potential energy function. The scheme is implemented in a general fashion and can be used with various choices for the descriptions of the QM or MM regions. Tests on H2O clusters, ranging from dimer to decamer show that no systematic energy errors are introduced by the coupling that exceeds the differences in the QM and MM descriptions. Over 1 ns of liquid water, Born-Oppenheimer QM/MM molecular dynamics (MD) are sampled combining 10 parallel simulations, showing consistent liquid water structure over the QM/MM border. The method is applied in extensive parallel MD simulations of an aqueous solution of the diplatinum [Pt2(P2O5H2)4]4- complex (PtPOP), spanning a total time period of roughly half a nanosecond. An average Pt-Pt distance deviating only 0.01 Å from experimental results, and a ground-state Pt-Pt oscillation frequency deviating by <2% from experimental results were obtained. The simulations highlight a remarkable harmonicity of the Pt-Pt oscillation, while also showing clear signs of Pt-H hydrogen bonding and directional coordination of water molecules along the Pt-Pt axis of the complex.

Layered van der Waals crystals with hyperbolic light dispersion.

Compared to artificially structured hyperbolic metamaterials, whose performance is limited by the finite size of the metallic components, the sparse number of naturally hyperbolic materials recently discovered are promising candidates for the next generation of hyperbolic materials. Using first-principles calculations, we extend the number of known naturally hyperbolic materials to the broad class of layered transition metal dichalcogenides (TMDs). The diverse electronic properties of the transition metal dichalcogenides result in a large variation of the hyperbolic frequency regimes ranging from the near-infrared to the ultraviolet. Combined with the emerging field of van der Waals heterostructuring, we demonstrate how the hyperbolic properties can be further controlled by stacking different two-dimensional crystals opening new perspectives for atomic-scale design of photonic metamaterials. As an application, we identify candidates for Purcell factor control of emission from diamond nitrogen-vacancy centers.Natural hyperbolic materials retain the peculiar optical properties of traditional metamaterials whilst not requiring artificial structuring. Here, the authors perform a theoretical screening of a large class of natural materials with hyperbolic dispersion among the family of layered transition metal dichalcogenides.

The impact of hematopoietic stem cell transplantation on sexuality: a systematic review of the literature.

In this paper we review evidence concerning the impact of hematopoietic SCT (HSCT) on sexuality. The aims are to determine: (1) the sexual changes experienced by patients following allogeneic or autologous HSCT, and its consequences; (2) changes in the sexual function over time and (3) the impact of physiological changes induced by intensive treatment with radiation and chemotherapy on sexual functioning. Four databases were searched for articles published between January 1995 and May 2011. A total of 14 studies were identified and analyzed. We found that (1) multiple aspects of sexuality were affected, and the impact and etiology of these sexual alterations were different between genders, and (2) recovery of sexual activity and pleasure occurred in the first 2 years after HSCT, although it appears that some survivors are more likely to experience sexual dysfunction even 5-10 years after HSCT as compared with controls; and (3) there was contradictory evidence concerning possible differences between allogeneic and autologous HSCT, although there was a significant relation between the sexual dysfunctions and the type of chemotherapy administrated as conditioning and chronic GVHD. Future prospective research in sexual dysfunction with specific reliable validated instruments and more adequate sample sizes will be required to definitively evaluate the impact of HSCT on sexuality.

Electrical conductivity in Li2O2 and its role in determining capacity limitations in non-aqueous Li-O2 batteries.

Non-aqueous Li-air or Li-O(2) cells show considerable promise as a very high energy density battery couple. Such cells, however, show sudden death at capacities far below their theoretical capacity and this, among other problems, limits their practicality. In this paper, we show that this sudden death arises from limited charge transport through the growing Li(2)O(2) film to the Li(2)O(2)-electrolyte interface, and this limitation defines a critical film thickness, above which it is not possible to support electrochemistry at the Li(2)O(2)-electrolyte interface. We report both electrochemical experiments using a reversible internal redox couple and a first principles metal-insulator-metal charge transport model to probe the electrical conductivity through Li(2)O(2) films produced during Li-O(2) discharge. Both experiment and theory show a "sudden death" in charge transport when film thickness is ~5 to 10 nm. The theoretical model shows that this occurs when the tunneling current through the film can no longer support the electrochemical current. Thus, engineering charge transport through Li(2)O(2) is a serious challenge if Li-O(2) batteries are ever to reach their potential.

Communication: strong excitonic and vibronic effects determine the optical properties of Li2O2.

The band structure and optical absorption spectrum of lithium peroxide (Li(2)O(2)) is calculated from first-principles using the G(0)W(0) approximation and the Bethe-Salpeter equation, respectively. A strongly localized (Frenkel type) exciton corresponding to the π(∗)→σ(∗) transition on the O(2)(-2) peroxide ion gives rise to a narrow absorption peak around 1.2 eV below the calculated bandgap of 4.8 eV. In the excited state, the internal O(2)(-2) bond is significantly weakened due to the population of the σ(∗) orbital. As a consequence, the bond is elongated by almost 0.5 Å leading to an extreme Stokes shift of 2.6 eV. The strong vibronic coupling entails significant broadening of the excitonic absorption peak in good agreement with diffuse reflectance data on Li(2)O(2) which shows a rather featureless spectrum with an absorption onset around 3.0 eV. These results should be important for understanding the origin of the high potential losses and low current densities, which are presently limiting the performance of Li-air batteries.

Ab initio calculations of the electronic properties of polypyridine transition metal complexes and their adsorption on metal surfaces in the presence of solvent and counterions.

Os(II)/(III) and Co(II)/(III) polypyridine complexes in aqueous solution are robust molecular entities both in freely solute state and adsorbed on Au(111)- and Pt(111)-electrode surfaces. This class of robust coordination chemical compounds have recently been characterized by electrochemical scanning tunneling microscopy (in situ STM). The Os-complexes were found to display strong tunneling spectroscopic (STS) features at the level of resolution of the single molecule while STS features of the Co complexes, although clear, were much weaker. The data was framed by concise but phenomenological theory of interfacial electrochemical electron transfer extended to the electrochemical in situ STM configuration. With a view on first-principle insight into the in situ STM behavior of robust redox (as opposed to nonredox) molecules, we present in this report a density functional theory (DFT) study of the complexes in both free and adsorbate state, in either state exposed to both stoichiometric counterions and a large assembly of solvent water molecules. The oxidation states of the complexes were controlled, first by introducing chlorine counter atoms followed by spontaneous attraction of electrons from the complexes, also at first in electrostatically neutral form. Second, the solvent is found to provide strong dielectric screening of this charge transfer process and to be crucial for achieving the full chemically meaningful charge separated ionic oxidation states. The molecular charge and structure of the complexes in the presence of the solvent, are conserved upon adsorption, whereas the structural features of the different oxidation states are completely lost upon adsorption under vacuum conditions. Detailed microscopic insight such as offered by the present study will be important in molecular-based approaches to "smart" redox molecules enclosed in in situ STM or other nanoscale and single-molecules scale configurations in condensed matter environments.

Renormalization of optical excitations in molecules near a metal surface.

The lowest electronic excitations of benzene and a set of donor-acceptor molecular complexes are calculated for the gas phase and on the Al(111) surface using the many-body Bethe-Salpeter equation. The energy of the charge-transfer excitations obtained for the gas phase complexes are found to be around 10% lower than the experimental values. When the molecules are placed outside the surface, the enhanced screening from the metal reduces the exciton binding energies by several eVs and the transition energies by up to 1 eV depending on the size of the transition-generated dipole. As a striking consequence we find that close to the metal surface the optical gap of benzene can exceed its quasiparticle gap. A classical image charge model for the screened Coulomb interaction can account for all these effects which, on the other hand, are completely missed by standard time-dependent density functional theory.

Pre-hospital treatment of STEMI patients. A scientific statement of the Working Group Acute Cardiac Care of the European Society of Cardiology.

In ST-elevation myocardial infarction (STEMI) the pre-hospital phase is the most critical, as the administration of the most appropriate treatment in a timely manner is instrumental for mortality reduction. STEMI systems of care based on networks of medical institutions connected by an efficient emergency medical service are pivotal. The first steps are devoted to minimize the patient's delay in seeking care, rapidly dispatch a properly staffed and equipped ambulance to make the diagnosis on scene, deliver initial drug therapy and transport the patient to the most appropriate (not necessarily the closest) cardiac facility. Primary PCI is the treatment of choice, but thrombolysis followed by coronary angiography and possibly PCI is a valid alternative, according to patient's baseline risk, time from symptoms onset and primary PCI-related delay. Paramedics and nurses have an important role in pre-hospital STEMI care and their empowerment is essential to increase the effectiveness of the system. Strong cooperation between cardiologists and emergency medicine doctors is mandatory for optimal pre-hospital STEMI care. Scientific societies have an important role in guideline implementation as well as in developing quality indicators and performance measures; health care professionals must overcome existing barriers to optimal care together with political and administrative decision makers.

Communications: Elementary oxygen electrode reactions in the aprotic Li-air battery.

We discuss the electrochemical reactions at the oxygen electrode of an aprotic Li-air battery. Using density functional theory to estimate the free energy of intermediates during the discharge and charge of the battery, we introduce a reaction free energy diagram and identify possible origins of the overpotential for both processes. We also address the question of electron conductivity through the Li(2)O(2) electrode and show that in the presence of Li vacancies Li(2)O(2) becomes a conductor.

Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method.

Electronic structure calculations have become an indispensable tool in many areas of materials science and quantum chemistry. Even though the Kohn-Sham formulation of the density-functional theory (DFT) simplifies the many-body problem significantly, one is still confronted with several numerical challenges. In this article we present the projector augmented-wave (PAW) method as implemented in the GPAW program package (https://wiki.fysik.dtu.dk/gpaw) using a uniform real-space grid representation of the electronic wavefunctions. Compared to more traditional plane wave or localized basis set approaches, real-space grids offer several advantages, most notably good computational scalability and systematic convergence properties. However, as a unique feature GPAW also facilitates a localized atomic-orbital basis set in addition to the grid. The efficient atomic basis set is complementary to the more accurate grid, and the possibility to seamlessly switch between the two representations provides great flexibility. While DFT allows one to study ground state properties, time-dependent density-functional theory (TDDFT) provides access to the excited states. We have implemented the two common formulations of TDDFT, namely the linear-response and the time propagation schemes. Electron transport calculations under finite-bias conditions can be performed with GPAW using non-equilibrium Green functions and the localized basis set. In addition to the basic features of the real-space PAW method, we also describe the implementation of selected exchange-correlation functionals, parallelization schemes, ΔSCF-method, x-ray absorption spectra, and maximally localized Wannier orbitals.

Impact of exchange-correlation effects on the IV characteristics of a molecular junction.

The role of exchange-correlation effects in nonequilibrium quantum transport through molecular junctions is assessed by analyzing the IV curve of a generic two-level model using self-consistent many-body perturbation theory (second Born and GW approximations) on the Keldysh contour. It is demonstrated how the variation of the molecule's energy levels with the bias voltage can produce anomalous peaks in the dI/dV curve. This effect is suppressed by electronic self-interactions and is therefore underestimated in standard transport calculations based on density functional theory. Inclusion of dynamic correlations introduces quasiparticle (QP) scattering which in turn broadens the molecular resonances. The broadening increases strongly with bias and can have a large impact on the calculated IV characteristic.

Influence of functional groups on charge transport in molecular junctions.

Using density functional theory (DFT), we analyze the influence of five classes of functional groups, as exemplified by NO(2), OCH(3), CH(3), CCl(3), and I, on the transport properties of a 1,4-benzenedithiolate (BDT) and 1,4-benzenediamine (BDA) molecular junction with gold electrodes. Our analysis demonstrates how ideas from functional group chemistry may be used to engineer a molecule's transport properties, as was shown experimentally and using a semiempirical model for BDA [Nano Lett. 7, 502 (2007)]. In particular, we show that the qualitative change in conductance due to a given functional group can be predicted from its known electronic effect (whether it is sigma/pi donating/withdrawing). However, the influence of functional groups on a molecule's conductance is very weak, as was also found in the BDA experiments. The calculated DFT conductances for the BDA species are five times larger than the experimental values, but good agreement is obtained after correcting for self-interaction and image charge effects.

Benchmark density functional theory calculations for nanoscale conductance.

We present a set of benchmark calculations for the Kohn-Sham elastic transmission function of five representative single-molecule junctions. The transmission functions are calculated using two different density functional theory methods, namely an ultrasoft pseudopotential plane-wave code in combination with maximally localized Wannier functions and the norm-conserving pseudopotential code SIESTA which applies an atomic orbital basis set. All calculations have been converged with respect to the supercell size and the number of k|| points in the surface plane. For all systems we find that the SIESTA transmission functions converge toward the plane-wave result as the SIESTA basis is enlarged. Overall, we find that an atomic basis with double zeta and polarization is sufficient (and in some cases, even necessary) to ensure quantitative agreement with the plane-wave calculation. We observe a systematic downshift of the SIESTA transmission functions relative to the plane-wave results. The effect diminishes as the atomic orbital basis is enlarged; however, the convergence can be rather slow.

Comparative study of anchoring groups for molecular electronics: structure and conductance of Au-S-Au and Au-NH(2)-Au junctions.

The electrical properties of single-molecule junctions, consisting of an organic molecule coupled to metal electrodes, are sensitive to the detailed atomic structure of the molecule-metal contact. This, in turn, is determined by the anchoring group linking the molecule to the metal. With the aim of identifying and comparing the intrinsic properties of two commonly used anchoring groups, namely thiol and amine groups, we have calculated the atomic structure and conductance traces of different Au-S-Au and Au-NH(2)-Au nanojunctions using density functional theory (DFT). Whereas NH(2) shows a strong structural selectivity towards atop-gold configurations, S shows large variability in its bonding geometries. As a result, the conductance of the Au-NH(2)-Au junction is less sensitive to the structure of the gold contacts than the Au-S-Au junction. These findings support recent experiments which show that amine-bonded molecules exhibit more well-defined conductance properties than do thiol-bonded molecules.

Partly occupied Wannier functions.

We introduce a scheme for constructing partly occupied, maximally localized Wannier functions (WFs) for both molecular and periodic systems. Compared to the traditional occupied WFs the partly occupied WFs possess improved symmetry and localization properties achieved through a bonding-antibonding closing procedure. We demonstrate the equivalence between bonding-antibonding closure and the minimization of the average spread of the WFs in the case of a benzene molecule and a linear chain of Pt atoms. The general applicability of the method is demonstrated through the calculation of WFs for a metallic system with an impurity: a Pt wire with a hydrogen molecular bridge.

Conduction mechanism in a molecular hydrogen contact.

We present first principles calculations for the conductance of a hydrogen molecule bridging a pair of Pt electrodes. The transmission function has a wide plateau with T approximately 1 which extends across the Fermi level and indicates the existence of a single, robust conductance channel with nearly perfect transmission. Through a detailed Wannier function analysis we show that the H(2) bonding state is not involved in the transport and that the plateau forms due to strong hybridization between the H(2) antibonding state and states on the adjacent Pt atoms. The Wannier functions furthermore allow us to derive a resonant-level model for the system with all parameters determined from the fully self-consistent Kohn-Sham Hamiltonian.

Long term risk stratification of patients with acute coronary syndromes: characteristics of troponin T testing and continuous ST segment monitoring.

OBJECTIVE: To examine the long term prognostic characteristics of troponin T testing and continuous multi-lead ST segment monitoring in combination with clinical and 12 lead ECG risk indicators in patients with acute coronary syndromes (ACS). PATIENTS AND DESIGN: Patients with suspected ACS (n = 213) were studied. Troponin T was analysed in blood samples collected during the first 12 hours after admission. Continuous vectorcardiography ST segment monitoring was performed for 24 hours and the number of ST vector magnitude episodes was registered. Patients were followed up for a median of 28 months. The end point was a composite of cardiac death and acute myocardial infarction. RESULTS: Thirty eight (18%) patients reached the composite end point. The median (interquartile range) time from study inclusion to the time of the composite end point was longer for patients predicted to be at risk by troponin T testing (n = 27) than for those predicted to be at risk by ST segment monitoring (n = 20) (8.4 (0.2-15) months v 0.3 (0.1-4.3) months, p = 0.04). Significant univariate predictors of the composite end point were age > or = 65 years, diabetes, previous myocardial infarction, congestive heart failure, use of beta blockers or diuretics at admission, 12 lead ECG ST segment depression at admission, troponin T concentration > or = 0.10 microg/l, and > or = 1 ST vector magnitude episodes. Age > or = 65 years, previous myocardial infarction, and troponin T concentration > or = 0.10 microg/l provided independent prognostic information after multivariate analysis of potential risk variables. The prognostic value of transient ischaemic episodes in ACS seems to be confined to the short term. CONCLUSIONS: Both biochemical and continuous ECG markers reflect an increased risk for patients with ACS; however, the methods exhibit different temporal risk characteristics.