Dimer Coupling Energies of the Si(001) Surface.

The coupling energies between the buckled dimers of the Si(001) surface were determined through analysis of the anisotropic critical behavior of its order-disorder phase transition. Spot profiles in high-resolution low-energy electron diffraction as a function of temperature were analyzed within the framework of the anisotropic two-dimensional Ising model. The validity of this approach is justified by the large ratio of correlation lengths, ξ_{∥}^{+}/ξ_{⊥}^{+}=5.2 of the fluctuating c(4×2) domains above the critical temperature T_{c}=(190.6±10) K. We obtain effective couplings J_{∥}=(-24.9±1.3) meV along the dimer rows and J_{⊥}=(-0.8±0.1) meV across the dimer rows, i.e., antiferromagneticlike coupling of the dimers with c(4×2) symmetry.

All-electron real-time and imaginary-time time-dependent density functional theory within a numeric atom-centered basis function framework.

Real-time time-dependent density functional theory (RT-TDDFT) is an attractive tool to model quantum dynamics by real-time propagation without the linear response approximation. Sharing the same technical framework of RT-TDDFT, imaginary-time time-dependent density functional theory (it-TDDFT) is a recently developed robust-convergence ground state method. Presented here are high-precision all-electron RT-TDDFT and it-TDDFT implementations within a numerical atom-centered orbital (NAO) basis function framework in the FHI-aims code. We discuss the theoretical background and technical choices in our implementation. First, RT-TDDFT results are validated against linear-response TDDFT results. Specifically, we analyze the NAO basis sets' convergence for Thiel's test set of small molecules and confirm the importance of the augmentation basis functions for adequate convergence. Adopting a velocity-gauge formalism, we next demonstrate applications for systems with periodic boundary conditions. Taking advantage of the all-electron full-potential implementation, we present applications for core level spectra. For it-TDDFT, we confirm that within the all-electron NAO formalism, it-TDDFT can successfully converge systems that are difficult to converge in the standard self-consistent field method. We finally benchmark our implementation for systems up to ∼500 atoms. The implementation exhibits almost linear weak and strong scaling behavior.

A fresh look at the structure of aromatic thiols on Au surfaces from theory and experiment.

A detailed study of the adsorption structure of self-assembled monolayers of 4-nitrothiophenol on the Au(111) surface was performed from a theoretical perspective via first-principles density functional theory calculations and experimentally by Raman and vibrational sum frequency spectroscopy (vSFS) with an emphasis on the molecular orientation. Simulations-including an explicit van der Waals (vdW) description-for different adsorbate structures, namely, for (3×3), (2 × 2), and (3 × 3) surface unit cells, reveal a significant tilting of the molecules toward the surface with decreasing coverage from 75° down to 32° tilt angle. vSFS suggests a tilt angle of 50°, which agrees well with the one calculated for a structure with a coverage of 0.25. Furthermore, calculated vibrational eigenvectors and spectra allowed us to identify characteristic in-plane (NO2 scissoring) and out-of-plane (C-H wagging) modes and to predict their strength in the spectrum in dependence of the adsorption geometry. We additionally performed calculations for biphenylthiol and terphenylthiol to assess the impact of multiple aromatic rings and found that vdW interactions are significantly increasing with this number, as evidenced by the absorption energy and the molecule adopting a more upright-standing geometry.

Crystal Structure Induced Preferential Surface Alloying of Sb on Wurtzite/Zinc Blende GaAs Nanowires.

We study the surface diffusion and alloying of Sb into GaAs nanowires (NWs) with controlled axial stacking of wurtzite (Wz) and zinc blende (Zb) crystal phases. Using atomically resolved scanning tunneling microscopy, we find that Sb preferentially incorporates into the surface layer of the {110}-terminated Zb segments rather than the {112̅0}-terminated Wz segments. Density functional theory calculations verify the higher surface incorporation rate into the Zb phase and find that it is related to differences in the energy barrier of the Sb-for-As exchange reaction on the two surfaces. These findings demonstrate a simple processing-free route to compositional engineering at the monolayer level along NWs.

The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface.

Using first-principles calculations based on density-functional theory (DFT), we investigated the effects of the van der Waals (vdW) interactions on the structural and electronic properties of anthracene and pentacene adsorbed on the Ag(111) surface. We found that the inclusion of vdW corrections strongly affects the binding of both anthracene/Ag(111) and pentacene/Ag(111), yielding adsorption heights and energies more consistent with the experimental results than standard DFT calculations with generalized gradient approximation (GGA). For anthracene/Ag(111) the effect of the vdW interactions is even more dramatic: we found that "pure" DFT-GGA calculations (without including vdW corrections) result in preference for a tilted configuration, in contrast to the experimental observations of flat-lying adsorption; including vdW corrections, on the other hand, alters the binding geometry of anthracene/Ag(111), favoring the flat configuration. The electronic structure obtained using a self-consistent vdW scheme was found to be nearly indistinguishable from the conventional DFT electronic structure once the correct vdW geometry is employed for these physisorbed systems. Moreover, we show that a vdW correction scheme based on a hybrid functional DFT calculation (HSE) results in an improved description of the highest occupied molecular level of the adsorbed molecules.

Interplay of hydrogen treatment and nitrogen doping in ZnO nanoparticles: a first-principles study.

With the help of density functional calculations using the HSE and PBE functionals, it is shown that incorporation of nitrogen into ZnO nanoparticles is energetically less costly compared to ZnO bulk, due to charge transfer between Zn dangling bonds and the NO impurity. Neutral NO results after full passivation of the doped nanoparticles by a treatment with atomic hydrogen. A nanocomposite made from such ZnO particles could show thermally activated p-type hopping conductivity.

Accelerated Electron-Hole Separation at the Organic-Inorganic Anthracene/Janus MoSSe Interface.

Organic light-absorbing materials with two-dimensional semiconductor layers as contact electrodes are promising for efficient and flexible low-cost solar cells. Considering anthracene as an absorber and a MoSSe Janus monolayer, we use non-adiabatic molecular dynamics to show that electron transfer from anthracene to MoSSe is faster on the Se side than the S side. The transfer from anthracene to MoS2 and MoSe2 monolayers takes intermediate times. As a rule, we find that a shorter adsorption distance produces a stronger donor-acceptor coupling. The smaller distance on the Se side is rationalized by the attractive force between the intrinsic dipole moment of the Janus structure and that of the molecule induced due to adsorption. Quantum coherence also affects the transfer time. The study provides detailed insights into adsorption of molecules on Janus structures and the resulting electronic and electron vibrational interactions. The results suggest that the dipole interaction plays an important role in the thermodynamic stability, alignment of electronic levels, and electron vibrational dynamics.

Comparison of density functionals for nitrogen impurities in ZnO.

Hybrid functionals and empirical correction schemes are compared to conventional semi-local density functional theory (DFT) calculations in order to assess the predictive power of these methods concerning the formation energy and the charge transfer level of impurities in the wide-gap semiconductor ZnO. While the generalized gradient approximation fails to describe the electronic structure of the N impurity in ZnO correctly, methods that widen the band gap of ZnO by introducing additional non-local potentials yield the formation energy and charge transfer level of the impurity in reasonable agreement with hybrid functional calculations. Summarizing the results obtained with different methods, we corroborate earlier findings that the formation of substitutional N impurities at the oxygen site in ZnO from N atoms is most likely slightly endothermic under oxygen-rich preparation conditions, and introduces a deep level more than 1 eV above the valence band edge of ZnO. Moreover, the comparison of methods elucidates subtle differences in the predicted electronic structure, e.g., concerning the orientation of unoccupied orbitals in the crystal field and the stability of the charged triplet state of the N impurity. Further experimental or theoretical analysis of these features could provide useful tests for validating the performance of DFT methods in their application to defects in wide-gap materials.

Catalytic role of gold nanoparticle in GaAs nanowire growth: a density functional theory study.

The energetics of Ga, As, and GaAs species on the Au(111) surface (employed as a model for Au nanoparticles) is investigated by means of density functional calculations. Apart from formation of the compound Au(7)Ga(2), Ga is found to form a surface alloy with gold with comparable ΔH ~ -0.5 eV for both processes. Dissociative adsorption of As(2) is found to be exothermic by more than 2 eV on both clean Au(111) and AuGa surface alloys. The As-Ga species formed by reaction of As with the surface alloy is sufficiently stable to cover the surface of an Au particle in vacuo in contact with a GaAs substrate. The results of the calculations are interpreted in the context of Au-catalyzed growth of GaAs nanowires. We argue that arsenic is supplied to the growth zone of the nanowire mainly by impingement of molecules on the gold particle and identify a regime of temperatures and As(2) partial pressures suitable for Au-catalyzed nanowire growth in molecular beam epitaxy.

Evaluating strain and doping of Janus MoSSe from phonon mode shifts supported by ab initio DFT calculations.

With the study of Janus monolayer transition metal dichalcogenides, in which one of the two chalcogen layers is replaced by another type of chalcogen atom, research on two-dimensional materials is advancing into new areas. Yet only little is known about this new kind of material class, mainly due to the difficult synthesis. In this work, we synthesize MoSSe monolayers from exfoliated samples and compare their Raman signatures with density functional theory calculations of phonon modes that depend in a nontrivial way on doping and strain. With this as a tool, we can infer limits for the possible combinations of strain and doping levels. This reference data can be applied to all MoSSe Janus samples in order to quickly estimate their strain and doping, providing a reliable tool for future work. In order to narrow down the results for our samples further, we analyze the temperature-dependent photoluminescence spectra and time-correlated single-photon counting measurements. The lifetime of Janus MoSSe monolayers exhibits two decay processes with an average total lifetime of 1.57 ns. Moreover, we find a strong trion contribution to the photoluminescence spectra at low temperature which we attribute to excess charge carriers, corroborating our ab initio calculations.

Isotopic effect on the vibrational lifetime of the carbon-deuterium stretch excitation on graphene.

The relaxation of vibrational energy in the H and D stretch modes has been studied on the graphene surface using ab initio calculations. The dissipation of the vibrational energy stored in the stretching modes proceeds through vibration-phonon coupling, while the dissipation through electronic excitations makes only minor contributions. Recently, we reported the fast relaxation of the H stretch energy on graphene [S. Sakong and P. Kratzer, J. Chem. Phys. 133, 054505 (2010)]. Interestingly, we predict the lifetime of the D stretch to be markedly longer compared to the relaxation of the H stretch. This is unexpected since the vibrational amplitudes at carbon atoms in the joint C-D vibrational modes are larger than in the joint C-H modes, due to the mass ratio m(D)/m(C) > m(H)/m(C). However, the vibrational relaxation rate for the D stretch is smaller than for the H stretch, because the energy is dissipated to an acoustic phonon of graphene in the case of C-D rather than an optical phonon as is the case in C-H, and hence, the corresponding phonon density of states is lower in the C-D case. To rationalize our findings, we propose a general scheme for estimating vibrational lifetimes of adsorbates based on four factors: the density of states of the phonons that mediates the transitions, the vibration-phonon coupling strength, the anharmonic coupling between local modes, and the number of quanta involved in the transitions. Mainly the first two of these factors are responsible for the differences in the lifetimes of the C-H and C-D stretches. The possible role of the other factors is illustrated in the context of vibrational lifetimes in other recently studied systems.

First-principles computational exploration of ferromagnetism in monolayer GaS via substitutional doping.

Using first-principles calculations, functionalization of the monolayer-GaS crystal structure through N or Cr-doping at all possible lattice sites has been investigated. Our results show that pristine monolayer-GaS is an indirect-bandgap, non-magnetic semiconductor. The bandgap can be tuned and a magnetic moment (MM) can be induced by the introduction of N or Cr atomic anion/cation doping in monolayer GaS. For instance, the intrinsic character of monolayer GaS can be changed by substitution of N for the S-site to p-type, while substitution of Cr at the S-site or Ga-site induces half-metallicity at sufficiently high concentrations. The defect states are located in the electronic bandgap region of the GaS monolayer. These findings help to extend the application of monolayer-GaS structures in nano-electronics and spintronics. Since the S-sites at the surface are more easily accessible to doping in experiment, we chose the S-site for further investigations. Finally, we perform calculations with ferromagnetic (FM) and antiferromagnetic (AFM) alignment of the MMs at the dopants. For pairs of impurities of the same species at low concentrations we find Cr atoms to prefer the FM state, while N atoms prefer the AFM state, both for impurities on opposite surfaces of the GaS monolayer and for impurities sharing a common Ga neighbor sitting at the same surface. Extending our study to higher concentrations of Cr atoms, we find that clusters of four Cr atoms prefer AFM coupling, whereas the FM coupling is retained for Cr atoms at larger distance arranged on a honeycomb lattice. For the latter arrangement, we estimate the FM Curie temperatureTCto be 241 K. We conclude that the Cr-doped monolayer-GaS crystal structure offers enhanced electronic and magnetic properties and is an appealing candidate for spintronic devices operating close to room temperature.

Indium-gallium segregation in CuIn(x)Ga(1-x)Se2: an ab initio-based Monte Carlo study.

Thin-film solar cells with CuIn(x)Ga(1-x)Se2 (CIGS) absorber are still far below their efficiency limit, although lab cells already reach 20.1%. One important aspect is the homogeneity of the alloy. Large-scale simulations combining Monte Carlo and density functional calculations show that two phases coexist in thermal equilibrium below room temperature. Only at higher temperatures, CIGS becomes more and more a homogeneous alloy. A larger degree of inhomogeneity for Ga-rich CIGS persists over a wide temperature range, which contributes to the observed low efficiency of Ga-rich CIGS solar cells.

Magnetism in C- or N-doped MgO and ZnO: a density-functional study of impurity pairs.

It is shown that substitution of C or N for O recently proposed as a way to create ferromagnetism in otherwise nonmagnetic oxide insulators is curtailed by formation of impurity pairs, and the resultant C2 spin=1 dimers as well as the isoelectronic N2(2+) interact antiferromagnetically in p-type MgO. For C-doped ZnO, however, we demonstrate using the Heyd-Scuseria-Ernzerhof hybrid functional that a resonance of the spin-polarized C2 ppπ* states with the host conduction band results in a long-range ferromagnetic interaction. Magnetism of open-shell impurity molecules is proposed as a possible route to d(0)-ferromagnetism in oxide spintronic materials.

Hydrogen vibrational modes on graphene and relaxation of the C-H stretch excitation from first-principles calculations.

Density functional theory (DFT) calculations are used to determine the vibrational modes of hydrogen adsorbed on graphene in the low-coverage limit. Both the calculated adsorption energy of a H atom of 0.8 eV and calculated C-H stretch vibrational frequency of 2552 cm(-1) are unusually low for hydrocarbons, but in agreement with data from electron energy loss spectroscopy on hydrogenated graphite. The clustering of two adsorbed H atoms observed in scanning tunneling microscopy images shows its fingerprint also in our calculated spectra. The energetically preferred adsorption on different sublattices correlates with a blueshift of the C-H stretch vibrational modes in H adatom clusters. The C-H bending modes are calculated to be in the 1100 cm(-1) range, resonant with the graphene phonons. Moreover, we use our previously developed methods to calculate the relaxation of the C-H stretch mode via vibration-phonon interaction, using the Born-Oppenheimer surface for all local modes as obtained from the DFT calculations. The total decay rate of the H stretch into other H vibrations, thereby creating or annihilating one graphene phonon, is determined from Fermi's golden rule. Our calculations using the matrix elements derived from DFT calculations show that the lifetime of the H stretch mode on graphene is only several picoseconds, much shorter than on other semiconductor surfaces such as Ge(001) and Si(001).

Ordering of the nanoscale step morphology as a mechanism for droplet self-propulsion.

We establish a new mechanism for self-propelled motion of droplets, in which ordering of the nanoscale step morphology by sublimation beneath the droplets themselves acts to drive them perpendicular and up the surface steps. The mechanism is demonstrated and explored for Ga droplets on GaP(111)B, using several experimental techniques allowing studies of the structure and dynamics from micrometers to the atomic scale. We argue that the simple assumptions underlying the propulsion mechanism make it relevant for a wide variety of materials systems.

Isotope effects in the vibrational lifetime of hydrogen on germanium(100): theory and experiment.

Combining first-principles calculations and sum frequency generation spectroscopy, we elucidate the microscopic details in the relaxation of the stretching vibration of hydrogen adsorbed on Ge(100). The dominant decay channels involve energy transfer from the stretching to the hydrogen bending modes, with the remaining energy difference being transferred to or from substrate phonons. The coupling between stretching and bending modes is treated from first principles using the calculated multidimensional adiabatic potential energy surface, while the coupling to phonons is treated in perturbation theory. For a surface solely saturated with light hydrogen, we calculate a vibrational lifetime of 1.56 ns at 400 K, in good agreement with experiment, and find a similar temperature dependence of the lifetime in both experiment and theory. The calculations show that the stretching energy dissipates to a vibrational state involving four bending quanta of hydrogen, concurrently absorbing a thermally excited surface phonon related to the Ge dimer rocking mode. For a Ge surface saturated with a mixture of H and D, our experiments find that the relaxation rate of the H stretching vibration is markedly increased when compared to a surface saturated with H only. Experimentally, a single decay is observed although H and D atoms will statistically pair on the surface dimers. The vibrational lifetime of the Ge-H stretching mode is up to six times shorter in the presence of adsorbed D atoms. The calculated relaxation rates are consistent with the experimentally observed trend. The theoretical analysis shows that the breaking of symmetry within the Ge surface dimer due to coadsorption of D opens up further relaxation channels that involve absorption or emission of a substrate phonon at various energies. Moreover, the calculations predict an even shorter vibrational lifetime of the Ge-D stretch mode due to efficient coupling to the Ge dimer rocking mode.

The Basics of Electronic Structure Theory for Periodic Systems.

When density functional theory is used to describe the electronic structure of periodic systems, the application of Bloch's theorem to the Kohn-Sham wavefunctions greatly facilitates the calculations. In this paper of the series, the concepts needed to model infinite systems are introduced. These comprise the unit cell in real space, as well as its counterpart in reciprocal space, the Brillouin zone. Grids for sampling the Brillouin zone and finite k-point sets are discussed. For metallic systems, these tools need to be complemented by methods to determine the Fermi energy and the Fermi surface. Various schemes for broadening the distribution function around the Fermi energy are presented and the approximations involved are discussed. In order to obtain an interpretation of electronic structure calculations in terms of physics, the concepts of bandstructures and atom-projected and/or orbital-projected density of states are useful. Aspects of convergence with the number of basis functions and the number of k-points need to be addressed specifically for each physical property. The importance of this issue will be exemplified for force constant calculations and simulations of finite-temperature properties of materials. The methods developed for periodic systems carry over, with some reservations, to less symmetric situations by working with a supercell. The chapter closes with an outlook to the use of supercell calculations for surfaces and interfaces of crystals.

[New perspectives on health prevention. Prevalence of hypertension, hypacusis and balance disorders at the Munich Oktoberfest 2016]. / Neue Perspektiven zur Gesundheitsprävention : Prävalenz von Hypertonie, Hypakusis und Gleichgewichtsstörungen beim Münchner Oktoberfest.

BACKGROUND: The prevalence of hypertension, hypacusis and balance disorders will increase due to demographic change and thus represent an increasing public health problem. OBJECTIVE: To determine the point prevalence of the diseases in focus outside the classical medical setting. METHOD: At the "Bavarian Central Agriculture Festival", on the margins of the Oktoberfest 2016, visitors were offered a free health check with three health stations (blood pressure measurement, hearing test, balance test). By means of standardized examinations, the prevalence of the diseases was recorded. RESULTS: 1,727 people participated in the blood pressure measurement, 510 in the hearing test and 1,320 in the balance test. At all study sites, an increase in prevalence was observed with increasing age. Overall, the prevalence of hypertensive blood pressure values (> 140/> 90 mmHg) was 23.6%, with a high rate of 30.8% among over-65s. In the hearing test, 41.6% of all participants had a low-grade (20-40 dB) and 15.5% a higher-grade (> 40 dB) hypacusis. A balance value in the normal range was achieved by only 25.2% of the participants. CONCLUSION: The prevalence of the investigated diseases was very high, especially older men were more often affected by these health problems. Overall, there is a large primary and secondary prevention potential for the prevention and early treatment of the diseases. In order to increase the use, it would be possible in particular to consider expanding access to prevention programs outside of classic medical settings.

Density-functional theory study of vibrational relaxation of CO stretching excitation on Si(100).

A first-principles theory is presented for calculating the lifetime of adsorbate vibrations on semiconductor or insulator surfaces, where dissipation of the vibrational energy to substrate phonons is the dominant relaxation mechanism. As an example, we study the stretching vibration of CO/Si(100), where a lifetime of 2.3 ns has been measured recently [K. Lass, X. Han, and E. Hasselbrink, J. Chem. Phys. 123, 051102 (2005)]. Density-functional theory (DFT) calculations for the local modes of the adsorbate, including their anharmonic coupling, are combined with force field calculations for the substrate phonons. Using the DFT-Perdew-Burke-Ernzerhof functional, we have determined the most stable adsorption site for CO on top of the lower Si atom of the Si surface dimer, the local normal modes of CO, and the multidimensional potential energy surface for the CO vibrations. The anharmonic stretching frequency of adsorbed CO obtained in DFT-PBE is 5% lower than the experimental value, while the B3LYP functional reproduces the CO stretching frequency with only 1.4% error. The coupling between the anharmonic vibrational modes and the phonon continuum is evaluated within first-order perturbation theory, and transition rates for the CO vibrational relaxation are calculated using Fermi's golden rule. The lifetime of 0.5 ns obtained with DFT-PBE is in qualitative agreement with experiment, while using vibrational frequencies from the B3LYP functional gives a much too long lifetime as compared to experiment. We find that the numerical value of the lifetime is very sensitive to the harmonic frequencies used as input to the calculation of the transition rate. An empirical adjustment of these frequencies yields excellent agreement between our theory and experiment. From these calculations we conclude that the most probable microscopic decay channel of the CO stretching mode is into four lateral shift/bending quanta and one phonon.