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The effects of electron-hole interaction on the optical properties of a variety of materials have been calculated using an ab initio method based on solving the Bethe-Salpeter equation. Results on selected semiconductors, insulators, and semiconducting polymers are presented. In the cases of alpha-quartz (SiO2) and poly-phenylene-vinylene, resonant excitonic states qualitatively alter the absorption spectra.

Experimental and theoretical studies have shown that excitonic effects play an important role in the optical properties of conjugated polymers. The optical absorption spectrum of trans-polyacetylene, for example, can be understood as completely dominated by the formation of exciton bound states. We review a recently developed first-principles method for computing the excitonic effects and optical spectrum, with no adjustable parameters. This theory is used to study the absorption spectrum of two conjugated polymers: trans-polyacetylene and poly-phenylene-vinylene(PPV).

A route towards covalent functionalization of chemically inert 2H-MoS2 exploiting sulfur vacancies is explored by means of (TD)DFT and GW/BSE calculations. Functionalization via nitrogen incorporation at sulfur vacancies is shown to result in more stable covalent binding than via thiol incorporation. In this way, defective monolayer MoS2 is repaired and the quasiparticle band structure as well as the remarkable optical properties of pristine MoS2 are restored. Hence, defect-free functionalization with various molecules is possible. Our results for covalently attached azobenzene, as a prominent photo-switch, pave the way to create photoresponsive two-dimensional (2D) materials. [ABSTRACT FROM AUTHOR]

Abstract Problem To describe immunohistochemical features encountered in ovarian fibrothecoma with correlation to clinical presentation and surgical management. Method of study A female age 75 presented for evaluation of melena. The patient reported total abdominal hysterectomy and removal of both ovaries 40 years earlier. Results CA-125 was normal and there was no evidence of hyperestrogen effect. Pelvic CT revealed a partially calcified 7 cm pelvic mass without adenopathy or ascites; ultrasound was confirmatory. Endoscopy identified three benign intestinal tubular adenomas. Following laparoscopic excision of the pelvic tumor immunohistochemichal analysis of the mass showed negative staining for keratin, S100 protein, inhibin, calretinin, melan A, smooth muscle actin, CD34, CD117, and desmin. The tissue was positive for vimentin, however. Conclusion Ovarian fibrothecomas represent an ovarian stromal neoplasm developing in a wide spectrum of clinical settings. Particularly if oophorectomy is stated to have been performed remote from the time of index presentation, the status of the ovaries must be considered whenever pelvic pathology is encountered. We describe a calcified ovarian fibrothecoma identified during gastroenterology investigation and confirmed immunohistochemically via high amplitude vimentin signal.

We present the quasiparticle band structure and the optical excitation spectrum of bulk LiCl, using many-body perturbation theory. Density-functional theory is used to calculate the ground-state geometry of the system. The quasiparticle band structure is calculated within the GW approximation. Taking the electron-hole interaction into consideration, electron-hole pair states and optical excitations are obtained by solving the Bethe-Salpeter equation for the electron-hole two-particle Green function. The calculated band gap is 9.5 eV, which is in good agreement with the experimental result of 9.4 eV. And the calculated optical absorption spectrum, which contains an exciton peak at 8.8 eV and a resonant-exciton peak at 9.8 eV, is also in good agreement with experimental data. [ABSTRACT FROM AUTHOR]

The research field of two dimensional (2D) materials strongly relies on optical microscopy characterization tools to identify atomically thin materials and to determine their number of layers. Moreover, optical microscopy-based techniques opened the door to study the optical properties of these nanomaterials. We presented a comprehensive study of the differential reflectance spectra of 2D semiconducting transition metal dichalcogenides (TMDCs), MoS2, MoSe2, WS2, and WSe2, with thickness ranging from one layer up to six layers. We analyzed the thickness-dependent energy of the different excitonic features, indicating the change in the band structure of the different TMDC materials with the number of layers. Our work provided a route to employ differential reflectance spectroscopy for determining the number of layers of MoS2, MoSe2, WS2, and WSe2. [ABSTRACT FROM AUTHOR]

Almost all experiments and future applications of transition metal dichalcogenide monolayers rely on a substrate for mechanical stability, which can significantly modify the optical spectra of the monolayer. Doping from the substrate might lead to the domination of the spectra by trions. Here we show by ab initio many-body theory that the negative trion (A-) splits into three excitations, with both inter- and intra-valley character, while the positive counterpart (A+) consists of only one inter-valley excitation. Furthermore, the substrate enhances the screening, which renormalizes both band gap and exciton as well as the trion-binding energies. We verify that these two effects do not perfectly cancel each other, but lead to redshifts of the excitation energies for three different substrates ranging from a wide-bandgap semiconductor up to a metal. Our results explain recently found experimental splittings of the lowest trion line as well as excitation red-shifts on substrates. [ABSTRACT FROM AUTHOR]

One- and two-dimensional materials are being intensively investigated due to their interesting properties for next-generation optoelectronic devices. Among these, armchair-edged graphene nanoribbons are very promising candidates with optical properties that are dominated by excitons. In the presence of additional charges, trions (i.e., charged excitons) can occur in the optical spectrum. With our recently developed first-principle many-body approach (Phys. Rev. Lett. 116, 196804), we predict strongly bound trions in free-standing nanoribbons with large binding energies of 140-660 meV for widths of 14.6-3.6 Å. Both for the trions and for the excitons, we observe an almost linear dependency of their binding energies on the band gap. We observe several trion states with different character derived from the corresponding excitons. Because of the large bindings energies, this opens a route to applications by which optical properties are easily manipulated, for example, by electrical fields. [ABSTRACT FROM AUTHOR]

Bound electron-hole pairs called excitons govern the electronic and optical response of many organic and inorganic semiconductors. Excitons with spatially displaced wave functions of electrons and holes (interlayer excitons) are important for Bose-Einstein condensation, superfluidity, dissipationless current flow, and the light-induced exciton spin Hall effect. Here we report on the discovery of interlayer excitons in a bulk van der Waals semiconductor. They form due to strong localization and spin-valley coupling of charge carriers. By combining high-field magneto-reflectance experiments and ab initio calculations for 2H-MoTe2, we explain their salient features: the positive sign of the g-factor and the large diamagnetic shift. Our investigations solve the long-standing puzzle of positive g-factors in transition metal dichalcogenides, and pave the way for studying collective phenomena in these materials at elevated temperatures. [ABSTRACT FROM AUTHOR]

Optical excitations of molecular systems can be modified by their physical environment. We analyze the underlying mechanisms within many-body perturbation theory, which is particularly suited to study nonlocal polanzability effects on the electronic structure. Here we focus on the example of a semiconducting carbon nanotube, which observes redshifts of its excitons when the tube is touched by another nanotube or other physisorbates. We show that the redshifts mostly result from the polanzability of the attached ad system. Electronic coupling may enhance the redshifts, but depends very sensitively on the structural details of the contact. [ABSTRACT FROM AUTHOR]

Abstract: Electronic excitations are often accompanied by displacement of the ions from their ground-state equilibrium positions. This leads to line broadening of optical spectra, Stokes shifts, conformational changes, and photoinduced reactions. Here we discuss approaches to these features within ab-initio methods, in particular within many-body perturbation theory. A number of various systems, including molecules, point defects, polymers, and surfaces, are discussed to illustrate issues like localization and self-trapping that are relevant for a detailed understanding of the interrelation between excited states and geometrical structure. To cite this article: M. Rohlfing, C. R. Physique 10 (2009). [Copyright &y& Elsevier]

Problem: To describe immunohistochemical features encountered in ovarian fibrothecoma with correlation to clinical presentation and surgical management. Method of study: A female age 75 presented for evaluation of melena. The patient reported total abdominal hysterectomy and removal of both ovaries 40 years earlier. Results: CA-125 was normal and there was no evidence of hyperestrogen effect. Pelvic CT revealed a partially calcified 7 cm pelvic mass without adenopathy or ascites; ultrasound was confirmatory. Endoscopy identified three benign intestinal tubular adenomas. Following laparoscopic excision of the pelvic tumor immunohistochemichal analysis of the mass showed negative staining for keratin, S100 protein, inhibin, calretinin, melan A, smooth muscle actin, CD34, CD117, and desmin. The tissue was positive for vimentin, however. Conclusion: Ovarian fibrothecomas represent an ovarian stromal neoplasm developing in a wide spectrum of clinical settings. Particularly if oophorectomy is stated to have been performed remote from the time of index presentation, the status of the ovaries must be considered whenever pelvic pathology is encountered. We describe a calcified ovarian fibrothecoma identified during gastroenterology investigation and confirmed immunohistochemically via high amplitude vimentin signal. [ABSTRACT FROM AUTHOR]

We discuss topological and electronic properties of thin films of the topological insulator Bi2Se3 employing the GW method. We obtain a topologically trivial phase for films of one to six quintuple layers thickness, whereas a quantum spin Hall phase is observed in neither of these films. This challenges recent contradictory reports on quantum spin Hall phases in Bi2Se3 films from both theory and experiment. Moreover, we argue that one cannot conclude the topological phase from the band structures measured in those studies. The reliability of our results is supported by the excellent agreement of all calculated spectral features with photoemission experiments, i.e., the band gaps and the energy and slope of the Dirac state. [ABSTRACT FROM AUTHOR]

We investigate the influence of potassium adsorption and selenium vacancies in the surface layer on the electronic properties of the prototypical topological insulator Bi2Se3. These modifications of the surface give rise to oscillations in the charge density that extend deep into the crystal. They result in a long-ranged potential perpendicular to the surface (also referred to as band bending) and new states in the band structure that are reminiscent of the states of a two-dimensional electron gas. Very similar effects have been observed in several experiments. The reorganization of the charge deep inside the crystal as a reaction to the surface modification constitutes a remarkable property of Bi2Se3 and is closely related to its layered structure. The emergence of the long-ranged potential as a direct consequence of the charge reorganization turns out to be a generic property of Bi2Se3. However, calculations without spin-orbit coupling show that the band bending is not related to the nontrivial topological character of Bi2Se3. [ABSTRACT FROM AUTHOR]

The topological crystalline insulator SnTe belongs to the recently discovered class of materials in which a crystalline symmetry ensures the existence of topologically protected surface states. The bulk band structure of SnTe is characterized by a band inversion at the four equivalent L points, giving rise to a mirror Chern number of nM = -2. The (001) surface exhibits four Dirac cones which lie at non-time-reversal-invariant points close to X and Y and are protected by the (110) and (110) mirror symmetries. In contrast to topological insulators, this symmetry can be broken via deformations of the crystal. This opens up new possibilities for manipulating the Dirac states and inducing a controllable gap. Here, we have employed density-functional theory to investigate the response of the Dirac states to applied distortions from first principles. Our calculations show that a local gap of up to ≈ 30 meV can be introduced via lattice deformations that break at least one of the underlying mirror symmetries. It is formed at either all four or just two cones, depending on the direction of the displacement vector, making it possible to create either a global gap or a state where opened and intact Dirac cones coexist. Notably, applying these deformations at the surface only can already induce the gap. If the complete slab is distorted, bulk bands are pushed into the gap making the whole system metallic. [ABSTRACT FROM AUTHOR]

We investigate the adsorption of a single tetracyanoethylene (TCNE) molecule on the silver (001) surface. Adsorption structures, electronic properties, and scanning tunneling microscopy (STM) images are calculated within density-functional theory. Adsorption occurs most favorably in on-top configuration, with the C=C double bond directly above a silver atom and the four N atoms bound to four neighboring Ag atoms. The lowest unoccupied molecular orbital of TCNE becomes occupied due to electron transfer from the substrate. This state dominates the electronic spectrum and the STM image at moderately negative bias. We discuss and employ a spatial extrapolation technique for the calculation of STM and scanning tunneling spectroscopy (STS) images. Our calculated images are in good agreement with experimental data. [ABSTRACT FROM AUTHOR]

The effect of a magnetic field on the optical absorption in semiconductors has been measured experimentally and modeled theoretically for various systems in previous decades. We present a new first-principles approach to systematically determine the response of excitons to magnetic fields, i.e., exciton g factors. By utilizing the GW-Bethe-Salpeter equation methodology we show that g factors extracted from the Zeeman shift of electronic bands are strongly renormalized by many-body effects which we trace back to the extent of the excitons in reciprocal space. We apply our approach to monolayers of transition metal dichalcogenides (MoS2, MoSe2, MoTe2, WS2, and WSe2) with strongly bound excitons for which g factors are weakened by about 30%. [ABSTRACT FROM AUTHOR]

The research field of two dimensional (2D) materials strongly relies on optical microscopy characterization tools to identify atomically thin materials and to determine their number of layers. Moreover, optical microscopy-based techniques opened the door to study the optical properties of these nanomaterials. We presented a comprehensive study of the differential reflectance spectra of 2D semiconducting transition metal dichalcogenides (TMDCs), MoS2, MoSe2, WS2, and WSe2, with thickness ranging from one layer up to six layers. We analyzed the thickness-dependent energy of the different excitonic features, indicating the change in the band structure of the different TMDC materials with the number of layers. Our work provided a route to employ differential reflectance spectroscopy for determining the number of layers of MoS2, MoSe2, WS2, and WSe2. [ABSTRACT FROM AUTHOR]

Atomically thin materials such as graphene or MoS2 are of high in-plane symmetry. Crystals with reduced symmetry hold the promise for novel optoelectronic devices based on their anisotropy in current flow or light polarization. Here, we present polarization-resolved optical transmission and photoluminescence spectroscopy of excitons in 1T'-ReSe2. On reducing the crystal thickness from bulk to a monolayer, we observe a strong blue shift of the optical band gap from 1.37 to 1.50 eV. The excitons are strongly polarized with dipole vectors along different crystal directions, which persist from bulk down to monolayer thickness. The experimental results are well reproduced by ab initio calculations based on the GW-BSE approach within LDA+GdW approximation. The excitons have high binding energies of 860 meV for the monolayer and 120 meV for bulk. They are strongly confined within a single layer even for the bulk crystal. In addition, we find in our calculations a direct band gap in 1T'-ReSe2 regardless of crystal thickness, indicating weak interlayer coupling effects on the band gap characteristics. Our results pave the way for polarization-sensitive applications, such as optical logic circuits operating in the infrared spectral region. [ABSTRACT FROM AUTHOR]

Employing the GW method, we discuss the electronic and topological properties of Bi2Te3 and Sb2Te3 thin films consisting of one to six quintuple layers (QLs). Although both bulk materials are three-dimensional topological insulators, the two-dimensional topological phases of their thin films differ. We find the nontrivial quantum spin Hall phase, together with a sizable band gap of 0.13 eV, for a Bi2Te3 film of 2 QL thickness, whereas the 2 QL Sb2Te3 film hosts a topologically trivial band structure. All our GW results are in excellent agreement with experiments. This concerns the dispersions of the highest valence bands and lowest conduction bands around Γ, the band gaps of thin films, and, in particular, the dispersion of the topological surface state and its energetic position relative to the bulk bands. A crucial technical issue of our study is that we go beyond the "one-shot" GW approach by diagonalizing the GW Hamiltonian. This yields improved quasiparticle wave functions and band structures. The physical origin of the respective off-diagonal elements in the GW Hamiltonian is analyzed in detail. Without the additional diagonalization, the GW band structures are unphysical for many film thicknesses. [ABSTRACT FROM AUTHOR]

Trion states of three correlated particles (e.g., two electrons and one hole) are essential to understand the optical spectra of doped or gated nanostructures, like carbon nanotubes or transition-metal dichalcogenides. We develop a theoretical many-body description for such correlated states using an ab initio approach. It can be regarded as an extension of the widely used GW method and Bethe-Salpeter equation, thus allowing for a direct comparison with excitons. We apply this method to a semiconducting (8,0) carbon nanotube, and find that the lowest optically active trions are redshifted by ~130 meV compared to the excitons, confirming experimental findings for similar tubes. Moreover, our method provides detailed insights in the physical nature of trion states. In the prototypical carbon nanotube we find a variety of different excitations, discuss the spectra, energy compositions, and correlated wave functions. [ABSTRACT FROM AUTHOR]

We introduce a scanning probe technique that enables three-dimensional imaging of local electrostatic potential fields with subnanometer resolution. Registering single electron charging events of a molecular quantum dot attached to the tip of an atomic force microscope operated at 5 K, equipped with a qPlus tuning fork, we image the quadrupole field of a single molecule. To demonstrate quantitative measurements, we investigate the dipole field of a single metal adatom adsorbed on a metal surface. We show that because of its high sensitivity the technique can probe electrostatic potentials at large distances from their sources, which should allow for the imaging of samples with increased surface roughness. [ABSTRACT FROM AUTHOR]

By means of low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS), we have investigated the adsorption of single Au atoms on a PTCDA monolayer physisorbed on the Au(111) surface. A chemical reaction between the Au atom and the PTCDA molecule leads to the formation of a radical that has an unpaired electron in its highest occupied orbital. This orbital is a π orbital that extends over the whole Au-PTCDA complex. Because of the large Coulomb repulsion in this orbital, the unpaired electron generates a local moment when the molecule is adsorbed on the Au(111) surface. We demonstrate the formation of the radical and the existence of the local moment after adsorption by observing a zero-bias differential conductance peak that originates from the Kondo effect. By temperature dependent measurements of the zero-bias differential conductance, we determine the Kondo temperature to be TK = (38 ± 8) K. For the theoretical description of the properties of the Au-PTCDA complex we use a hierarchy of methods, ranging from density functional theory (DFT) including a van der Waals correction to many-body perturbation theory (MBPT) and the numerical renormalization group (NRG) approach. Regarding the high-energy orbital spectrum, we obtain an excellent agreement with experiments by both spin-polarized DFT/MBPT and NRG. Moreover, the NRG provides an accurate description of the low-energy excitation spectrum of the spin degree of freedom, predicting a Kondo temperature very close to the experimental value. This is achieved by a detailed analysis of the universality of various definitions of TK and by taking into account the full energy dependence of the coupling function between the molecule-metal complex and the metallic substrate. [ABSTRACT FROM AUTHOR]

Charge-transfer (CT) excited states play an important role in the excited-state dynamics of DNA in aqueous solution. However, there is still much controversy on their energies. By ab initio many-body Green's function theory, together with classical molecular dynamics simulations, we confirm the existence of CT states at the lower energy side of the optical absorption maximum in aqueous DNA as observed in experiments. We find that the hydration shell can exert strong effects (~1 eV) on both the electronic structure and CT states of DNA molecules through dipole electric fields. In this case, the solvent cannot be simply regarded as a macroscopic screening medium as usual. The influence of base stacking and base pairing on the CT states is also discussed. [ABSTRACT FROM AUTHOR]

Recent experiments have indicated that dopants and defects can trigger new redshifted photoluminescence (PL) peaks below the E11 peak in single-walled carbon nanotubes (SWCNTs). To understand the origin of the new PL peaks, we study theoretically the excited-state properties of SWCNTs with some typical dopants and defects by ab initio many-body perturbation theory. Our calculations demonstrate that the Stokes shift in doped centers can be as large as 170 meV, which is much larger than that of intact SWCNTs and must be taken into account. We find dipole-allowed transitions from localized midgap and shallow impurity levels, which can give rise to pronounced PL peaks. Dark excitons, on the other hand, seem to have oscillator strengths that are too small to account for the new PL peaks. [ABSTRACT FROM AUTHOR]

We discover an excited bound three-particle state, the 2s trion, appearing energetically below the 2s exciton in monolayer WS2, using absorption spectroscopy and ab initio GW and Bethe-Salpeter equation calculations. The measured binding energy of the 2s trion (22 meV) is smaller compared to the 1s intravalley and intervalley trions (37 and 31 meV). With increasing temperature, the 1s and 2s trions transfer their oscillator strengths to the respective neutral excitons, establishing an optical fingerprint of trion-exciton resonance pairs. Our discovery underlines the importance of trions for the entire excitation spectrum of two-dimensional semiconductors. [ABSTRACT FROM AUTHOR]

We present a physically intuitive model of molecular quantum dots beyond the constant interaction approximation. It accurately describes their charging behavior and allows the extraction of important molecular properties that are otherwise experimentally inaccessible. The model is applied to data recorded with a noncontact atomic force microscope on three different molecules that act as a quantum dot when attached to the microscope tip. The results are in excellent agreement with first-principles simulations. [ABSTRACT FROM AUTHOR]