Anomalous non-equilibrium response in black phosphorus to sub-gap mid-infrared excitation.

The competition between the electron-hole Coulomb attraction and the 3D dielectric screening dictates the optical properties of layered semiconductors. In low-dimensional materials, the equilibrium dielectric environment can be significantly altered by the ultrafast excitation of photo-carriers, leading to renormalized band gap and exciton binding energies. Recently, black phosphorus emerged as a 2D material with strongly layer-dependent electronic properties. Here, we resolve the response of bulk black phosphorus to mid-infrared pulses tuned across the band gap. We find that, while above-gap excitation leads to a broadband light-induced transparency, sub-gap pulses drive an anomalous response, peaked at the single-layer exciton resonance. With the support of DFT calculations, we tentatively ascribe this experimental evidence to a non-adiabatic modification of the screening environment. Our work heralds the non-adiabatic optical manipulation of the electronic properties of 2D materials, which is of great relevance for the engineering of versatile van der Waals materials.

Evidence of ideal excitonic insulator in bulk MoS2 under pressure.

Spontaneous condensation of excitons is a long-sought phenomenon analogous to the condensation of Cooper pairs in a superconductor. It is expected to occur in a semiconductor at thermodynamic equilibrium if the binding energy of the excitons-electron (e) and hole (h) pairs interacting by Coulomb force-overcomes the band gap, giving rise to a new phase: the "excitonic insulator" (EI). Transition metal dichalcogenides are excellent candidates for the EI realization because of reduced Coulomb screening, and indeed a structural phase transition was observed in few-layer systems. However, previous work could not disentangle to which extent the origin of the transition was in the formation of bound excitons or in the softening of a phonon. Here we focus on bulk [Formula: see text] and demonstrate theoretically that at high pressure it is prone to the condensation of genuine excitons of finite momentum, whereas the phonon dispersion remains regular. Starting from first-principles many-body perturbation theory, we also predict that the self-consistent electronic charge density of the EI sustains an out-of-plane permanent electric dipole moment with an antiferroelectric texture in the layer plane: At the onset of the EI phase, those optical phonons that share the exciton momentum provide a unique Raman fingerprint for the EI formation. Finally, we identify such fingerprint in a Raman feature that was previously observed experimentally, thus providing direct spectroscopic confirmation of an ideal excitonic insulator phase in bulk [Formula: see text] above 30 GPa.

A monolayer transition-metal dichalcogenide as a topological excitonic insulator.

Monolayer transition-metal dichalcogenides in the T' phase could enable the realization of the quantum spin Hall effect1 at room temperature, because they exhibit a prominent spin-orbit gap between inverted bands in the bulk2,3. Here we show that the binding energy of electron-hole pairs excited through this gap is larger than the gap itself in the paradigmatic case of monolayer T' MoS2, which we investigate from first principles using many-body perturbation theory4. This paradoxical result hints at the instability of the T' phase in the presence of spontaneous generation of excitons, and we predict that it will give rise to a reconstructed 'excitonic insulator' ground state5-7. Importantly, we show that in this monolayer system, topological and excitonic order cooperatively enhance the bulk gap by breaking the crystal inversion symmetry, in contrast to the case of bilayers8-16 where the frustration between the two orders is relieved by breaking time reversal symmetry13,15,16. The excitonic topological insulator is distinct from the bare topological phase because it lifts the band spin degeneracy, which results in circular dichroism. A moderate biaxial strain applied to the system leads to two additional excitonic phases, different in their topological character but both ferroelectric17,18 as an effect of electron-electron interaction.

Interaction-Driven Giant Orbital Magnetic Moments in Carbon Nanotubes.

Carbon nanotubes continue to be model systems for studies of confinement and interactions. This is particularly true in the case of so-called "ultraclean" carbon nanotube devices offering the study of quantum dots with extremely low disorder. The quality of such systems, however, has increasingly revealed glaring discrepancies between experiment and theory. Here, we address the outstanding anomaly of exceptionally large orbital magnetic moments in carbon nanotube quantum dots. We perform low temperature magnetotransport measurements of the orbital magnetic moment and find it is up to 7 times larger than expected from the conventional semiclassical model. Moreover, the magnitude of the magnetic moment monotonically drops with the addition of each electron to the quantum dot directly contradicting the widely accepted shell filling picture of single-particle levels. We carry out quasiparticle calculations, both from first principles and within the effective-mass approximation, and find the giant magnetic moments can only be captured by considering a self-energy correction to the electronic band structure due to electron-electron interactions.

Angle-resolved photoemission spectroscopy from first-principles quantum Monte Carlo.

Angle-resolved photoemission spectroscopy allows one to visualize in momentum space the probability weight maps of electrons subtracted from molecules deposited on a substrate. The interpretation of these maps usually relies on the plane wave approximation through the Fourier transform of single particle orbitals obtained from density functional theory. Here we propose a first-principle many-body approach based on quantum Monte Carlo (QMC) to directly calculate the quasi-particle wave functions (also known as Dyson orbitals) of molecules in momentum space. The comparison between these correlated QMC images and their single particle counterpart highlights features that arise from many-body effects. We test the QMC approach on the linear C2H2, CO2, and N2 molecules, for which only small amplitude remodulations are visible. Then, we consider the case of the pentacene molecule, focusing on the relationship between the momentum space features and the real space quasi-particle orbital. Eventually, we verify the correlation effects present in the metal CuCl 4 2 - planar complex.

Carbon nanotubes as excitonic insulators.

Fifty years ago Walter Kohn speculated that a zero-gap semiconductor might be unstable against the spontaneous generation of excitons-electron-hole pairs bound together by Coulomb attraction. The reconstructed ground state would then open a gap breaking the symmetry of the underlying lattice, a genuine consequence of electronic correlations. Here we show that this excitonic insulator is realized in zero-gap carbon nanotubes by performing first-principles calculations through many-body perturbation theory as well as quantum Monte Carlo. The excitonic order modulates the charge between the two carbon sublattices opening an experimentally observable gap, which scales as the inverse of the tube radius and weakly depends on the axial magnetic field. Our findings call into question the Luttinger liquid paradigm for nanotubes and provide tests to experimentally discriminate between excitonic and Mott insulators.

Giant modulation of the electronic band gap of carbon nanotubes by dielectric screening.

Carbon nanotubes (CNTs) are a promising material for high-performance electronics beyond silicon. But unlike silicon, the nature of the transport band gap in CNTs is not fully understood. The transport gap in CNTs is predicted to be strongly driven by electron-electron (e-e) interactions and correlations, even at room temperature. Here, we use dielectric liquids to screen e-e interactions in individual suspended ultra-clean CNTs. Using multiple techniques, the transport gap is measured as dielectric screening is increased. Changing the dielectric environment from air to isopropanol, we observe a 25% reduction in the transport gap of semiconducting CNTs, and a 32% reduction in the band gap of narrow-gap CNTs. Additional measurements are reported in dielectric oils. Our results elucidate the nature of the transport gap in CNTs, and show that dielectric environment offers a mechanism for significant control over the transport band gap.

Correlation Effects in Scanning Tunneling Microscopy Images of Molecules Revealed by Quantum Monte Carlo.

Scanning tunneling microscopy (STM) and spectroscopy probe the local density of states of single molecules electrically insulated from the substrate. The experimental images, although usually interpreted in terms of single-particle molecular orbitals, are associated with quasiparticle wave functions dressed by the whole electron-electron interaction. Here we propose an ab initio approach based on quantum Monte Carlo to calculate the quasiparticle wave functions of molecules. Through the comparison between Monte Carlo wave functions and their uncorrelated Hartree-Fock counterparts we visualize the electronic correlation embedded in the simulated STM images, highlighting the many-body features that might be observed.

Nanoscale spin rectifiers controlled by the Stark effect.

The control of orbitals and spin states of single electrons is a key ingredient for quantum information processing and novel detection schemes and is, more generally, of great relevance for spintronics. Coulomb and spin blockade in double quantum dots enable advanced single-spin operations that would be available even for room-temperature applications with sufficiently small devices. To date, however, spin operations in double quantum dots have typically been observed at sub-kelvin temperatures, a key reason being that it is very challenging to scale a double quantum dot system while retaining independent field-effect control of individual dots. Here, we show that the quantum-confined Stark effect allows two dots only 5 nm apart to be independently addressed without the requirement for aligned nanometre-sized local gating. We thus demonstrate a scalable method to fully control a double quantum dot device, regardless of its physical size. In the present implementation we present InAs/InP nanowire double quantum dots that display an experimentally detectable spin blockade up to 10 K. We also report and discuss an unexpected re-entrant spin blockade lifting as a function of the magnetic field intensity.

Proposed alteration of images of molecular orbitals obtained using a scanning tunneling microscope as a probe of electron correlation.

Scanning tunneling spectroscopy (STS) allows us to image single molecules decoupled from the supporting substrate. The obtained images are routinely interpreted as the square moduli of molecular orbitals, dressed by the mean-field electron-electron interaction. Here we demonstrate that the effect of electron correlation beyond the mean field qualitatively alters the uncorrelated STS images. Our evidence is based on the ab initio many-body calculation of STS images of planar molecules with metal centers. We find that many-body correlations alter significantly the image spectral weight close to the metal center of the molecules. This change is large enough to be accessed experimentally, surviving to molecule-substrate interactions.

Tunneling theory of two interacting atoms in a trap.

A theory for the tunneling of one atom out of a trap containing two interacting cold atoms is developed. The quasiparticle wave function, dressed by the interaction with the companion atom in the trap, replaces the noninteracting orbital at resonance in the tunneling matrix element. The computed decay time for two ^{6}Li atoms agrees with recent experimental results [G. Zürn, F. Serwane, T. Lompe, A. N. Wenz, M. G. Ries, J. E. Bohn, and S. Jochim, Phys. Rev. Lett. 108, 075303 (2012)], unveiling the "fermionization" of the wave function and a novel two-body effect.

Visualizing electron correlation by means of ab initio scanning tunneling spectroscopy images of single molecules.

Scanning tunneling microscopy (STM) has been a fundamental tool to characterize many-body effects in condensed matter systems, from extended solids to quantum dots. STM of molecules decoupled from the supporting conductive substrate has the potential to extend STM characterization of many-body effects to the molecular world as well. In this paper, we describe a many-body tunneling theory for molecules decoupled from the STM substrate, and we report on the use of standard quantum chemical methods to calculate the quantities necessary to provide the "correlated" STM molecular image. The developed approach has been applied to 18 different molecules to explore the effects of their chemical nature and of their substituents, as well as to verify the possible contribution by transition metal centers. Whereas the bulk of calculations has been performed with the configuration interaction method with single and double excitations (CISD), because of the computational cost some tests have been also performed with the more accurate coupled cluster with single and double excitations (CCSD) method to quantify the importance of the computational level on many-body STM images. We have found that correlation induces a remarkable squeezing of the images, and that correlated images are not derived from Hartree-Fock HOMO or LUMO alone, but include contributions from other orbitals as well. Although correlation effects are too small to be resolved by present STM experiments for the studied molecules, our results provide hints for seeking out other species with larger, and possibly experimentally detectable, correlation effects.

Correlated electrons in optically tunable quantum dots: building an electron dimer molecule.

We observe the low-lying excitations of a molecular dimer formed by two electrons in a GaAs semiconductor quantum dot in which the number of confined electrons is tuned by optical illumination. By employing inelastic light scattering we identify the intershell excitations in the one-electron regime and the distinct spin and charge modes in the interacting few-body configuration. In the case of two electrons, a comparison with configuration-interaction calculations allows us to link the observed excitations with the breathing mode of the molecular dimer and to determine the singlet-triplet energy splitting.

Correlation effects in wave function mapping of molecular beam epitaxy grown quantum dots.

We investigate correlation effects in the regime of a few electrons in uncapped InAs quantum dots by tunneling spectroscopy and wave function (WF) mapping at high tunneling currents where electron-electron interactions become relevant. Four clearly resolved states are found, whose approximate symmetries are roughly s and p, in order of increasing energy. Because the major axes of the p-like states coincide, the WF sequence is inconsistent with the imaging of independent-electron orbitals. The results are explained in terms of many-body tunneling theory, by comparing measured maps with those calculated by taking correlation effects into account.

Friedel sum rule for an interacting multiorbital quantum dot.

A generalized Friedel sum rule is derived for a quantum dot with internal orbital and spin degrees of freedom. The result is valid when all many-body correlations are taken into account and it links the phase shift of the scattered electron to the displacement of its spectral density into the dot.

Full configuration interaction approach to the few-electron problem in artificial atoms.

We present a new high performance configuration interaction code optimally designed for the calculation of the lowest-energy eigenstates of a few electrons in semiconductor quantum dots (also called artificial atoms) in the strong interaction regime. The implementation relies on a single-particle representation, but it is independent of the choice of the single-particle basis and, therefore, of the details of the device and configuration of external fields. Assuming no truncation of the Fock space of Slater determinants generated from the chosen single-particle basis, the code may tackle regimes where Coulomb interaction very effectively mixes many determinants. Typical strongly correlated systems lead to very large diagonalization problems; in our implementation, the secular equation is reduced to its minimal rank by exploiting the symmetry of the effective-mass interacting Hamiltonian, including square total spin. The resulting Hamiltonian is diagonalized via parallel implementation of the Lanczos algorithm. The code gives access to both wave functions and energies of first excited states. Excellent code scalability in a parallel environment is demonstrated; accuracy is tested for the case of up to eight electrons confined in a two-dimensional harmonic trap as the density is progressively diluted up to the Wigner regime, where correlations become dominant. Comparison with previous quantum Monte Carlo simulations in the Wigner regime demonstrates power and flexibility of the method.

Reduced electron relaxation rate in multielectron quantum dots.

We use a configuration-interaction approach and the Fermi golden rule to investigate electron-phonon interaction in multielectron quantum dots. Lifetimes are computed in the low-density, highly correlated regime. We report numerical evidence that electron-electron interaction generally leads to reduced decay rates of excited electronic states in weakly confined quantum dots, where carrier relaxation is dominated by the interaction with longitudinal acoustic phonons.

Coherent transport in a homojunction between an excitonic insulator and semimetal.

From the solution of a two-band model, we predict that the thermal and electrical transport across the junction of a semimetal and an excitonic insulator will exhibit high resistance behavior and low entropy production at low temperatures, distinct from a junction of a semimetal and a normal semiconductor. This phenomenon, ascribed to the dissipationless exciton flow which dominates over the charge transport, is based on the much longer length scale of the change of the effective interface potential for electron scattering due to the coherence of the condensate than in the normal state.

Evidence of correlation in spin excitations of few-electron quantum dots.

We report inelastic light scattering measurements of spin and charge excitations in nanofabricated AlGaAs/GaAs quantum dots with few electrons. A narrow spin excitation peak is observed and assigned to the intershell triplet-to-singlet monopole mode of dots with four electrons. Configuration-interaction theory provides precise quantitative interpretations that uncover large correlation effects that are comparable to exchange Coulomb interactions.