States Of Different Symmetry Research Articles

Symmetry-selective quasiparticle scattering and electric field tunability of the ZrSiS surface electronic structure

Three-dimensional Dirac semimetals with square-net non-symmorphic symmetry, such as ternary ZrXY (X = Si, Ge; Y = S, Se, Te) compounds, have attracted significant attention owing to the presence of topological nodal lines, loops, or networks in their bulk. Orbital symmetry plays a profound role in such materials as the different branches of the nodal dispersion can be distinguished by their distinct orbital symmetry eigenvalues. The presence of different eigenvalues suggests that scattering between states of different orbital symmetry may be strongly suppressed. Indeed, in ZrSiS, there has been no clear experimental evidence of quasiparticle scattering reported between states of different symmetry eigenvalues at small wave vector q⃗. Here we show, using quasiparticle interference, that atomic step-edges in the ZrSiS surface facilitate quasiparticle scattering between states of different symmetry eigenvalues. This symmetry eigenvalue mixing quasiparticle scattering is the first to be reported for ZrSiS and contrasts quasiparticle scattering with no mixing of symmetry eigenvalues, where the latter occurs with scatterers preserving the glide mirror symmetry of the crystal lattice, e.g. native point defects in ZrSiS. Finally, we show that the electronic structure of the ZrSiS surface, including its unique floating band surface state, can be tuned by a vertical electric field locally applied by the tip of a scanning tunneling microscope (STM), enabling control of a spin–orbit induced avoided crossing near the Fermi level by as much as 300%.

Strain‐driven Switching Between Antiferromagnetic States in Frustrated Antiferromagnet UO2 Probed by Exchange Bias Effect

AbstractFrustrated antiferromagnets offer a captivating platform to study the intricate relationship of magnetic interactions, geometric constraints, and emergent phenomena. By controlling spin orientations, these materials can be tailored for applications in spintronics and quantum information processing. The research focuses on the interplay of magnetic and exchange anisotropy effects in artificial heterostructures based on a canonical frustrated antiferromagnet, UO2. The potential to manipulate the spin directions in this material and switch between distinct antiferromagnetic (AFM) states is investigated using substrate‐induced strain. The phenomenon is probed using exchange bias effects in stoichiometric UO2/Fe3O4 bilayers. By employing many‐body first‐principles calculations magnetic configurations in the UO2 layers are identified. Even a minor tetragonal distortion triggers a transition between AFM states of different symmetries, driven by a robust alteration of single‐ion anisotropy due to the distortion. Consequently, this change influences the arrangement of magnetic moments at the UO2/Fe3O4 interface, affecting the magnitude of exchange bias. The findings showcase how epitaxial strain can effectively manipulate the AFM states in frustrated antiferromagnets by controlling single‐site anisotropy.

Engineering Symmetry-Selective Couplings of a Superconducting Artificial Molecule to Microwave Waveguides.

Tailoring the decay rate of structured quantum emitters into their environment opens new avenues for nonlinear quantum optics, collective phenomena, and quantum communications. Here, we demonstrate a novel coupling scheme between an artificial molecule comprising two identical, strongly coupled transmon qubits and two microwave waveguides. In our scheme, the coupling is engineered so that transitions between states of the same (opposite) symmetry, with respect to the permutation operator, are predominantly coupled to one (the other) waveguide. The symmetry-based coupling selectivity, as quantified by the ratio of the coupling strengths, exceeds a factor of 30 for both waveguides in our device. In addition, we implement a Raman process activated by simultaneously driving both waveguides, and show that it can be used to coherently couple states of different symmetry in the single-excitation manifold of the molecule. Using that process, we implement frequency conversion across the waveguides, mediated by the molecule, with efficiency of about 95%. Finally, we show that this coupling arrangement makes it possible to straightforwardly generate spatially separated Bell states propagating across the waveguides. We envisage further applications to quantum thermodynamics, microwave photodetection, and photon-photon gates.

FCI calculations of the adiabatic electronic structure of KRb highlighting the K−Rb+ ionic limit effect

A non-relativistic description of the electronic structure for the heteronuclear molecule KRb was developed through the Full Configuration Interaction (FCI) and pseudo-potential method. Below the ionic limit K−Rb+, the ground and all excited singlet and triplet states of different symmetries Σ+, Π and Δ (in the Hund's case (a): 2s + 1Λ±) were intensively investigated. Several adiabatic results including potential energy curves (PECs), permanent and transition electric dipole moments (PEDM, TEDM) were analyzed in short and long-range of internuclear distances. Tables of these properties as functions of separation are presented. The spectroscopic constants with the vibrational levels were derived using the “Numerov” algorithm. These molecular parameters were compared with those published in the literature, feature a good agreement. In the adiabatic representation, strong couplings between successive 1Σ+ states were reached by series of avoided crossing, yielding to the appearance of the ionic character and the good illustration of charge transfer. This description of the KRb molecule was helpful in the design of the prospect photo-association experiments and the obtaining of the quantum-degenerate gas of the polar molecule.

Tailoring CIPSI Expansions for QMC Calculations of Electronic Excitations: The Case Study of Thiophene.

The perturbatively selected configuration interaction scheme (CIPSI) is particularly effective in constructing determinantal expansions for quantum Monte Carlo (QMC) simulations with Jastrow–Slater wave functions: fast and smooth convergence of ground-state properties and balanced descriptions of ground and excited states of different symmetries have been reported. In particular, accurate excitation energies have been obtained by the pivotal requirement of using CIPSI expansions with similar second-order perturbation corrections for each state, that is, a similar estimated distance to the full configuration interaction limit. Here, we elaborate on the CIPSI selection criterion for excited states of the same symmetry as the ground state, generating expansions from a common orbital set. Using these expansions in QMC as determinantal components of Jastrow–Slater wave functions, we compute the lowest, bright excited state of thiophene, which is challenging due to its significant multireference character. The resulting vertical excitation energies are within 0.05 eV of the best theoretical estimates, already with expansions of only a few thousand determinants. Furthermore, we relax the ground- and excited-state structures following the corresponding root in variational Monte Carlo and obtain bond lengths that are accurate to better than 0.01 Å. Therefore, while the full treatment at the CIPSI level of this system is quite demanding, in QMC, we can compute high-quality excitation energies and excited-state structural parameters building on affordable CIPSI expansions with relatively few, well-chosen determinants.

Dissipative switching waves and solitons in the systems with spontaneously broken symmetry.

The paper addresses the bistability caused by spontaneous symmetry breaking bifurcation in a one-dimensional periodically corrugated nonlinear waveguide pumped by coherent light at normal incidence. The formation and the stability of the switching waves connecting the states of different symmetries are studied numerically. It is shown that the switching waves can form stable resting and moving bound states (dissipative solitons). The protocols of the creation of the discussed nonlinear localized waves are suggested and verified by numerical simulations.

The Nature of CVC Nonlinearity in Low-Voltage Scanning Tunneling Spectroscopy of Semiconductors

A new model of field emission in a scanning tunnelling microscope was developed. The model describes the tunnelling current from a surface of semiconductor (semimetal) and allows estimating the preexponential factor in the expression for the tunneling probability. It is shown that this factor is directly related to the degree of localization of the electron density and determines the shape of the local tunnel current-voltage characteristics (LTCVCs) at low voltages. The model allows separating the contributions of surface electronic states of different symmetry (dimension) of the tunnelling current. The practical application of the model is demonstrated by the example of mathematical processing of the LTCVCs of HOPG surface containing different structural defects.

Energy levels of a coupled-rotors model

We calculate the energy levels of a coupled-rotors model that has proved useful for the analysis of the multiple tunnelling peaks in the inelastic neutron scattering from 4-methylpyridine crystals. We resort to the Rayleigh–Ritz variational method with a basis set for each irreducible representation. The energy levels in terms of the rotor coupling strength exhibit a rich pattern of crossings between states of different symmetry and avoided crossings between states of the same symmetry.

Kilohertz electron paramagnetic resonance spectroscopy of single nitrogen centers at zero magnetic field.

Electron paramagnetic resonance (EPR) spectroscopy is among the most important analytical tools in physics, chemistry, and biology. The emergence of nitrogen-vacancy (NV) centers in diamond, serving as an atomic-sized magnetometer, has promoted this technique to single-spin level, even under ambient conditions. Despite the enormous progress in spatial resolution, the current megahertz spectral resolution is still insufficient to resolve key heterogeneous molecular information. A major challenge is the short coherence times of the sample electron spins. Here, we address this challenge by using a magnetic noise-insensitive transition between states of different symmetry. We demonstrate a 27-fold narrower spectrum of single substitutional nitrogen (P1) centers in diamond with a linewidth of several kilohertz, and then some weak couplings can be resolved. Those results show both spatial and spectral advances of NV center-based EPR and provide a route toward analytical (EPR) spectroscopy at the single-molecule level.

Dimer Radical Anions of Polyfluoroarenes. Two More to a Small Family.

While there is a body of experimental data concerning dimers formed by an aromatic molecule and its radical cation, information on the corresponding dimer radical anions (DRAs) is scarce. In this work, evidence for the formation of the DRAs of decafluorobiphenyl and 4-aminononafluorobiphenyl has been obtained by the optically detected electron paramagnetic resonance and the time-resolved magnetic field effect techniques. Theoretical investigation (DFT B3LYP-D3/6-31+G*) of these DRAs and the DRAs of octafluoronaphtalene and 1,2,4,5-tetrafluorobenzene previously detected by Werst has been undertaken to gain greater insight into the structure of the polyfluoroarene DRAs. Without substituents different from a fluorine atom, an extra electron is evenly delocalized over two fragments; the bonding interaction is π stacking. On the potential energy surfaces (PES), there are two minima of nearly equal energy corresponding to the structures of perfect and parallel displaced sandwiches. Such a PES structure is due to a conical intersection between two electronic states of different symmetry. The DRA of 4-aminononafluorobiphenyl is an ion-molecular associate stabilized by electrostatic interactions involving NH2 groups. The complex cyclic structure of the PES of this DRA suits the successive electron transfers between the dimer fragments. The calculated hyperfine coupling constants averaged over the PES minima agree well with the experimental ones.

Do extra compactified dimensions of space cause a substructure underlying the expected eigenstates of a molecule?

Experimental results on NO2 are explained based on the ADD-model of large extra compactified dimensions of space. We assume that gravity is sufficiently strong in a compactification space of the size of the molecule to affect the vibrational motion of the nuclei by causing an asymmetric perturbation in the symmetric stretch vibrational motion of the optically excited state. At the same excitation energy, there are also other electronic states of different symmetry (conical intersection of potential energy surfaces), which may couple with the optically excited state. Due to the gravitational perturbation the nuclei being in the symmetric stretch vibration mode of the optically excited electronic state pass over into the asymmetric stretch vibration mode of an isoenergetic electronic state. This parity conserving change of the vibronic wave function enhances a small gravitational perturbation to an optically detectable signal. The perturbation is associated with a time constant of about 3 μs, which we attribute to fluctuations of the shape of the compactification space induced by a background cosmic field.

Images of molecular orbitals in strong-field photoelectron momentum distributions generated by circularly polarized pulses

Strong-field photoelectron momentum distributions (PEMDs) generated in the ionization of molecules by circularly polarized laser pulses contain valuable information on the structure of the ionizing molecular orbital. In this paper, we investigate using the adiabatic theory how this information is imprinted in and can be extracted from such PEMDs. The PEMDs have a donutlike shape. The variation of a PEMD along the donut reproduces the orientation dependence of the ionization rate of the ionizing orbital, and hence reflects its nodal structure and shape. The transverse structure of the PEMD in cross sections of the donut corresponding to orientations of the molecule at which the ionizing orbital has a node in the direction opposite to that of the instantaneous laser field reflects the interplay of two competing ionization channels, which provides additional information on the orbital structure. We illustrate these features by the analysis of PEMDs for three states of different symmetries of the hydrogen molecular ion ${\mathrm{H}}_{2}{}^{+}$.

Coexistence of MLCT Excited States of Different Symmetry upon Photoexcitation of a Single Molecular Species

Photoexcitation of [Ru(tpy)(bpy)(μ-CN)Ru(py)4Cl]2+ ([RuRu]2+) at 387 nm results in the population of two 3MLCT excited states of different symmetry that coexist on the nanosecond scale. Common to both states is an excited electron in a tpy-based orbital. Their configuration differs in the position of the hole. In one excited state, 3MLCTz, the hole sits in an orbital parallel to the intermetallic axis allowing for a strong metal–metal electronic interaction. As a result, 3MLCTz is highly delocalized over both metal centers and shows an intense photoinduced intervalence charge transfer (PIIVCT) NIR signature. In the other excited state, 3MLCTxy, the hole is localized in an orbital perpendicular to the intermetallic axis and hence, significant intermetallic coupling is absent. This state shows no PIIVCT in the NIR and its spectrum is very similar to the one observed for the monometallic [Ru(tpy)(bpy)(CN)]+ reference. Both 3MLCT excited states have nanosecond lifetimes. The intervening energy barrier for a h...

Prandtl number dependence of convective fluids in tall laterally heated slots

The influence of the Prandtl number on the stable stationary and periodic flows of the fluids contained in laterally heated slots under realistic conditions, namely non-slip boundaries, insulated top and bottom horizontal limits and perfectly conducting lateral sides, is analyzed by using continuation methods. The branches of solutions are computed by decreasing the Prandtl number, for four Rayleigh numbers. The dynamical behavior depends strongly on both parameters. For a Rayleigh number, Ra = 103, the steady flow remains stable in the wide range of Prandtl numbers computed. At Ra = 104 and O(105) the first bifurcations are of Hopf type giving rise to a type of oscillations that affects the bulk of the fluid, alternating from a general circulation to multi-vortex solutions, or the boundary layer, respectively. However, it is found that, in any case, the location of the shear determines the type of the oscillations. Moreover, at Ra = 104 the critical multipliers at the secondary bifurcations on the main branch of POs are real, giving rise to different kinds of very bounded stable periodic states of different symmetries and periods. At Ra of order 105 the instability of the periodic orbits gives rise directly to quasi-periodic flows.

Effect of density of states peculiarities on Hund's metal behavior

We investigate a possibility of Hund's metal behavior in the Hubbard model with asymmetric density of states having peak(s). Specifically, we consider the degenerate two-band model and compare its results to the five-band model with realistic density of states of iron and nickel, showing that the obtained results are more general, provided that the hybridization between states of different symmetry is sufficiently small. We find that quasiparticle damping and the formation of local magnetic moments due to Hund's exchange interaction are enhanced by both, the density of states asymmetry, which yields stronger correlated electron or hole excitations, and the larger density of states at the Fermi level, increasing the number of virtual electron-hole excitations. For realistic densities of states these two factors are often interrelated because the Fermi level is attracted towards peaks of the density of states. We discuss the implication of the obtained results to various substances and compounds, such as transition metals, iron pnictides, and cuprates.

Dynamics of the C1s→π*excitation and decay inCO2probed by vibrationally and angularly resolved Auger spectroscopy

Participator resonant Auger decay spectra populating the $X, A, B$, and $C$ states of ${\mathrm{CO}}_{2}{}^{+}$ are recorded with angular and vibrational resolution for selected photon energies in the vicinity of the C $1s\ensuremath{\rightarrow}{\ensuremath{\pi}}^{*}$ resonance of ${\mathrm{CO}}_{2}$ using a narrow photon bandwidth and a high-resolution electron spectrometer. The measured electron spectra and the corresponding angular distribution parameters exhibit significant changes as functions of the photon energy across the resonance and with respect to the vibrational sublevels of a final ionic state. The measured spectra are interpreted by ab initio electronic structure and nuclear dynamics calculations which attribute observed variations to the effects of lifetime vibrational interference and of electronic state interference between the direct ionization amplitude and the resonant amplitudes for the excitation and decay of two overlapping resonant states of different symmetry. The present results provide deeper insight into the femtosecond relaxation dynamics of the core-excited ${\mathrm{CO}}_{2}$, which is not achievable with lower resolution, angle-averaged measurements.

Computational Benchmarking for Ultrafast Electron Dynamics: Wave Function Methods vs Density Functional Theory.

Attosecond electron dynamics in small- and medium-sized molecules, induced by an ultrashort strong optical pulse, is studied computationally for a frozen nuclear geometry. The importance of exchange and correlation effects on the nonequilibrium electron dynamics induced by the interaction of the molecule with the strong optical pulse is analyzed by comparing the solution of the time-dependent Schrödinger equation based on the correlated field-free stationary electronic states computed with the equationof-motion coupled cluster singles and doubles and the complete active space multi-configurational self-consistent field methodologies on one hand, and various functionals in real-time time-dependent density functional theory (TDDFT) on the other. We aim to evaluate the performance of the latter approach, which is very widely used for nonlinear absorption processes and whose computational cost has a more favorable scaling with the system size. We focus on LiH as a toy model for a nontrivial molecule and show that our conclusions carry over to larger molecules, exemplified by ABCU (C10H19N). The molecules are probed with IR and UV pulses whose intensities are not strong enough to significantly ionize the system. By comparing the evolution of the time-dependent field-free electronic dipole moment, as well as its Fourier power spectrum, we show that TD-DFT performs qualitatively well in most cases. Contrary to previous studies, we find almost no changes in the TD-DFT excitation energies when excited states are populated. Transitions between states of different symmetries are induced using pulses polarized in different directions. We observe that the performance of TD-DFT does not depend on the symmetry of the states involved in the transition.

Photoelectron spectrum and dynamics of the uracil cation.

The photoelectron spectrum of uracil and the molecular dynamics of its radical cation are investigated using the multiconfigurational time-dependent Hartree (MCTDH) method. For this aim, the vibronic coupling model Hamiltonian is used including up to ten important a' modes. Moreover, to account for coupling through conical intersections between states of different symmetry in the system, coupling constants of two a″ modes are taken into account. The parameters used in the model are obtained by fitting to ab inito data obtained with extensive EOM-IP-CCSD calculations. The first four cationic states were investigated, which are either of A″ (hole in a π orbital) or A' (hole in a nO orbital) symmetry. The results of the wavepacket propagations were used to calculate the corresponding photoelectron spectrum and compare to the experimental spectrum. The MCTDH simulations reproduce the experimental spectrum well. The dynamics starting from the D2 and D3 ionic states show a fast relaxation to the cationic ground state often involving direct D2-D0 or D3-D1 transitions.

Symmetry-dependent electron-electron interaction in coherent tunnel junctions resolved by measurements of zero-bias anomaly

We provide conclusive experimental evidence that zero bias anomaly in the differential resistance of magnetic tunnel junctions (MTJs) is due to electron-electron interaction (EEI), clarifying a long standing issue. Magnon effect that caused confusion is now excluded by measuring at low temperatures down to 0.2 K and with reduced AC measurement voltages down to 0.06 mV. The normalized change of conductance is proportional to $\ln{(eV/k_{B}T)}$, consistent with the Altshuler-Aronov theory of tunneling that describes the reduction of density of states due to EEI, but inconsistent with magnetic impurity scattering. The slope of the $\ln{(eV/k_{B}T)}$ dependence is symmetry dependent: the slopes for P and AP states are different for coherent tunnel junctions with symmetry filtering, while nearly the same for those without symmetry filtering (amorphous barriers). This observation may be helpful for verifying symmetry preserved filtering in search of new coherent tunneling junctions, and for probing and separating electron Bloch states of different symmetries in other correlated systems.

Two-dimensional electron gases at LaAlO3/SrTiO3 interfaces: orbital symmetry and hierarchy engineered by crystal orientation.

Recent findings show the emergence of two-dimensional electron gases (2DEGs) at LaAlO(3)/SrTiO(3) interfaces along different orientations; yet details on band reconstructions have remained so far unknown. Via x-ray linear dichroism spectroscopy, we demonstrate that crystal symmetry imposes distinctive 2DEG orbital hierarchies on (001)-and (110)-oriented quantum wells, allowing selective occupancy of states of different symmetry. Such orientational tuning expands the possibilities for electronic engineering of 2DEGs and opens up enticing opportunities to understand the link between orbital symmetry and complex correlated states at LaAlO(3)/SrTiO(3) quantum wells.