C2v Symmetry Research Articles

Fragile dislocation modes in obstructed atomic topological phases

We here introduce the concept of fragile dislocation modes, which are localized only in a fraction of a topological phase while otherwise leaking into the bulk continuum. As we demonstrate here, such dislocation modes are hosted in an obstructed atomic topological phase in the two-dimensional Su-Schrieffer-Heeger model but only in a finite region with an indirect gap at high energy. They are realized as chiral pairs at finite energies with protection stemming from a combination of the chiral (unitary particle-hole) and the point group (C4v) symmetries, but only when the indirect gap is open. In this regime, we corroborate the stability of the defect modes by following their localization and also by explicitly adding a weak chemical potential disorder. Our findings should, therefore, be consequential for the experimental observation of such modes in designer topological crystals and classical metamaterials. Published by the American Physical Society 2024

Investigation of Isolated IrF5 -, IrF6 - Anions and M[IrF6] (M=Na, K, Rb, Cs) Ion Pairs by Matrix-Isolation Spectroscopy and Relativistic Quantum-Chemical Calculations.

The molecular IrF5 -, IrF6 - anions and M[IrF6] (M=Na, K, Rb, Cs) ion pairs were prepared by co-deposition of laser-ablated alkali metal fluorides MF with IrF6 and isolated in solid neon or argon matrices under cryogenic conditions. The free anions were obtained as well by co-deposition of IrF6 with laser-ablated metals (Ir or Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using two-component quasi-relativistic DFT methods accounting for spin-orbit coupling (SOC) effects as well as multi-reference configuration-interaction (MRCI) approaches with SOC. Inclusion of SOC is crucial in the prediction of spectra and properties of IrF6 - and its alkali-metal ion pairs. The observed IR bands and the computations show that the IrF6 - anion adopts an Oh structure in a nondegenerate ground state stabilized by SOC effects, and not a distorted D4h structure in a triplet ground state as suggested by scalar-relativistic calculations. The corresponding "closed-shell" M[IrF6] ion pairs with C3v symmetry are stabilized by coordination of an alkali metal ion to three F atoms, and their structural change in the series from M=Na to Cs was proven spectroscopically. There is no evidence for the formation of IrF7, IrF7 - or M[IrF7] (M=Na, K, Rb, Cs) ion pairs in our experiments.

Gate-Tunable Asymmetric Quantum Dots in Graphene-Based Heterostructures: Pure Valley Polarization and Confinement

We explore the possibility of attaining valley-dependent tunnelling and confinement using proximity-induced spin-orbit couplings (SOCs) in graphene-based heterostructures. We consider gate-tunable asymmetric quantum dots (AQDs) on graphene heterostructures and exhibiting a C3v and/or C6v symmetry. By employing a tight-binding model, we explicitly reveal a pure valley confinement and valley signal in AQDs by streaming the valley local density, leading to valley-charge separation in real space. The confinement of the valley quasi-bound states is sensitive to the locally induced SOCs and to the spatial distribution of the induced AQDs; it is also robust against on-site disorder. The adopted process of attaining a pure valley-Hall conductivity and confinement with zero charge currents is expected to provide more options towards valley-dependent electron optics.

Electronic structure and optical spectral analysis of the MnO42- anion with consideration of site and Jahn-Teller distortion.

The ground state of 3d1 MnO42- was studied by density functional theory (DFT) and complete active space self-consistent field (CASSCF) methods in terms of a variety of molecular point group structures to ascertain the site and Jahn-Teller (JT) distortion effect. Modeling results from UB3LYP/6-31+G(d) calculations with natural bond orbital analysis show the four Mn-O bonds are coordinate covalent. The one-electron matrix elements from CASSCF(AILFT) (abinitio ligand field theory) with a second order perturbation treatment were used to calculate the parameters of the angular overlap model. These allowed the calculation of JT stabilization energies and first and second order JT coupling constants for MnO42- with C2v and D2d symmetry. Absorption spectra and excited state transition energies were calculated assuming the lattice distorted geometry was C2v with time-dependent DFT (TDDFT) using the unrestricted coulomb-attenuating UCAM-B3LYP density functional and with the spin-adapted spin-flip DFT using the UBH&HLYP density functional, both with the AUG-CC-PVTZ basis set. The mean absolute deviation of the calculations from experimental excited states for the ligand field and ligand-to-metal charge transfer (LMCT) bands was better than 0.1eV. Several new assignments for LMCT excited states were made on the basis of the TDDFT excitation results.

Role of Pyramidal Low-Dimensional Semiconductors in Advancing the Field of Optoelectronics

Numerous optoelectronic devices based on low-dimensional nanostructures have been developed in recent years. Among these, pyramidal low-dimensional semiconductors (zero- and one-dimensional nanomaterials) have been favored in the field of optoelectronics. In this review, we discuss in detail the structures, preparation methods, band structures, electronic properties, and optoelectronic applications (photocatalysis, photoelectric detection, solar cells, light-emitting diodes, lasers, and optical quantum information processing) of pyramidal low-dimensional semiconductors and demonstrate their excellent photoelectric performances. More specifically, pyramidal semiconductor quantum dots (PSQDs) possess higher mobilities and longer lifetimes, which would be more suitable for photovoltaic devices requiring fast carrier transport. In addition, the linear polarization direction of exciton emission is easily controlled via the direction of magnetic field in PSQDs with C3v symmetry, so that all-optical multi-qubit gates based on electron spin as a quantum bit could be realized. Therefore, the use of PSQDs (e.g., InAs, GaN, InGaAs, and InGaN) as effective candidates for constructing optical quantum devices is examined due to the growing interest in optical quantum information processing. Pyramidal semiconductor nanorods (PSNRs) and pyramidal semiconductor nanowires (PSNWRs) also exhibit the more efficient separation of electron-hole pairs and strong light absorption effects, which are expected to be widely utilized in light-receiving devices. Finally, this review concludes with a summary of the current problems and suggestions for potential future research directions in the context of pyramidal low-dimensional semiconductors.

Engineering Spin-Orbit Interactions in Silicon Qubits at the Atomic-Scale.

Spin-orbit interactions arise whenever the bulk inversion symmetry and/or structural inversion symmetry of a crystal is broken providing a bridge between a qubit's spin and orbital degree of freedom. While strong interactions can facilitate fast qubit operations by all-electrical control, they also provide a mechanism to couple charge noise thereby limiting qubit lifetimes. Previously believed to be negligible in bulk silicon, recent silicon nano-electronic devices have shown larger than bulk spin-orbit coupling strengths from Dresselhaus and Rashba couplings. Here, it is shown that with precision placement of phosphorus atoms in silicon along the [110] direction (without inversion symmetry) or [111] direction (with inversion symmetry), a wide range of Dresselhaus and Rashba coupling strength can be achieved from zero to 1113 × 10-13eV-cm. It is shown that with precision placement of phosphorus atoms, the local symmetry (C2v, D2d, and D3d) can be changed to engineer spin-orbit interactions. Since spin-orbit interactions affect both qubit operation and lifetimes, understanding their impact is essential for quantum processordesign.

Tailoring coupled topological corner states in photonic crystals via symmetry breaking induced by defects

In this paper, we present an effective approach to tailor the optical properties of coupled corner states in photonic crystal (PhC) supercell arrays by symmetry breaking. Defects are strategically introduced into unit cells to break the in-plane C4v symmetry, and numerical simulations confirm the preservation of the band gap and two-dimensional Zak phases, in spite of the presence of defects. Notably, the size of defects is demonstrated to play a significant role in tuning the eigenfrequencies, quality (Q) factors, and band structures of the coupled corner states. Furthermore, these defects exhibit the ability to transform topological dark states into bright states, enabling efficient excitation by external plane waves and polarization-dependent Q factors. The resonant origin of the coupled corner states is comprehensively elucidated using a multipole decomposition analysis. This study further releases the potential of the topological light-matter interaction, holding significant implications for the design and advancement of topological photonic devices with on-demand tunability and multifrequency regions for various applications such as lasing, sensing, and quantum information processing. Published by the American Physical Society 2024

Crystal-field analysis of photoluminescence from orthorhombic Eu centers and energy transfer from host to Eu in GaN co-doped with Mg and Eu

Gallium nitride co-doped with magnesium and europium shows great potential for active layers in red light emitting diode structures due to strong and sharp luminescence emission around 620 nm. In this work, sharp and intense Eu3+ luminescence lines from the excited states of the 5DJ (J = 0, 1) multiplets to the ground states of the 7FJ (J = 0, 1, 2) multiplets have been analyzed using a C2v crystal-field equivalent operator Hamiltonian. A model of Eu centers with the C2v symmetry has been proposed to be an Eu3+ complex accompanied by either a pair of nitrogen and gallium vacancies (VN-VGa) or a pair consisting of a nitrogen vacancy and magnesium impurity (VN-MgGa) in the vicinity of the Eu ion based on the crystal-field analysis, the selection rules and the observed polarization of the Eu3+ luminescence lines. Energy transfer from the host to the Eu ions under band-to-band excitation occurs through electron-hole recombination between VN with the electron-like state and VGa or MgGa with the hole-like state; these may be associated with the shallow-trapped or deep-trapped states, respectively, proposed as the energy transfer mechanism in previous literature.

Helicity-dependent photocurrent of topological surface states in the intrinsic magnetic topological insulator MnBi2Te4

Helicity-dependent photocurrent (HDPC) of the topological surface states (TSSs) in the intrinsic magnetic topological insulator MnBi2Te4 is investigated. It is revealed that the HDPC is mainly contributed by the circular photogalvanic effect (CPGE) current when the incident plane is perpendicular to the connection of the two electrodes, while the circular photon drag effect plays the dominant role when the incident plane is parallel to the connection of the two electrodes. The CPGE current shows an odd function dependence on incident angles, which is consistent with the C3v symmetry group of the TSSs in MnBi2Te4. The amplitude of the CPGE current increases with the decrease in temperature, which can be attributed to the increase in mobility at low temperatures, confirmed by the transport measurements. Furthermore, we modulate the CPGE of MnBi2Te4 by applying top gate and source–drain voltages. Compared to Bi2Te3 of the same thickness, the CPGE current of MnBi2Te4 can be more effectively tuned by the top gate because the Fermi level of MnBi2Te4 can be effectively regulated by the top gate, and it is tuned across the Dirac point. This work suggests that the intrinsic magnetic topological insulator MnBi2Te4 is a good candidate for designing opto-spintronics devices.

Efficient polarization-insensitive quasi-BIC modulation by VO2 thin films.

Bound states in the continuum (BIC) offer great design freedom for realizing high-quality factor metasurfaces. By deliberately disrupting the inherent symmetries, BIC can degenerate into quasi-BIC exhibiting sharp spectra with strong light confinement. This transformation has been exploited to develop cutting-edge sensors and modulators. However, most proposed quasi-BICs in metasurfaces are composed of unit cells with Cs symmetry that may experience performance degradation due to polarization deviation, posing challenges in practical applications. Addressing this critical issue, our research introduces an innovative approach by incorporating metasurfaces with C4v unit cell symmetry to eliminate polarization response sensitivity. Vanadium Dioxide (VO2) is a phase-change material with a relatively low transition temperature and reversibility. Here, we theoretically investigate the polarization-insensitive quasi-BIC modulation in Si-VO2 hybrid metasurfaces. By introducing defects into metasurfaces with Cs, C4, and C4v symmetries, we enable the emergence of quasi-BICs characterized by strong Fano resonance in their transmission spectra. Via numerically calculating the multipole decomposition, distinct dominant multipoles for different quasi-BICs are identified. A comprehensive investigation into the polarization responses of these structures under varying directions of linearly polarized light reveals the superior polarization-independent characteristics of metasurfaces with C4 and C4v symmetries, a feature that ensures the maintenance of maximum resonance peaks irrespective of polarization direction. Utilizing the polarization-insensitive quasi-BIC, we thus designed two different Si-VO2 hybrid metasurfaces with C4v symmetry. Each configuration presents complementary benefits, leveraging the VO2 phase transition's loss change to facilitate efficient modulation. Our quantitative calculation indicates notable achievements in modulation depth, with a maximum relative modulation depth reaching up to 342%. For the first time, our research demonstrates efficient modulation using polarization-insensitive quasi-BICs in designed Si-VO2 hybrid metasurfaces, achieving identical polarization responses for quasi-BIC-based applications. Our work paves the way for designing polarization-independent quasi-BICs in metasurfaces and marks a notable advancement in the field of tunable integrated devices.

Preference of C2v Symmetry in Low-Spin Hexacarbonyls of Rare-Earth and f Elements

The structures and bonding of selected neutral M(CO)6 complexes (M = Sc, Y, La, Lu, Ac and U) have been studied by density functional theory calculations. The calculations revealed the preference for C2v symmetry and low-spin electronic state for most of these complexes. The relative stability of the low-symmetry species increases gradually with the size of the metal atom. While the characteristic Oh hexa-coordinated structure is favored in the high-spin electronic state of the smaller metals, for heavier metals, important advantages of the C2v vs. Oh structures include larger charge transfer interactions in terms of transferred electrons as well as better steric conditions. Our joint experimental–theoretical analysis detected and confirmed the Oh structure of the Sc(CO)6 complex in cryogenic CO/Ar matrices.

Capturing CO2 in Quadrupolar Binding Pockets: Broadband Microwave Spectroscopy of Pyrimidine-(CO2)n, n = 1,2.

Pyrimidine has two in-plane CH(δ+)/N̈(δ-)/CH(δ+) binding sites that are complementary to the (δ-/2δ+/δ-) quadrupole moment of CO2. We recorded broadband microwave spectra over the 7.5-17.5 GHz range for pyrimidine-(CO2)n with n = 1 and 2 formed in a supersonic expansion. Based on fits of the rotational transitions, including nuclear hyperfine splitting due to the two 14N nuclei, we have assigned 313 hyperfine components across 105 rotational transitions for the n = 1 complex and 208 hyperfine components across 105 rotational transitions for the n = 2 complex. The pyrimidine-CO2 complex is planar, with CO2 occupying one of the quadrupolar binding sites, forming a structure in which the CO2 is stabilized in the plane by interactions with the C-H hydrogens adjacent to the nitrogen atom. This structure is closely analogous to that of the pyridine-CO2 complex studied previously by (Doran, J. L. J. Mol. Struct. 2012, 1019, 191-195). The fit to the n = 2 cluster gives rotational constants consistent with a planar cluster of C2v symmetry in which the second CO2 molecule binds in the second quadrupolar binding pocket on the opposite side of the ring. The calculated total binding energy in pyrimidine-CO2 is -13.7 kJ mol-1, including corrections for basis set superposition error and zero-point energy, at the CCSD(T)/ 6-311++G(3df,2p) level, while that in pyrimidine-(CO2)2 is almost exactly double that size, indicating little interaction between the two CO2 molecules in the two binding sites. The enthalpy, entropy, and free energy of binding are also calculated at 300 K within the harmonic oscillator/rigid-rotor model. This model is shown to lack quantitative accuracy when it is applied to the formation of weakly bound complexes.

Photoelectron velocity map imaging spectroscopy of group 14 elements and iron tetracarbonyl anionic clusters MFe(CO)4- (M = Si, Ge, Sn).

The heteronuclear group 14 M-iron tetracarbonyl clusters MFe(CO)4- (M = Si, Ge, Sn) anions have been generated in the gas phase by laser ablation of M-Fe alloys and detected by mass and photoelectron spectroscopy. With the support of quantum chemical calculations, the geometric and electronic structures of MFe(CO)4- (M = Si, Ge, Sn) are elucidated, which shows that all the MFe(CO)4- clusters have the M-Fe bonded, iron-centered, and carbonyl-terminal M-Fe(CO)4 structure with the C2v symmetry and a 2B2 ground state. The M-Fe bond can be considered a double bond, which includes one σ electron sharing bond and one π dative bond. The C-O bonds in those anionic clusters are calculated to be elongated to different extents, and in particular, the C-O bonds in SiFe(CO)4- are elongated more. The Si-Fe alloy thus turns out to be a better collocation to activate the C-O bonds in the gas phase among group 14. The present findings have important implications for the rational development of high-performance catalysts with isolated metal atoms/clusters dispersed on supports.

Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+)

We performed quantum chemical calculations on the geometries, electronic structures, bonding properties, and stability strategy of endohedral metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+). Our calculations revealed that there are three different lowest-energy structures with C2v, C3v, and Td symmetries for TM@C28. The HOMO–LUMO gap of all these structures ranges from 1.35 eV to 2.31 eV, in which [V@C28]+ has the lowest HOMO–LUMO gap of 1.35 eV. The molecular orbitals are mainly composed of fullerene cage orbitals and slightly encapsulated metal orbitals. The bonding analysis on the metal–cage interactions reveals they are dominated by the Coulomb term ΔEelstat and the orbital interaction term ΔEorb, in which the orbital interaction term ΔEorb contributes more than the Coulomb term ΔEelstat. The addition of one or two CF3 groups to [V@C28]+ could increase the HOMO–LUMO gap and further increase the stability of [V@C28]+.

Angle-Dependent Raman Spectra of Crystal Polymorphs of GaO: A Computational Study.

Two crystal polymorphs of GaO consisting of GaO-H and GaO-T monolayers are proposed in this study. Based on the density functional theory calculations, the phonon dispersion demonstrates that both GaO-H and GaO-T monolayers could be stable. The band gaps of GaO-H and GaO-T monolayers are 1.51 and 1.43 eV, respectively. When an external electric field is applied, the band gaps of GaO monolayers are reduced dramatically, down to 0.13 eV with the field of 0.7 V/Å. Because of the decreased symmetry of C3v under an external electric field, more peaks of Raman spectra can be obtained. The angle-dependent Raman spectra of and of GaO-H monolayer, and and of GaO-T monolayer are discussed seperately, with the incident lasers of 488 and 532 nm. Additionally, the Raman intensity distribution shows that the incident light should be parallel to the plane of the GaO monolayer to obtain more comparable Raman spectra. These investigations of the crystal polymorphs of GaO monolayers may guide the experimental investigations of GaO monolayers and potential optoelectronic applications.

Crystal Symmetry-Dependent In-Plane Hall Effect.

The Hall effect has played a vital role in unraveling the intricate properties of electron transport in solid materials. Here, we report on a crystal symmetry-dependent in-plane Hall effect (CIHE) observed in a CuPt/CoPt ferromagnetic heterostructure. Unlike the planar Hall effect (PHE), the CIHE in CuPt/CoPt strongly depends on the current flowing direction (ϕI) with respect to the crystal structure. It reaches its maximum when the current is applied along the low crystal-symmetry axes and vanishes when applied along the high crystal-symmetry axes, exhibiting an unconventional angular dependence of cos(3ϕI). Utilizing a symmetry analysis based on the Invariant Theory, we demonstrate that the CIHE can exist in magnetic crystals possessing C3v symmetry. Using a tight-binding model and realistic first-principles calculations on the metallic heterostructure, we find that the CIHE originates from the trigonal warping of the Fermi surface. Our observations highlight the critical role of crystal symmetry in generating new types of Hall effects.

Water-carbon disulfide dimers: observation of a new isomer and ab initio structure theory.

The weakly bound dimer water-carbon disulfide is studied by ab initio structure theory and high-resolution infrared spectroscopy. The calculations yield three stable minima in the potential energy surface, all planar. The most stable, isomer 1, was observed previously by microwave spectroscopy. It has C2v symmetry, an S-O bond, and a linear O-S-C-S backbone. Isomer 2, the next most stable, has not been considered previously by theory or experiment. It also has C2v symmetry, but with a side-by-side structure. Isomer 3, which is slightly less stable, is side-by-side with one O-H bond pointing toward an S atom. The first gas phase water-CS2 infrared spectra are reported. For isomer 1, H2O-, HDO-, and D2O-CS2 are observed in the CS2ν1 + ν3 region, H2O-CS2 in the H2O ν2 bend region, and D2O-CS2 in the D2O ν1 and ν3 stretch regions. The latter ν3 spectrum enables an experimental determination of the A rotational parameter, which turns out to be larger than expected. The new isomer 2 is observed by means of a band in the H2O ν2 region, confirming its C2v symmetry and calculated structure.

Exploring the structure and hydrogen storage capacity of CeHn0/+ clusters.

The unique 4f orbitals and abundant electronic energy levels of rare earth elements enable effective doping and modification to enhance hydrogen storage performance, making it an increasingly prominent focus of research. The structures of neutral and cationic CeHn0/+ (n = 2-20) clusters have been determined using the Crystal Structure AnaLYsis by Particle Swarm Optimization (CALYPSO) method in conjunction with density functional theory (DFT). Interestingly, the CeH13 and CeH14+ exhibit remarkable stability in the doublet state with Cs and C2v symmetry, respectively. The adsorption energy of CeHn0/+ (n = 2-20) suggests a preference for H atoms to chemically adsorb on Ce atoms. The analysis of molecular orbital composition reveals that the stability of both CeH13 and CeH14+ is attributed to the significant hybridization between the H 1s and Ce 4f orbitals. Both CeH13 and CeH14+ demonstrate significant hydrogen storage capacities, with values reaching 8.5 wt% and 9.1 wt%, respectively.

Influence of H-bond competitors on the solvent-dependent structures of an octaurea-calix[4]tube.

A novel octaurea-calix[4]tube (UC4T) has been synthesized in three steps from the original Beer's p-tert-butylcalix[4]tube ionophore. In a polar solvent (DMSO-d6), UC4T rapidly interconverts between two identical conformations with C2v symmetry for the two calix[4]arene subunits. However, in a less polar solvent mixture (CDCl3/DMSO-d6, 98 : 2), UC4T adopts a highly distorted asymmetric structure, which hinders the formation of typical tetraurea calix[4]arene capsular assemblies. The complexation of potassium (or barium) cations inside the dioxyethylene ionophoric binding site of UC4T triggers a C2v to C4v symmetry rearrangement of the two calix[4]arene subunits. This rearrangement leads to the formation of a transient capsular dimeric species observed in solution upon the addition of KI or BaCl2·2H2O to a solution (CDCl3/DMSO-d6, 98 : 2) of the macrocycle. X-ray studies confirm UC4T's ability to adopt different asymmetric conformations, depending on its interactions with solvent molecules. Two distinct crystal forms (α and β) of UC4T have been obtained, each displaying divergent calix[4]arene subunits with pinched-cone conformations. These conformations exhibit distinctive head-to-tail (α) or head-to-head/tail-to-tail (β) orientations of the ureido groups, which are involved in hydrogen bonding with solvent molecules. Notably, the pseudo-capsular 1D supramolecular polymeric arrays observed in the β form of UC4T assemble to create large parallel solvent channels.

A triple Fano resonance Si-graphene metasurface for multi-channel tunable ultra-narrow band sensing.

In this work, a dielectric metasurface composed of a silicon nanodisk etched with a square hole is proposed. By introducing C4v symmetry breaking, the symmetry-protected bound states in the continuum (SP-BIC) is transformed into a quasi-BIC (Q-BIC), simultaneously inducing triple Fano resonances in the near-infrared light band corresponding to one dipole and two Q-BIC resonances. The characteristics of Q-BIC resonances are elucidated through multipole decomposition and near-field distribution analysis. Subsequently, monolayer graphene is integrated into the Si metasurface. The light field in the composite metasurface can be flexibly modulated by changing the Fermi level of graphene. This modulation enables optimal transmission with an enhancement of up to 252%, while the confined electromagnetic energy experiences a remarkable increase of about 1020%. Simulation results demonstrate that the Si-graphene composite metasurface exhibits a high refractive index sensitivity of 162 nm RIU-1, accompanied by a figure of merit of 170.526 RIU-1. This composite metasurface holds promise as a high-performance sensor in the near-infrared band and has potential for application in the fields of active tunable optical devices and biochemical sensing.