Spin-orbit States Research Articles

High-Level ab Initio Predictions for the Ionization Energies, Bond Dissociation Energies, and Heats of Formation of Vanadium Methylidene, Vanadium Methyl Species, and Their Cations (VCH2/VCH2+, VCH3/VCH3+).

The ionization energies of VCH2 and VCH3, the various 0 K bond dissociation energies (D0s) in their neutrals and cations, and their respective heats of formation at 0 and 298 K are computed by the single-reference, wave function-based CCSDTQ/CBS procedure. The core of the composite method is the approximation to the complete basis set (CBS) limit at the coupled cluster (CC) level which includes up to full quadruple excitations. The zero-point vibrational energy, core-valence correlation, spin-orbit coupling, and scalar relativistic effects have their contributions incorporated in an additive manner. For the species in the current study, this protocol requires geometry optimizations and harmonic frequency calculations practically no higher than the CCSD(T)/aug-cc-pwCVTZ and CCSD(T)/aug-cc-pVTZ levels, respectively. The present calculations successfully predict D0(V+-CH3) = 2.126 eV and D0(V+-CH2) = 3.298 eV in remarkable agreement with the data recently measured by a spin-orbit state selected V+ + CH4 collision experiment (Phys. Chem. Chem. Phys. 2021, 23, 273-286). The good accord encourages the use of CCSDTQ/CBS protocol in thermochemical predictions of various feasible product channels identified in methane activation by transition metal species.

Anomalous magnetism of uranium(IV)-oxo and -imido complexes reveals unusual doubly degenerate electronic ground states

Anomalous magnetism of uranium(IV)-oxo and -imido complexes reveals unusual doubly degenerate electronic ground states

Strong spin-orbit coupling inducing Autler-Townes effect in lead halide perovskite nanocrystals

Manipulation of excitons via coherent light-matter interaction is a promising approach for quantum state engineering and ultrafast optical modulation. Various excitation pathways in the excitonic multilevel systems provide controllability more efficient than that in the two-level system. However, these control schemes have been restricted to limited control-light wavelengths and cryogenic temperatures. Here, we report that lead halide perovskites can lift these restrictions owing to their multiband structure induced by strong spin-orbit coupling. Using CsPbBr3 perovskite nanocrystals, we observe an anomalous enhancement of the exciton energy shift at room temperature with increasing control-light wavelength from the visible to near-infrared region. The enhancement occurs because the interconduction band transitions between spin-orbit split states have large dipole moments and induce a crossover from the two-level optical Stark effect to the three-level Autler-Townes effect. Our finding establishes a basis for efficient coherent optical manipulation of excitons utilizing energy states with large spin-orbit splitting.

Heralded Generation of Vectorially Structured Photons With a High Purity

Engineering vector spatial modes of photons is an important approach for manipulating high-dimension photonic states in various quantum optical experiments. In this work, we demonstrate the generation of heralded single photons with well-defined vector spatial modes by using a self-stable polarizing interferometer comprising a spatial light modulator. Specifically, it is shown that, by carefully tailoring and compensating the spatial and temporal amplitudes of manipulated photons, one can exactly convert ultrafast single photons into desired spin-orbit states with an extremely high purity. This compact and robust device provides a versatile way for not only the generation, but also the manipulation and characterization of arbitrary photonic spin-orbit states.

Perpendicular magnetic anisotropy at the Fe/Au(111) interface studied by Mössbauer, x-ray absorption, and photoemission spectroscopies

The origin of the interfacial perpendicular magnetic anisotropy (PMA) induced in the ultrathin Fe layer on the Au(111) surface was examined using synchrotron-radiation-based M\"{o}ssbauer spectroscopy (MS), X-ray magnetic circular dichroism (XMCD), and angle-resolved photoemission spectroscopy (ARPES). To probe the detailed interfacial electronic structure of orbital hybridization between the Fe 3$d$ and Au 6$p$ bands, we detected the interfacial proximity effect, which modulates the valence-band electronic structure of Fe, resulting in PMA. MS and XMCD measurements were used to detect the interfacial magnetic structure and anisotropy in orbital magnetic moments, respectively. $In$-$situ$ ARPES also confirms the initial growth of Fe on large spin-orbit coupled surface Shockley states under Au(111) modulated electronic states in the vicinity of the Fermi level. This suggests that PMA in the Fe/Au(111) interface originates from the cooperation effects among the spin, orbital magnetic moments in Fe, and large spin-orbit coupling in Au. These findings pave the way to develop interfacial PMA using $p$-$d$ hybridization with a large spin-orbit interaction.

Topological spin textures of exciton-polaritons manipulating by spin-orbit coupling

The topological spin textures of exciton-polariton in microcavities are governed by the interplay of the spin-orbit coupling and longitudinal-transverse splitting. We demonstrate the generation of exciton-polariton spin vortices by a linearly polarized optical pump and analyze the arising exciton-polariton topological spin textures in microcavities. By manipulating the spin-orbit coupling and polarization states, one can control the density, phase, and polarization distributions of exciton-polaritons. Moreover, we obtain a vortex of the pure phase winding number and spin-vortices characterized by quantized polarization winding, which holds a potential application for spinoptronic devices and quantum information.

Ultrafast intraband Auger process in self-doped colloidal quantum dots

Summary Investigating the separate dynamics of electrons and holes has been challenging, although it is critical for the fundamental understanding of semiconducting nanomaterials. n-Type self-doped colloidal quantum dots (CQDs) with excess electrons occupying the low-lying state in the conduction band (CB) have attracted a great deal of attention because of not only their potential applications to infrared optoelectronics but also their intrinsic system that offers a platform for investigating electron dynamics without elusive contributions from holes in the valence band. Here, we show an unprecedented ultrafast intraband Auger process, electron relaxation between spin-orbit coupling states, and exciton-to-ligand vibrational energy transfer process that all occur exclusively in the CB of the self-doped β-HgS CQDs. The electron dynamics obtained by femtosecond mid-infrared spectroscopy will pave the way for further understanding of the blinking phenomenon, disproportionate charging in light-emitting diodes, and hot electron dynamics in higher quantum states coupled to surface states of CQDs.

Quantum electronic control on chemical activation of methane by collision with spin-orbit state selected vanadium cation.

By coupling a newly developed quantum-electronic-state-selected supersonically cooled vanadium cation (V+) beam source with a double quadrupole-double octopole (DQDO) ion-molecule reaction apparatus, we have investigated detailed absolute integral cross sections (σ's) for the reactions, V+[a5DJ (J = 0, 2), a5FJ (J = 1, 2), and a3FJ (J = 2, 3)] + CH4, covering the center-of-mass collision energy range of Ecm = 0.1-10.0 eV. Three product channels, VH+ + CH3, VCH2+ + H2, and VCH3+ + H, are unambiguously identified based on Ecm-threshold measurements. No J-dependences for the σ curves (σ versus Ecm plots) of individual electronic states are discernible, which may indicate that the spin-orbit coupling is weak and has little effect on chemical reactivity. For all three product channels, the maximum σ values for the triplet a3FJ state [σ(a3FJ)] are found to be more than ten times larger than those for the quintet σ(a5DJ) and σ(a5FJ) states, showing that a reaction mechanism favoring the conservation of total electron spin. Without performing a detailed theoretical study, we have tentatively interpreted that a weak quintet-to-triplet spin crossing is operative for the activation reaction. The σ(a5D0, a5F1, and a3F2) measurements for the VH+, VCH2+, and VCH3+ product ion channels along with accounting of the kinetic energy distribution due to the thermal broadening effect for CH4 have allowed the determination of the 0 K bond dissociation energies: D0(V+-H) = 2.02 (0.05) eV, D0(V+-CH2) = 3.40 (0.07) eV, and D0(V+-CH3) = 2.07 (0.09) eV. Detailed branching ratios of product ion channels for the titled reaction have also been reported. Excellent simulations of the σ curves obtained previously for V+ generated by surface ionization at 1800-2200 K can be achieved by the linear combination of the σ(a5DJ, a5FJ, and a3FJ) curves weighted by the corresponding Boltzmann populations of the electronic states. In addition to serving as a strong validation of the thermal equilibrium assumption for the populations of the V+ electronic states in the hot filament ionization source, the agreement between these results also confirmed that the V+(a5DJ, a5FJ, and a3FJ) states prepared in this experiment are in single spin-orbit states with 100% purity.

Controlling the Spin-Orbit Branching Fraction in Molecular Collisions.

The collision geometry, that is, the relative orientation of reactants before interaction, can have a large effect on how a collision or reaction proceeds. Certain geometries may prevent access to a given product channel, while others might enhance it. In this Letter, we demonstrate how the initial orientation of NO molecules relative to approaching Ar atoms determines the branching between the spin-orbit changing and the spin-orbit conserving rotational product channels. We use a recently developed quantum treatment to calculate differential and integral branching fractions, at any arbitrary orientation, from theoretical and experimental data points. Our results show that a substantial degree of control over the final spin-orbit state of the scattering products can be achieved by tuning the initial collision geometry.

Dynamical Zeeman resonance in spin-orbit-coupled spin-1 Bose gases

We predict a dynamical resonant effect, which is driven by externally applied linear and quadratic Zeeman fields, in a spin-orbit-coupled spin-1 Bose-Einstein condensate. The Bose-Einstein condensate is assumed to be initialized in some superposed state of Zeeman sublevels and subject to a sudden shift of the trapping potential. It is shown that the time-averaged center-of-mass oscillation and the spin polarizations of the Bose-Einstein condensate exhibit remarkable resonant peaks when the Zeeman fields are tuned to certain strengths. The underlying physics behind this resonance can be traced back to the out-of-phase interference of the dynamical phases carried by different spinorbit states. By analyzing the single particle spectrum, the resonant condition is summarized as a simple algebraic relation, connecting the strengths of the linear and quadratic Zeeman fields. This property is potentially applicable in quantum information and quantum precision measurement.

Timing angular momentum transfer for parity-unfavored transitions in multiphoton ionization

When a bound electron is photoionized from an atom or molecule, the remaining multielectron ion with excess internal energy will relax towards lower-energy states. The subsequent transverse angular momentum transfer between the parent ion and the ejected electron can lead to an electron parity-unfavored transition. Here we perform a self-calibrated timing experiment to measure the time delay of the angular momentum transfer of parity-unfavored transitions during the multiphoton ionization. We use a strong linearly polarized 400-nm light field to trigger a parity-unfavored transition in the channel of the spin-orbit excited ionic state of krypton atoms and then selectively probe the phases of the electron wave functions with different magnetic quantum numbers with a weak parallelly (orthogonally) polarized 800-nm light field. The parallel and orthogonal probes serve as the start and the stop of a stopwatch, respectively. Hence, this allows us to access the characteristic time of such an ultrafast intra-atom multielectron process.

Orbital and Spin Dynamics of Single Neutrally-Charged Nitrogen-Vacancy Centers in Diamond.

The neutral charge state plays an important role in quantum information and sensing applications based on nitrogen-vacancy centers. However, the orbital and spin dynamics remain unexplored. Here, we use resonant excitation of single centers to directly reveal the fine structure, enabling selective addressing of spin-orbit states. Through pump-probe experiments, we find the orbital relaxation time (430ns at 4.7K) and measure its temperature dependence up to 11.8K. Finally, we reveal the spin relaxation time (1.5s) and realize projective high-fidelity single-shot readout of the spin state (≥98%).

Magnetic dipole excitations based on the relativistic nuclear energy density functional

Magnetic dipole (M1) excitations build not only a fundamental mode of nucleonic transitions, but they are also relevant for nuclear astrophysics applications. We have established a theory framework for description of M1 transitions based on the relativistic nuclear energy density functional. For this purpose the relativistic quasiparticle random phase approximation (RQRPA) is established using density dependent point coupling interaction DD-PC1, supplemented with the isovector-pseudovector interaction channel in order to study unnatural parity transitions. The introduced framework has been validated using the M1 sum rule for core-plus-two-nucleon systems, and employed in studies of the spin, orbital, isoscalar and isovector M1 transition strengths, that relate to the electromagnetic probe, in magic nuclei $^{48}$Ca and $^{208}$Pb, and open shell nuclei $^{42}$Ca and $^{50}$Ti. In these systems, the isovector spin-flip M1 transition is dominant, mainly between one or two spin-orbit partner states. It is shown that pairing correlations have a significant impact on the centroid energy and major peak position of the M1 mode. The M1 excitations could provide an additional constraint to improve nuclear energy density functionals in the future studies.

Ultrafast Intraband Auger Process in Self-Doped Colloidal Quantum Dots

Investigating the separate dynamics of electrons and holes has been challenging although it is critical for fundamental understanding of semiconducting nanomaterials. N-type self-doped colloidal quantum dots (CQDs) with excess electrons occupying the low-lying state in the conduction band (CB) have attracted a great deal of attention because of not only their potential applications to infrared optoelectronics but also their intrinsic system offering a platform for investigating electron dynamics without elusive contributions from holes in the valence band. Here, we show an unprecedented ultrafast intraband Auger process, electron relaxation between spin-orbit coupling states, and exciton-to-ligand vibrational energy transfer process that all occur exclusively in the CB of the self-doped β-HgS CQDs. The electron dynamics obtained by femtosecond mid-IR spectroscopy will pave the way for further understanding of the blinking, disproportionately charging in LEDs, and hot electron dynamics in higher quantum states coupled to surface states of CQDs.

Charge transfer dynamics in Ar+ + CO

Differential cross sections for the charge transfer reaction between Ar+ and CO have been measured using three-dimensional velocity map imaging in a crossed beam setup at the two relative collision energies 0.55 and 0.74 eV. We find dominant forward scattering with CO+ product ions predominantly in the vibrational levels =6,7 of the electronic ground state X. This is indicative of a direct resonant mechanism for the two argon spin-orbit states. At both collision energies also an isotropic distribution with product ions exhibiting high internal excitation is observed. This is more pronounced at the higher collision energy, where the first electronically excited state A becomes accessible. We conclude that the A-state is partially populated by the product ions at 0.74 eV collision energy and suggest that the isotropic distribution stems from the formation of a charge-transfer complex, in concurrence with previously performed studies.

Velocity map imaging studies of the photodissociation of CS2 by two-photon excitation at around 303–315 nm

ABSTRACT Two-photon dissociation dynamics of carbon disulfide (CS2) have been studied by using the time-sliced velocity map ion imaging technique. Images of the S (1D2) and S (3P0) photoproducts formed in the CS2 photodissociation are acquired at four photolysis wavelengths from 303 nm to 315 nm. Vibrational states of the CS co-products are partially resolved and identified in the images. The CS (X1Σ+) products are highly vibrationally excited with moderate rotational excitation. The spin–orbit state-specific dissociation dynamics are also investigated by measuring the images of three S (3PJ) spin–orbit states (J=0, 1, and 2) at photolysis wavelength 303.878 nm. The branching ratios of CS (a3Φ)/CS (X1Σg +) are determined to be 0.05 ± 0.02, 0.17 ± 0.04, and 0.26 ± 0.05 for the three spin–orbit states S (3P0), S (3P1), and S (3P2) respectively, implying a strong spin–orbit coupling exists in the dissociation process. The averaged anisotropy parameters β 2>0 and β 4∼0 suggest that the CS2 molecules undergo a sequential transition 21 B 2(21Σ+)←11 B 2(1Δu)←X 1Σg + with the intermediate state 11 B 2 having a long lifetime, followed by nonadiabatic and spin–orbit couplings to other electronic states and then dissociate.

Controlling symmetry of spin-orbit entangled pseudospin state through uniaxial strain

In layer-structured $\mathrm{S}{\mathrm{r}}_{2}\mathrm{Ir}{\mathrm{O}}_{4}$, strong crystal electric field and spin-orbit coupling result in an intriguing spin-orbit entangled ${J}_{\mathrm{eff}}=1/2$ state, resembling the spin $S=1/2$ state of high-temperature superconducting cuprates. Our study unravels the intricate relationship between the lattice and the pseudospin interactions using uniaxial strain. Applied along the [1 1 0] direction, a compressive strain does not induce any effect. In contrast, the strain along [1 0 0] triggers a dramatic detwinning of the magnetic domains bringing the system to a single domain at around 0.04% strain. The strain driven detwinning rate is temperature independent showing that it does not exhibit a spontaneous orthorhombic lattice distortion driven by the pseudo-Jahn-Teller effect.

Spectroscopic and computational characterization of lanthanide-mediated N–H and C–H bond activation of methylamine

Ln (Ln = La and Ce) atom reactions with methylamine are carried out in a pulsed-laser vaporization supersonic molecular beam source. A series of dehydrogenation species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln-containing species in the formula Ln(NCH3) are characterized by mass-analyzed threshold ionization (MATI) spectroscopy and density functional theory and multiconfiguration spin-orbit coupling computations. The MATI spectrum of La(NCH3) consists of two vibronic band systems that are assigned to the ionization of the 2A1 ground state of the C3v isomer La(N-CH3) and the 2A' ground state of the Cs isomer La(NH-CH2). The MATI spectrum of Ce(NCH3) also displays two band systems, which are attributed to the ionization of the low-energy spin-orbit coupling states of the C3v isomer Ce(N-CH3). Ln(N-CH3) is formed by the concerted dehydrogenation of the amino group, while La(NH-CH2) is formed by the dehydrogenation of both amino and methyl groups. Ce(NH-CH2) is presumably formed in the reaction based on the computational predictions but not observed by the spectroscopic measurements.

Field-enabled quantum interference in atomic Auger decay

We demonstrate that an external terahertz (THz) field enables the formation of interference between two distinct Auger pathways leading to the same final ionic state. The kinetic energy of Auger electrons ejected from either of two spin-orbit split one-hole states of magnesium cations is recorded. In the presence of the THz field, a clear oscillatory structure in the Auger spectrum emerges, which we find to be in very good agreement with an analytical model based on perturbation theory. For this interference to occur, the THz field has to chirp the energy of both Auger electrons and photoelectrons simultaneously, in order to create states with indistinguishable quantum properties.

Direct observation of a Feshbach resonance by coincidence detection of ions and electrons in Penning ionization collisions

Observation of molecular dynamics with quantum state resolution is one of the major challenges in chemical physics. Complete characterization of collision dynamics leads to the microscopic understanding and unraveling of different quantum phenomena such as scattering resonances. Here we present an experimental approach for observing molecular dynamics involving neutral particles and ions that is capable of providing state-to-state mapping of the dynamics. We use Penning ionization reaction between argon and metastable helium to generate argon ion and ground state helium atom pairs at separation of several angstroms. The energy of an ejected electron carries the information about the initial electronic state of an ion. The coincidence detection of ionic products provides a state resolved description of the post-ionization ion-neutral dynamics. We demonstrate that correlation between the electron and ion energy spectra enables us to directly observe the spin-orbit excited Feshbach resonance state of HeAr+. We measure the lifetime of the quasi-bound HeAr+A2 state and discuss possible applications of our method.