Spin-flip Excitations Research Articles

Spin-State Switching of Spin-Crossover Complexes on Cu(111) Evidenced by Spin-Flip Spectroscopy.

Spin-crossover compounds can be switched between two stable states with different magnetic moments, conformations, electronic, and optical properties, which opens appealing perspectives for technological applications including miniaturization down to the scale of single molecules. Although control of the spin states is crucial their direct identification is challenging in single-molecule experiments. Here we investigate the spin-crossover complex [Fe(HB(1,2,4-triazol-1-yl)3)2] on a Cu(111) surface with scanning tunneling microscopy and density functional theory calculations. Spin crossover of single molecules in dense islands is achieved via electron injection. Spin-flip excitations are resolved in scanning tunneling spectra in a magnetic field enabling the direct identification of the molecular spin state, and revealing the existence of magnetic anisotropy in the HS molecules.

Electron spin resonance impact on the longitudinal resistance in the quantum Hall regime

The electron spin resonance impact on the longitudinal resistance in the quantum Hall regime near the integer filling factors is considered. For the odd filling factors extra spin excitons are created in the process of the microwave absorption, and the resistance increase due to the effective temperature rise. For the even filling factors in the absorption process depending on the temperature inspired spin polarization leads to transition of the spin-flip excitations to the higher energy short-lived excitations, and as a result the resistance is decreased due to effective temperature decrease.

Tilted Spins in Chains of Molecular Switches on Pb(100).

A complex based on a Ni(II) porphyrin exhibiting spin crossover on Ag(111) is studied on Pb(100) by scanning tunneling microscopy at 0.3 K. Strong molecular interactions between the phenyl and pentafluorophenyl moieties lead to the formation of molecular chains and cause a faceting of the substrate surface. The chains are located along double and multiple substrate steps that deviate from high-symmetry directions. Tunneling spectroscopy reveals spin-flip excitations of an S = 1 system. Measurements in high magnetic fields are used to identify a tilt of the complex and its hard anisotropy axis with respect to the surface normal. Electron injection into the substrate near the molecular rows induces a transition to a state with larger inelastic cross section, leaving the spin state unchanged.

Chiral excitations and the intermediate-field regime in the Kitaev magnet α−RuCl3

In the Kitaev magnet α-RuCl3, the existence of a magnetic-field-induced quantum spin-liquid phase and of anyonic excitations is controversially discussed. We address this elusive, exotic phase via helicity-dependent Raman scattering and analyze the Raman optical activity of excitations as a function of magnetic field and temperature. The hotly debated field regime between 7.5 and 10.5T is characterized by clear spectroscopic signatures such as a plateau of the Raman optical activity of the dominant, chiral spin-flip excitation. This provides direct evidence for the existence of a distinct intermediate-field regime with an intriguing ground state featuring chiral excitations. Published by the American Physical Society 2024

Spin-flip excitation and negative energy dispersion in rotating Bose atoms

We investigated the excitation spectra for the rotating Bose system in the fractional quantum Hall effect regime considering short-ranged P o¨ schl-Teller and long-ranged Coulomb type interaction. We found the anomalous negative dispersion in the excited spectra for Jain’s second and third series, whereas conventional spin-wave positive dispersion is observed in the case of Jain’s first series. The higher order Jain series display negative curvature with roton minima at lower momenta and exhibit spin-wave excitation similar to conventional ferromagnets at higher momenta. This anomalous spin-flip excitonic state of particle-hole pairs arises due to the merging of two types of spin-reversed modes i.e. spin-wave with no change in Landau level (LL) index and spin-flip with decreasing LL index.

Magnetic Properties of Mn–Triphyrin on Au(111) with Submolecular Resolution

[Mn(I)(CO)3(triphyrin)] was investigated on Au(111) with a low-temperature scanning tunneling microscope. The complex is intact in the adsorbed state, but the CO ligands may be selectively removed. The diamagnetic molecule acquires a spin on Au(111) and exhibits spin-flip excitations. Disorder of the molecular layer leads to rigid shifts of the frontier orbitals. These shifts significantly influence the spin-scattering rates but hardly impact the spin excitation energy. Removal of CO ligands from the Mn center changes the low-energy excitation spectra. With two and one CO remaining, lower excitation energies and a Kondo resonance are observed.

Nonlocal correlation effects due to virtual spin-flip processes in itinerant electron ferromagnets

We present an ab initio method for electronic structure calculations, which accounts for the interaction of electrons and magnons in ferromagnets. While it is based on a many-body perturbation theory we approximate numerically complex quantities with quantities from time-dependent density functional theory. This results in a simple and affordable algorithm which allows us to consider more complex materials than those usually studied in this context ($3d$ ferromagnets) while still being able to account for the nonlocality of the self-energy. Furthermore, our approach allows for a relatively simple way to incorporate self-consistency. Our results are in a good agreement with experimental and theoretical findings for iron and nickel. Especially the experimental exchange splitting of nickel is predicted accurately within our theory. Additionally, we study the half-metallic ferromagnet NiMnSb concerning its nonquasiparticle states appearing in the band gap due to spin-flip excitations.

Noncollinear and Spin-Flip TDDFT in Multicollinear Approach

Time-dependent density functional theory (TDDFT) is one of the most important tools for investigating the excited states of electrons. The TDDFT calculation for spin-conserving excitation, where collinear functionals are sufficient, has obtained great success and has become routine. However, TDDFT for noncollinear and spin-flip excitations, where noncollinear functionals are needed, is less widespread and still a challenge nowadays. This challenge lies in the severe numerical instabilities that root in the second-order derivatives of commonly used noncollinear functionals. To be free from this problem radically, noncollinear functionals with numerical stable derivatives are desired, and our recently developed approach, called the multicollinear approach, provides an option. In this work, the multicollinear approach is implemented in noncollinear and spin-flip TDDFT, and prototypical tests are given.

The Electronic Structures and Energies of the Lowest Excited States of the Ns0, Ns+, Ns− and Ns-H Defects in Diamond

This paper reports the energies and charge and spin distributions of the mono-substituted N defects, N0s, N+s, N-s and Ns-H in diamonds from direct Δ-SCF calculations based on Gaussian orbitals within the B3LYP function. These predict that (i) Ns0, Ns+ and Ns- all absorb in the region of the strong optical absorption at 270 nm (4.59 eV) reported by Khan et al., with the individual contributions dependent on the experimental conditions; (ii) Ns-H, or some other impurity, is responsible for the weak optical peak at 360 nm (3.44 eV); and that Ns+ is the source of the 520 nm (2.38 eV) absorption. All excitations below the absorption edge of the diamond host are predicted to be excitonic, with substantial re-distributions of charge and spin. The present calculations support the suggestion by Jones et al. that Ns+ contributes to, and in the absence of Ns0 is responsible for, the 4.59 eV optical absorption in N-doped diamonds. The semi-conductivity of the N-doped diamond is predicted to rise from a spin-flip thermal excitation of a CN hybrid orbital of the donor band resulting from multiple in-elastic phonon scattering. Calculations of the self-trapped exciton in the vicinity of Ns0 indicate that it is essentially a local defect consisting of an N and four nn C atoms, and that beyond these the host lattice is essential a pristine diamond as predicted by Ferrari et al. from the calculated EPR hyperfine constants.

Spin-State Splittings in 3d Transition-Metal Complexes Revisited: Toward a Reliable Theory Benchmark

A new composite method for the calculation of spin-crossover energies in 3d transition-metal complexes based on multireference methods is presented. The method reduces to MRCISD+Q at the complete-basis-set (CBS) level for atomic ions, for which it gives excitation energies with a mean absolute error of only ca. 0.01 eV. For molecular complexes, the CASPT2+δMRCI composite approach corresponds to a CASPT2/CBS calculation augmented by a high-level MRCISD+Q-CASPT2 correction with a smaller ligand basis set. For a set of test complexes, the approach reproduces full MRCISD+Q/CBS results to within better than 0.04 eV, without depending on any arbitrary IPEA shifts. The high-quality CASPT2+δMRCI method has then been applied to a series of 3d transition-metal hexaqua complexes in aqueous solution, augmented by an elaborate 3D-RISM-SCF solvent treatment of the underlying structures. It provides unprecedented agreement with experiment for the lowest-lying vertical spin-flip excitation energies, except for the Fe3+ system. Closer examination of the latter case provides strong evidence that the observed lowest-energy excitation at 1.56 eV, which has been used frequently for evaluating quantum-chemical methods, does not arise from the iron(III) hexaqua complex in solution, but from its singly deprotonated counterpart, .

Low-Energy M1 States in Deformed Nuclei: Spin Scissors or Spin-Flip?

The low-energy $$M$$ 1 states in deformed $${}^{164}$$ Dy and spherical $${}^{58}$$ Ni are explored in the framework of fully self-consistent Quasiparticle Random-Phase Approximation (QRPA) with various Skyrme forces. The main attention is paid to orbital and spin $$M$$ 1 excitations. The obtained results are compared with the prediction of the low-energy spin-scissors $$M$$ 1 resonance suggested within Wigner Function Moments (WFM) approach. A possible relation of this resonance to low-energy spin-flip excitations is analyzed. In connection with recent WFM studies, we consider evolution of the low-energy spin-flip states in $${}^{164}$$ Dy with deformation (from the equilibrium value to the spherical limit). The effect of tensor forces is briefly discussed. It is shown that two groups of $$1^{+}$$ states observed at 2.4–4 MeV in $${}^{164}$$ Dy are rather explained by fragmentation of the orbital $$M$$ 1 strength than by the occurrence of the collective spin-scissors resonance. In general, our calculations do not confirm the existence of this resonance.

Controlling the Spin States of FeTBrPP on Au(111).

Spin-flip excitations of iron porphyrin molecules on Au(111) are investigated with a low-temperature scanning tunneling microscope. The molecules adopt two distinct adsorption configurations on the surface that exhibit different magnetic anisotropy energies. Density functional theory calculations show that the different structures and excitation energies reflect unlike occupations of the Fe 3d levels. We demonstrate that the magnetic anisotropy energy can be controlled by changing the adsorption site, the orientation, or the tip-molecule distance.

Flat-band ferromagnetism in a correlated topological insulator on a honeycomb lattice

We study the flat-band ferromagnetic phase of a spinfull and time-reversal symmetric Haldane-Hubbard model on a honeycomb lattice within a bosonization formalism for flat-band Z$_2$ topological insulators. Such a study extend our previous one [L. S. G. Leite and R. L. Doretto, Phys. Rev. B {\bf 104}, 155129 (2021)] concerning the flat-band ferromagnetic phase of a correlated Chern insulator described by a Haldane-Hubbard model. We consider the topological Hubbard model at $1/4$ filling of its corresponding noninteracting limit and in the nearly flat band limit of its lower free-electronic bands. We show that it is possible to define boson operators associated with two distinct spin-flip excitations, one that changes (mixed-lattice excitations) and a second one that preserves (same-lattice excitations) the index related with the two triangular sublattices. Within the bosonization scheme, the fermionic model is mapped into an effective interacting boson model, whose quadratic term is considered at the harmonic approximation in order to determine the spin-wave excitation spectrum. For both mixed and same-lattice excitations, we find that the spin-wave spectrum is gapped and has two branches, with an energy gap between the lower and the upper bands at the $K$ and $K'$ points of the first Brillouin zone. Such a behavior is distinct from the one of the corresponding correlated Chern insulator, whose spin-wave spectrum has a Goldstone mode at the center of the first Brillouin zone and Dirac points at $K$ and $K'$ points. We also find some evidences that the spin-wave bands for the same-lattice excitations might be topologically nontrivial even in the completely flat band limit.

Localized Active Space-State Interaction: a Multireference Method for Chemical Insight.

Multireference electronic structure methods, like the complete active space (CAS) self-consistent field model, have long been used to characterize chemically interesting processes. Important work has been done in recent years to develop modifications having a lower computational cost than CAS, but typically these methods offer no more chemical insight than that from the CAS solution being approximated. In this paper, we present the localized active space-state interaction (LASSI) method that can be used not only to lower the intrinsic cost of the multireference calculation but also to improve interpretability. The localized active space (LAS) approach utilizes the local nature of the electron-electron correlation to express a composite wave function as an antisymmetrized product of unentangled wave functions in local active subspaces. LASSI then uses these LAS states as a basis from which to express complete molecular wave functions. This not only makes the molecular wave function more compact but also permits flexibility in choosing those states to be included in the basis. Such selective inclusion of states translates to the selective inclusion of specific types of interactions, thereby allowing a quantitative analysis of these interactions. We demonstrate the use of LASSI to study charge migration and spin-flip excitations in multireference organic molecules. We also compute the J coupling parameter for a bimetallic compound using various LAS bases to construct the Hamiltonian to provide insights into the coupling mechanism.

Dynamic structure factor of the antiferromagnetic Kitaev model in large magnetic fields

We investigate the dynamic structure factor of the antiferromagnetic Kitaev honeycomb model in a magnetic field by applying perturbative continuous unitary transformations about the high-field limit. One- and two-quasiparticle properties of the dressed elementary spin-flip excitations of the high-field polarized phase are calculated which account for most of the spectral weight in the dynamic structure factor. We discuss the evolution of spectral features in these quasiparticle sectors in terms of one-quasiparticle dispersions, two-quasiparticle continua, the formation of antibound states, and quasiparticle decay. In particular, a comparably strong spectral feature above the upper edge of the upmost two-quasiparticle continuum represents three antibound states which form due to nearest-neighbor density-density interactions.

Experimental and theoretical characterization of x-ray induced excitons, magnons, and dd transitions in MoO3 nanosheets

The Mo $4d$ shell in the ground state of ${\mathrm{MoO}}_{3}$ is widely believed to be unoccupied. However, this assumption lacks clear experimental and theoretical corroboration. Using x-ray absorption and emission spectroscopy along with resonant inelastic x-ray scattering, we provide experimental evidence of two-dimensional ${\mathrm{MoO}}_{3}$ exhibiting enhanced many-body effects due to its reduced dimensionality. The observed phenomena include many-body effects such as $dd$ and spin-flip excitations, valence-hole and excited electron, and core-hole and excited electron bound excitonic states. Moreover, density functional theory and ligand field-based calculations were performed to investigate and interpret the experimental spectra. Considering that these many-body effects can only be observed by the interaction of x-ray photons with ${\mathrm{MoO}}_{3}$ if the $4d$ state is partially occupied, our experimental and theoretical approach clearly demonstrates a partial occupation of the Mo $4d$ state, refuting the assumption that the ground state is a $4{d}^{0}$ state. The Mo d occupancy is $4{d}^{3.36}$ and $4{d}^{3.53}$ determined with two different theoretical approaches (density functional theory and multiplet, respectively) and the computed spectra agree very well with our measurements further supporting this finding. Both the two- and three-dimensional samples exhibit strong core-hole effects that reduce the absorption onset at both the Mo ${M}_{2,3}$ and O $K$ edge. The band gap of the three-dimensional sample is experimentally found to be 3.1 \ifmmode\pm\else\textpm\fi{} 0.2 eV; however, for the two-dimensional material, strong many-body effects, even at the O $K$ edge, prevent an accurate determination of this value. The presence of these quasiparticles influences the band dispersions near the Fermi level, and thus has a key role in the performance of possible ${\mathrm{MoO}}_{3}$-based devices.

Excitonic wave-packet evolution in a two-orbital Hubbard model chain: A real-time real-space study

Motivated by experimental developments introducing the concept of spin-orbit separation, we study the real-space time evolution of an excitonic wave-packet using a two-orbital Hubbard model. The exciton is created by exciting an electron from a lower energy half-filled orbital to a higher energy empty orbital. We carry out the real-time dynamics of the resulting excitonic wave-packet, using the time-dependent density matrix renormalization group method. We find clear evidence of charge-spin and spin-orbit separation in real-space, by tracking the time evolution of local observables. We show that the velocity of the orbiton can be tuned by varying the inter-orbital interactions. We also present a comparative study of a hole (in one orbital) and exciton (in two orbitals) dynamics in one-dimensional systems. Moreover, we analyze the dynamics of an exciton with spin-flip excitation, where we observe fractionalized spinons induced by Hund's interaction.

Renormalization of spin excitations and Kondo effect in open-shell nanographenes

We study spin excitations and Kondo effect in open-shell nanographenes, motivated by recent scanning tunneling inelastic spectroscopy experiments. Specifically, we consider three systems, the triangulene, the extended triangulene with rocket shape, both with an $S=1$ ground state, and a triangulene dimer with $S=0$ on account of intermolecular exchange. We focus on the consequences of hybridization of the nanographene zero-modes with a conducting substrate on the $dI/dV$ lineshapes associated with spin excitations. The partially filled nanographene zero-modes coupled to the conduction electrons in the substrate constitute multi-orbital Anderson impurity models that we solve in the one-crossing approximation which treats the coupling to the substrate to infinite order. We find that the coupling to the substrate leads to (i) renormalization of the spin flip excitation energies of the bare molecule, (ii) broadening of the spectral features and (iii) the emergence of zero bias Kondo peaks for the $S=1$ ground states. The calculated substrate induced shift of the spin excitation energies is found to be significantly larger than their broadening, which implies that this effect has to be considered when comparing experimental results and theory.

Isovector spin susceptibility: Isotopic evolution of collectivity in spin response

Background: Response to spin-dependent operators has been investigated in the magnetic dipole and Gamow-Teller transitions, which provides magnetic properties of a nuclear system. Purpose: I investigate an isotopic dependence of the collectivity generated by the spin-dependent interactions in the Ca and Ni isotopes through the isovector (IV) spin-flip excitations. The responses in the neutral $(t_z)$ and charge-exchange $(t_{\pm})$ channels are considered in a unified way. Method: A nuclear energy-density functional approach is employed for calculating the response functions based on the Skyrme-Kohn-Sham-Bogoliubov method and the quasiparticle-random-phase approximation (QRPA). I adopt the like-particle QRPA and the proton-neutron QRPA for the neutral and charge-exchange channels, respectively. I consider the fluctuation of the proton-neutron pair fields. Results: The collective shift due to RPA correlations for the response in the neutral channel is explained by the occupation probability of neutrons in the $j_>=\ell+1/2$ orbital. Many particle-hole or two-quasiparticle excitations have a coherent contribution to form a giant resonance in neutron-rich nuclei for the charge-exchange channel. The IV spin susceptibility displays the isotopic evolution of the collectivity and the underlying shell structure. Conclusions: A repulsive character of the residual interaction in the spin-isospin channel diminishes the IV spin susceptibility due to the collectivity, while the dynamic ${}^{3}S$ pairing appearing in the charge-exchange channel opposes the reduction.

Superconducting Scanning Tunneling Microscope Tip to Reveal Sub-millielectronvolt Magnetic Energy Variations on Surfaces.

Combining the complex ordering ability of molecules with their local magnetic properties is a little-explored technique to tailor spin structures on surfaces. However, revealing the molecular geometry can be demanding. Nickelocene (Nc) molecules present a large spin-flip excitation leading to clear changes of conductance at the excitation-threshold bias. Using a superconducting tip, we have the energy resolution to detect small shifts of the Nc spin-flip excitation thresholds, permitting us to reveal the different individual environments of Nc molecules in an ordered layer. This knowledge allows us to reveal the adsorption configuration of a complex molecular structure formed by Nc molecules in different orientations and positions. As a consequence, we infer that Nc layers present a strong noncollinear magnetic-moment arrangement.