Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Spin-phonon couplings in transition metal complexes with slow magnetic relaxation.

ABSTRACT: Spin-phonon coupling plays an important role in single-molecule magnets and molecular qubits. However, there have been few detailed studies of its nature. Here, we show for the first time distinct couplings of g phonons of Co^II(acac)₂(H₂O)₂ (acac = acetylacetonate) and its deuterated analogs with zero-field-split, excited magnetic/spin levels (Kramers doublet (KD)) of the S = 3/2 electronic ground state. The couplings are observed as avoided crossings in magnetic-field-dependent Raman spectra with coupling constants of 1-2 cm^-1. Far-IR spectra reveal the magnetic-dipole-allowed, inter-KD transition, shifting to higher energy with increasing field. Density functional theory calculations are used to rationalize energies and symmetries of the phonons. A vibronic coupling model, supported by electronic structure calculations, is proposed to rationalize the behavior of the coupled Raman peaks. This work spectroscopically reveals and quantitates the spin-phonon couplings in typical transition metal complexes and sheds light on the origin of the spin-phonon entanglement.

SUBMITTER: Moseley DH

PROVIDER: S-EPMC6030095 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium.

Project description:We report the spin dynamic properties of non-substituted ferrocenium complexes. Ferrocenium shows a field-induced single-molecule magnet behaviour in DMF solution while cobaltocene lacks slow spin relaxation neither in powder nor in solution. Multireference quantum mechanical calculations give a non-Aufbau orbital occupation for ferrocenium with small first excitation energy that agrees with the relatively large measured magnetic anisotropy for a transition metal S=1/2 system. The analysis of the spin relaxation shows an important participation of quantum tunnelling, Raman, direct and local-mode mechanisms which depend on temperature and the external field conditions. The calculation of spin-phonon coupling constants for the vibrational modes shows that the first vibrational mode, despite having a low spin-phonon constant, is the most efficient process for the spin relaxation at low temperatures. In such conditions, vibrational modes with higher spin-phonon coupling constants are not populated. Additionally, the vibrational energy of this first mode is in excellent agreement with the experimental fitted value obtained from the local-mode mechanism.

| S-EPMC9298439 | biostudies-literature

Slow magnetic relaxation in octahedral low-spin Ni(iii) complexes.

Project description:Herein we report the first examples of single-molecule magnet (SMM) behaviour in S = 1/2 Ni(iii) complexes. We find that low-spin 3d7 trans-[NiIII(cyclam)(X)2]Y complexes (cyclam = 1,4,8,11-tetraazacyclotetradecane; X and Y are singly charged anions) exhibit field-induced slow relaxation of magnetization for O-donor axial ligands (nitrate) but not for N-donor variants (isothiocyanate). Experimental and electronic structure computational investigations indicate that intrinsic spin polarisation of low-spin Ni(iii) is modulated significantly by local coordination geometry and supramolecular interactions. Solid state dilution of Ni(iii) with diamagnetic Co(iii) ions forms a related complex salt, [Ni x Co1-x (cyclam)(NO3)2](NO3)·2HNO3 (0.1 < x < 1), which preserves slow magnetic dynamics, thus supporting a molecular component to slow relaxation. An initial analysis of magnetic relaxation lifetime fits best to a combination of Raman and direct relaxation processes.

| S-EPMC6115677 | biostudies-literature

Slow magnetic relaxation in distorted tetrahedral Dy(III) aryloxide complexes.

Project description:Three distorted tetrahedral Dy(III) aryloxide complexes, [Na(THF)6][Dy(OArAd2tBu)2Cl2] (1) (OArAd2tBu = OC6H2Adamantyl2-2,6-tBu-4) and [Na(THF)6][Dy(OMes*)3X] (X = Cl, 2; BH4, 3), (OMes* = OC6H2tBu3-2,4,6) exhibit easy axis magnetic anisotropy and slow magnetic relaxation at zero field, with relaxation rates 1 < 2 < 3.

| S-EPMC8438701 | biostudies-literature

Metal-Organic Framework of Lanthanoid Dinuclear Clusters Undergoes Slow Magnetic Relaxation.

Project description:Lanthanoid metal-organic frameworks (Ln-MOFs) can adopt a variety of new structures due to the large coordination numbers of Ln metal ions, and Ln-MOFs are expected to show new luminescence and magnetic properties due to the localized f electrons. In particular, some Ln metal ions, such as Dy(III) and Tb(III) ions, work as isolated quantum magnets when they have magnetic anisotropy. In this work, using 4,4',4″-s-triazine-2,4,6-triyl-tribenzoic acid (H₃TATB) as a ligand, two new Ln-MOFs, [Dy(TATB)(DMF)₂] (1) and [Tb(TATB)(DMF)₂] (2), were obtained. The Ln-MOFs contain Ln dinuclear clusters as secondary building units, and 1 underwent slow magnetic relaxation similar to single-molecule magnets.

| S-EPMC5344597 | biostudies-literature

Multiple structural transitions driven by spin-phonon couplings in a perovskite oxide.

Project description:Spin-phonon interactions are central to many interesting phenomena, ranging from superconductivity to magnetoelectric effects. However, they are believed to have a negligible influence on the structural behavior of most materials. For example, magnetic perovskite oxides often undergo structural transitions accompanied by magnetic signatures whose minuteness suggests that the underlying spin-phonon couplings are largely irrelevant. We present an exception to this rule, showing that novel effects can occur as a consequence. Our first-principles calculations reveal that spin-phonon interactions are essential to reproduce the experimental observations on the phase diagram of magnetoelectric multiferroic BiCoO3. Moreover, we predict that, under compression, these couplings lead to an unprecedented temperature-driven double-reentrant sequence of ferroelectric transitions. We propose how to modify BiCoO3 via chemical doping to reproduce such marked effects under ambient conditions, thereby yielding useful multifunctionality.

| S-EPMC5493420 | biostudies-literature

Hyperfine-phonon spin relaxation in a single-electron GaAs quantum dot.

Project description:Understanding and control of the spin relaxation time T1 is among the key challenges for spin-based qubits. A larger T1 is generally favored, setting the fundamental upper limit to the qubit coherence and spin readout fidelity. In GaAs quantum dots at low temperatures and high in-plane magnetic fields B, the spin relaxation relies on phonon emission and spin-orbit coupling. The characteristic dependence T1 ? B-5 and pronounced B-field anisotropy were already confirmed experimentally. However, it has also been predicted 15 years ago that at low enough fields, the spin-orbit interaction is replaced by the coupling to the nuclear spins, where the relaxation becomes isotropic, and the scaling changes to T1 ? B-3. Here, we establish these predictions experimentally, by measuring T1 over an unprecedented range of magnetic fields-made possible by lower temperature-and report a maximum T1 = 57 ± 15 s at the lowest fields, setting a record electron spin lifetime in a nanostructure.

| S-EPMC6110844 | biostudies-literature

Spin-phonon relaxation from a universal ab initio density-matrix approach.

Project description:Designing new quantum materials with long-lived electron spin states urgently requires a general theoretical formalism and computational technique to reliably predict intrinsic spin relaxation times. We present a new, accurate and universal first-principles methodology based on Lindbladian dynamics of density matrices to calculate spin-phonon relaxation time of solids with arbitrary spin mixing and crystal symmetry. This method describes contributions of Elliott-Yafet and D'yakonov-Perel' mechanisms to spin relaxation for systems with and without inversion symmetry on an equal footing. We show that intrinsic spin and momentum relaxation times both decrease with increasing temperature; however, for the D'yakonov-Perel' mechanism, spin relaxation time varies inversely with extrinsic scattering time. We predict large anisotropy of spin lifetime in transition metal dichalcogenides. The excellent agreement with experiments for a broad range of materials underscores the predictive capability of our method for properties critical to quantum information science.

| S-EPMC7270186 | biostudies-literature

Inter-Kramers Transitions and Spin-Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet.

Project description:Spin-phonon coupling plays a critical role in magnetic relaxation in single-molecule magnets (SMMs) and molecular qubits. Yet, few studies of its nature have been conducted. Phonons here refer to both intermolecular and intramolecular vibrations. In the current work, we show spin-phonon couplings between IR-active phonons in a lanthanide molecular complex and Kramers doublets (from the crystal field). For the SMM Er[N(SiMe3)2]3 (1, Me = methyl), the couplings are observed in the far-IR magnetospectroscopy (FIRMS) of crystals with coupling constants ≈ 2-3 cm-1. In particular, one of the magnetic excitations couples to at least two phonon excitations. The FIRMS reveals at least three magnetic excitations (within the 4I15/2 ground state/manifold; hereafter, manifold) at 0 T at 104, ∼180, and 245 cm-1, corresponding to transitions from the ground state, MJ = ±15/2, to the first three excited states, MJ = ±13/2, ±11/2, and ±9/2, respectively. The transition between the ground and first excited Kramers doublet in 1 is also observed in inelastic neutron scattering (INS) spectroscopy, moving to a higher energy with an increasing magnetic field. INS also gives complete phonon spectra of 1. Periodic DFT computations provide the energies of all phonon excitations, which compare well with the spectra from INS, supporting the assignment of the inter-Kramers doublet (magnetic) transitions in the spectra. The current studies unveil and measure the spin-phonon couplings in a typical lanthanide complex and throw light on the origin of the spin-phonon entanglement.

| S-EPMC7935416 | biostudies-literature

Intra-molecular origin of the spin-phonon coupling in slow-relaxing molecular magnets.

Project description:We perform a systematic investigation of the spin-phonon coupling leading to spin relaxation in the prototypical mononuclear single molecule magnet [(tpaPh)Fe]-. In particular we analyze in detail the nature of the most relevant vibrational modes giving rise to the relaxation. Our fully ab initio calculations, where the phonon modes are evaluated at the level of density functional theory and the spin-phonon coupling by mapping post-Hartree-Fock electronic structures onto an effective spin Hamiltonian, reveal that acoustic phonons are not active in the spin-phonon relaxation process of dilute SMMs crystals. Furthermore, we find that intra-molecular vibrational modes produce anisotropy tensor modulations orders of magnitude higher than those associated to rotations. In light of these results we are able to suggest new designing rules for spin-long-living SMMs which go beyond the tailoring of static molecular features but fully take into account dynamical features of the vibrational thermal bath evidencing those internal molecular distortions more relevant to the spin dynamics.

| S-EPMC5625570 | biostudies-literature

Semiquinone radical-bridged M<sub>2</sub> (M = Fe, Co, Ni) complexes with strong magnetic exchange giving rise to slow magnetic relaxation.

Project description:The use of radical bridging ligands to facilitate strong magnetic exchange between paramagnetic metal centers represents a key step toward the realization of single-molecule magnets with high operating temperatures. Moreover, bridging ligands that allow the incorporation of high-anisotropy metal ions are particularly advantageous. Toward these ends, we report the synthesis and detailed characterization of the dinuclear hydroquinone-bridged complexes [(Me6tren)2MII 2(C6H4O2 2-)]2+ (Me6tren = tris(2-dimethylaminoethyl)amine; M = Fe, Co, Ni) and their one-electron-oxidized, semiquinone-bridged analogues [(Me6tren)2MII 2(C6H4O2 -˙)]3+. Single-crystal X-ray diffraction shows that the Me6tren ligand restrains the metal centers in a trigonal bipyramidal geometry, and coordination of the bridging hydro- or semiquinone ligand results in a parallel alignment of the three-fold axes. We quantify the p-benzosemiquinone-transition metal magnetic exchange coupling for the first time and find that the nickel(ii) complex exhibits a substantial J < -600 cm-1, resulting in a well-isolated S = 3/2 ground state even as high as 300 K. The iron and cobalt complexes feature metal-semiquinone exchange constants of J = -144(1) and -252(2) cm-1, respectively, which are substantially larger in magnitude than those reported for related bis(bidentate) semiquinoid complexes. Finally, the semiquinone-bridged cobalt and nickel complexes exhibit field-induced slow magnetic relaxation, with relaxation barriers of U eff = 22 and 46 cm-1, respectively. Remarkably, the Orbach relaxation observed for the Ni complex is in stark contrast to the fast processes that dominate relaxation in related mononuclear NiII complexes, thus demonstrating that strong magnetic coupling can engender slow magnetic relaxation.

| S-EPMC8163326 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data