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1.
Nano Lett ; 20(6): 4588-4593, 2020 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-32402200

RESUMO

When surface states (SSs) form in topological insulators (TIs), they inherit the properties of bulk bands, including the electron-hole (e-h) asymmetry but with much more profound impacts. Here via combining magneto-infrared spectroscopy with theoretical analysis, we show that e-h asymmetry significantly modifies the SS electronic structures when interplaying with the quantum confinement effect. Compared with the case without e-h asymmetry, the SSs now bear not only a band asymmetry, such as that in the bulk, but also a shift of the Dirac point relative to the bulk bands and a reduction of the hybridization gap of up to 70%. Our results signify the importance of e-h asymmetry in the band engineering of TIs in the thin-film limit.

2.
Inorg Chem ; 2020 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-32196322

RESUMO

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.

3.
Nat Commun ; 11(1): 1259, 2020 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-32144239

RESUMO

The experimental discovery of Weyl semimetals offers unprecedented opportunities to study Weyl physics in condensed matters. Unique electromagnetic response of Weyl semimetals such as chiral magnetic effect has been observed and presented by the axial θ E · B term in electromagnetic Lagrangian (E and B are the electric and magnetic field, respectively). But till now, the experimental progress in this direction in Weyl semimetals is restricted to the DC regime. Here we report experimental access to the dynamic regime in Weyl semimetal NbAs by combining the internal deformation potential of coupled phonons with applied static magnetic field. While the dynamic E · B field is realized, it produces an anomalous phonon activity with a characteristic angle-dependence. Our results provide an effective approach to achieve the dynamic regime beyond the widely-investigated DC limit which enables the coupling between the Weyl fermions and the electromagnetic wave for further study of novel light-matter interactions in Weyl semimetals.

4.
Inorg Chem ; 2020 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-32009403

RESUMO

We measured the infrared vibrational properties of two copper-containing coordination polymers, [Cu(pyz)2(2-HOpy)2](PF6)2 and [Cu(pyz)1.5(4-HOpy)2](ClO4)2, under different external stimuli in order to explore the microscopic aspects of spin-lattice coupling. While the temperature and pressure control hydrogen bonding, an applied field drives these materials from the antiferromagnetic → fully saturated state. Analysis of the pyrazine (pyz)-related vibrational modes across the magnetic quantum-phase transition provides a superb local probe of magnetoelastic coupling because the pyz ligand functions as the primary exchange pathway and is present in both systems. Strikingly, the PF6- compound employs several pyz-related distortions in support of the magnetically driven transition, whereas the ClO4- system requires only a single out-of-plane pyz bending mode. Bringing these findings together with magnetoinfrared spectra from other copper complexes reveals spin-lattice coupling across the magnetic quantum-phase transition as a function of the structural and magnetic dimensionality. Coupling is maximized in [Cu(pyz)1.5(4-HOpy)2](ClO4)2 because of its ladderlike character. Although spin-lattice interactions can also be explored under compression, differences in the local structure and dimensionality drive these materials to unique high-pressure phases. Symmetry analysis suggests that the high-pressure phase of the ClO4- compound may be ferroelectric.

5.
Inorg Chem ; 58(24): 16434-16444, 2019 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-31749359

RESUMO

Accurate determination of the spin Hamiltonian parameters in transition-metal complexes with large zero-field splitting (ZFS) is an actual challenge in studying magnetic and spectroscopic properties of high-spin transition metal complexes. Recent critical papers have convincingly shown that previous determinations of these parameters, based only on the magnetic data, have low accuracy and reliability. A combination of X-band electron paramagnetic resonance (EPR) spectroscopy and SQUID magnetometry seems to be a more convincing and accurate approach. However, even in this case, the accuracy of the determination of the spin Hamiltonian parameters is strongly limited. In this work, we propose a purely spectroscopic approach, in which three complementary EPR spectroscopic techniques are used to unambiguously with high accuracy determine the spin Hamiltonian parameters for transition-metal complexes with S = 3/2. The applicability of this approach is demonstrated by analyzing the new quasi-octahedral high-spin Co(II) complex [Co(hfac)2(bpy)] (I). Along with the conventional X-band EPR spectroscopy, we also use such advanced techniques as multi-high-frequency EPR spectroscopy (MHF-EPR) and frequency-domain Fourier-transform THz-EPR (FD-FT THz-EPR). We demonstrate that the experimental data derived from the X-band and MHF-EPR EPR spectra allow determination of the g tensor (gx = 2.388, gy = 2.417, gz = 2.221) and the ZFS rhombicity parameter E/D = 0.158. The axial ZFS parameter D = 37.1 cm-1 is measured for I with the aid of FD-FT THZ-EPR spectroscopy, which is able to detect the high-energy EPR transition between the two Kramers doublets. CASSCF/NEVPT2 quantum-chemical calculations of magnetic parameters and magnetic direct current (dc) measurements are performed as well as testing options, and the results obtained in these ways are in good agreement with those derived using the proposed spectroscopic approach.

6.
Inorg Chem ; 58(23): 15726-15740, 2019 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-31738531

RESUMO

Two mononuclear cobalt(II) compounds of formula [Co(dmphen)2(OOCPh)]ClO4·1/2H2O·1/2CH3OH (1) and [Co(dmbipy)2(OOCPh)]ClO4 (2) (dmphen = 2,9-dimethyl-1,10-phenanthroline, dmbipy = 6,6'-dimethyl-2,2'-bipyridine and HOOCPh = benzoic acid) are prepared and magnetostructurally investigated. Each cobalt(II) ion is six-coordinate with a distorted octahedral CoN4O2 environment. The complex cations are interlinked leading to supramolecular chains (1) and pairs (2) that grow along the crystallographic c-axis with racemic mixtures of (Δ,Λ)-Co units. FIRMS allowed us to directly measure the zero-field splitting between the two lowest Kramers doublets, which led to axial anisotropy values of 58.3 cm-1 ≤ D < 60.7 cm-1 (1) and 63.8 cm-1 ≤ D < 64.1 cm-1 (2). HFEPR spectra of polycrystalline samples of 1 and 2 at low temperatures confirm the positive sign of D and provide an estimate of the E/D quotient [0.147/0.187 (1) and 0.052 (2)]. Detailed ac and dc magnetic studies reveal that 1 and 2 are new examples of field-induced single-ion magnets (SIMs) with small transversal anisotropy. CASSCF/NEVPT2 calculations support these results. Two Orbach processes or one Orbach plus a direct relaxation mechanism provide similar agreements with the nonlinear experimental Arrhenius plots at Hdc = 500 and 2500 G for 1. Two independent relaxation processes occur in 2, but in contrast to 1, an observed linear dependence of ln(τ) vs 1/T substantiates Orbach processes against the most widely proposed Raman and direct mechanisms. The analysis of each relaxation process in 2 provided values for Ea and τ0 that are very close to those found for 1, validating the predominant role of the Orbach relaxations in both compounds and, probably, also in other cobalt(II) SIMs. A mechanism based on a spin-phonon coupling is proposed to account for the SIM behavior in 1 and 2 with any Raman or direct processes being discarded.

7.
Chemistry ; 25(69): 15846-15857, 2019 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-31529652

RESUMO

Large separations between ground and excited magnetic states in single-molecule magnets (SMMs) are desirable to reduce the likelihood of spin reversal in the molecules. Spin-phonon coupling is a process leading to magnetic relaxation. Both the reversal and coupling, making SMMs lose magnetic moments, are undesirable. However, direct determination of large magnetic states separations (>45 cm-1 ) is challenging, and few detailed investigations of the spin-phonon coupling have been conducted. The magnetic separation in [Co(12-crown-4)2 ](I3 )2 (12-crown-4) (1) is determined and its spin-phonon coupling is probed by inelastic neutron scattering (INS) and far-IR spectroscopy. INS, using oriented single crystals, shows a magnetic transition at 49.4(1.0) cm-1 . Far-IR reveals that the magnetic transition and nearby phonons are coupled, a rarely observed phenomenon, with spin-phonon coupling constants of 1.7-2.5 cm-1 . The current work spectroscopically determines the ground-excited magnetic states separation in an SMM and quantifies its spin-phonon coupling, shedding light on the process causing magnetic relaxation.

8.
Phys Chem Chem Phys ; 21(16): 8201-8204, 2019 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-30950488

RESUMO

Here we report a combined use of THz-EPR and NMR spectroscopy for obtaining a detailed electronic structure of a long-known high-spin complex, cobalt(ii) bis[tris(pyrazolyl)borate]. The lowest inter-Kramers transition was directly measured by THz-EPR spectroscopy, while the energies of higher Kramers doublets were estimated by a recently proposed NMR-based approach. Together, they produced magnetic parameters for a full model that explicitly includes spin-orbit coupling. This approach is applicable to all transition metal ions for which the spin-orbit coupling cannot be treated perturbatively.

9.
Chemphyschem ; 20(8): 1001-1005, 2019 04 16.
Artigo em Inglês | MEDLINE | ID: mdl-30897255

RESUMO

Herein, we report a new trigonal prismatic cobalt(II) complex that behaves as a single molecule magnet. The obtained zero-field splitting, which is also directly accessed by THz-EPR spectroscopy (-102.5 cm-1 ), results in a large magnetization reversal barrier U of 205 cm-1 . Its effective value, however, is much lower (101 cm-1 ), even though there is practically no contribution from quantum tunneling to magnetization relaxation.

10.
Inorg Chem ; 57(20): 12740-12755, 2018 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-30277381

RESUMO

Three pentacoordinate complexes of the type [Co( pypz)X2], where pypz is a tridentate ligand 2,6-bis(pyrazol-1-yl)pyridine and X = Cl- (1), NCS- (2), and NCO- (3), have been synthesized, and their structures have been determined by X-ray analysis. The DC magnetic data show a sizable magnetic anisotropy, which was confirmed by high-field high-frequency electron paramagnetic resonance (HF EPR) measurements. Well-resolved HF EPR spectra of high spin cobalt (II) were observed over the microwave frequency range 100-650 GHz. The experimental spectra of both complexes were simulated with axial g tensor components, a very large positive D value, and different E/ D ratios. To determine the exact D value for 2 (38.4 cm-1) and 3 (40.92 cm-1), the far-infrared magnetic spectroscopy method was used. Knowledge of the zero field splitting parameters and their signs is crucial in interpreting the single-molecule magnet or single chain magnet behavior. The AC susceptibility data confirm that these complexes exhibit a slow magnetic relaxation under small applied DC field with two (1 and 3) or three (2) relaxation modes.

11.
Nat Commun ; 9(1): 2572, 2018 07 03.
Artigo em Inglês | MEDLINE | ID: mdl-29968702

RESUMO

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 CoII(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.

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