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.

Here, we report the photoconducting response of field-effect transistors based on three atomic layers of chemical vapor transport grown WSe2 crystals mechanically exfoliated onto SiO2. We find that trilayered WSe2 field-effect transistors, built with the simplest possible architecture, can display high hole mobilities ranging from 350 cm(2)/(V s) at room temperature (saturating at a value of ∼500 cm(2)/(V s) below 50 K) displaying a strong photocurrent response, which leads to exceptionally high photoresponsivities up to 7 A/W under white light illumination of the entire channel for power densities p < 10(2) W/m(2). Under a fixed wavelength of λ = 532 nm and a laser spot size smaller than the conducting channel area, we extract photoresponsitivities approaching 100 mA/W with concomitantly high external quantum efficiencies up to ∼40% at room temperature. These values surpass values recently reported from more complex architectures, such as graphene and transition metal dichalcogenides based heterostructures. Also, trilayered WSe2 phototransistors display photoresponse times on the order of 10 μs. Our results indicate that the addition of a few atomic layers considerably decreases the photoresponse times, probably by minimizing the interaction with the substrates, while maintaining a very high photoresponsivity.

The electronic properties of as-prepared and purified unoriented single-walled carbon nanotube ͑SWCNT͒ films were studied by transmission measurements over a broad frequency range ͑far-infrared up to visible͒ as a function of temperature ͑15-295 K͒ and external pressure ͑up to 8 GPa͒. Both the as-prepared and the purified SWCNT films exhibit nearly temperature-independent properties. With increasing pressure the lowenergy absorbance decreases suggesting an increasing carrier localization due to pressure-induced deformations. The energy of the optical transitions in the SWCNTs decreases with increasing pressure, which can be attributed to pressure-induced hybridization and symmetry-breaking effects. We find an anomaly in the pressure-induced shift of the optical transitions at ϳ2 GPa due to a structural phase transition.

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 4 I 15/2 ground state/manifold; hereafter, manifold) at 0 T at 104, ∼180, and 245 cm–1, corresponding to transitions from the ground state, M J = ±15/2, to the first three excited states, M J = ±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.