DFT calculation of 229thorium-doped magnesium fluoride for nuclear laser spectroscopy.

The 229thorium nucleus has an extremely low-energy isomeric state that could be manipulated with light in the vacuum ultraviolet (VUV) range. Recent measurements based on internal conversion electrons place the isomer energy at 8.28(17) eV (Seiferle B et al 2019), within the transmission window of large-band-gap materials, such as fluoride single crystals. Doping 229Th into VUV-transparent materials realizes a spectroscopy target with a high nuclei density and might form the basis of a solid-state nuclear clock. This paper presents a theoretical study of the optical properties of a thorium-doped MgF2 crystal. Using the Vienna Ab-initio Simulation Package, we perform density functional theory calculations of the electronic and optical properties of Th:MgF2. We determine whether thorium will be accepted as a dopant and identify the charge compensation mechanism and geometry. The simulations indicate, that the band gap of Th-doped MgF2 will be significantly reduced compared to undoped MgF2, below the expected 229Th isomer energy. This result is in striking contrast to a similar study performed for Th-doped CaF2 (Dessovic P et al 2014 J. Phys. Condens. Matter 26 105402).

Solid-state electron spin lifetime limited by phononic vacuum modes.

Longitudinal relaxation is the process by which an excited spin ensemble decays into its thermal equilibrium with the environment. In solid-state spin systems, relaxation into the phonon bath usually dominates over the coupling to the electromagnetic vacuum1-9. In the quantum limit, the spin lifetime is determined by phononic vacuum fluctuations 10 . However, this limit was not observed in previous studies due to thermal phonon contributions11-13 or phonon-bottleneck processes10, 14,15. Here we use a dispersive detection scheme16,17 based on cavity quantum electrodynamics18-21 to observe this quantum limit of spin relaxation of the negatively charged nitrogen vacancy (NV-) centre 22 in diamond. Diamond possesses high thermal conductivity even at low temperatures 23 , which eliminates phonon-bottleneck processes. We observe exceptionally long longitudinal relaxation times T1 of up to 8 h. To understand the fundamental mechanism of spin-phonon coupling in this system we develop a theoretical model and calculate the relaxation time ab initio. The calculations confirm that the low phononic density of states at the NV- transition frequency enables the spin polarization to survive over macroscopic timescales.

229Thorium-doped calcium fluoride for nuclear laser spectroscopy.

The (229)thorium isotope presents an extremely low-energy isomer state of the nucleus which is expected around 7.8 eV, in the vacuum ultraviolet (VUV) regime. This unique system may bridge between atomic and nuclear physics, enabling coherent manipulation and precision spectroscopy of nuclear quantum states using laser light. It has been proposed to implant (229)thorium into VUV transparent crystal matrices to facilitate laser spectroscopy and possibly realize a solid-state nuclear clock. In this work, we validate the feasibility of this approach by computer modelling of thorium doping into calcium fluoride single crystals. Using atomistic modelling and full electronic structure calculations, we find a persistent large band gap and no additional electronic levels emerging in the middle of the gap due to the presence of the dopant, which should allow direct optical interrogation of the nuclear transition.Based on the electronic structure, we estimate the thorium nuclear quantum levels within the solid-state environment. Precision laser spectroscopy of these levels will allow the study of a broad range of crystal field effects, transferring Mössbauer spectroscopy into the optical regime.

Electronic structure and the magneto-caloric effect.

We present a theoretical investigation of the entropy changes upon the application of an external field leading to the magneto-caloric effect (MCE). The case of localized magnetic moments is treated within the Weiss molecular field model, but special emphasis is given to cases of itinerant electron magnetism. These are described within the Landau theory of phase transitions and the temperature dependence is included via spin fluctuations. Since the parameters of the Landau expansion can be calculated from first-principles calculations of the electronic and magnetic structure, an immediate connection to the electronic band structure and its properties becomes possible. We study ordinary ferromagnets, including magneto-volume coupling and itinerant electron metamagnets, where in a small external field range large changes of the magnetic moments occur. We find that such metamagnetic systems are the most promising candidates for a large MCE in itinerant electron systems. We apply our expressions to several transition metals and their alloys, as well as to the metamagnets YCo2 and Fe2P, and find reasonable agreement with available experimental data.

Covalent magnetism and magnetic impurities.

We use the model of covalent magnetism and its application to magnetic insulators applied to the case of insulating carbon doped BaTiO3. Since the usual Stoner mechanism is not applicable we study the possibility of the formation of magnetic order based on a mechanism favoring singly occupied orbitals. On the basis of our model parameters we formulate a criterion similar to the Stoner criterion but also valid for insulators. We describe the model of covalent magnetism using a molecular orbital picture and determine the occupation numbers for spin-up and spin-down states. Our model allows a simulation of the results of our ab initio calculations for E(ℳ) which are found to be in very good agreement.

p-electron magnetism in CdS doped with main group elements.

On the basis of ab initio supercell calculations employing density functional theory (DFT) and post-DFT methods, we investigate the behavior of main group element impurities (B, C, N, Al, Si, P, Ga, Ge) in wurtzite (w) and zincblende (zb) CdS lattices. It is found that the impurities prefer the sulfur position and most of them, depending on the concentration, exhibit magnetic order. We find that for small concentrations (64zb and 72w supercells) a half-metallic behavior is found. For a 16-atom supercell for both the zb- and w-structure partly also unsaturated magnetic moments occur. The field dependence of the magnetic moments in these materials may lead to new technological applications of these magnetic semiconductors as tunable spin injection materials.

Covalent magnetism, exchange interactions and anisotropy of the high temperature layered antiferromagnet MnB2.

The investigation of the electronic structure and magnetism for the compound MnB(2) with crystal structure type AlB(2) has been revisited to resolve contradictions between various experimental and theoretical results present in the literature. We find that MnB(2) exhibits an interesting example of a Kübler's covalent magnetism (Williams et al 1981 J. Appl. Phys. 52 2069). The covalent magnetism also appears to be the source of some disagreement between the calculated values of the magnetic moments and those given by neutron diffraction experiments. We show that this shortcoming is due to the atomic sphere approximation applied in earlier calculations. The application of the disordered local moment approach and the calculation of the inter-atomic exchange interactions within the Liechtenstein formalism reveal strong local moment antiferromagnetism with a high Néel temperature predicted from Monte Carlo simulations. A fully relativistic band structure calculation and then the application of the torque method yields a strong in-plane anisotropy of the Mn magnetic moments. The agreement of these results with neutron diffraction studies rules out any possible weak itinerant electron magnetism scenarios as proposed earlier for MnB(2).

YCo2: intrinsic magnetic surface of a paramagnetic bulk material.

Here we report on results of a spin-resolved photoelectron spectroscopic (SRPES) study of YCo2 thin films (150 A-thick) grown on a W(110) substrate. The films were prepared by co-deposition of stoichiometric amounts of Y and Co onto a clean W surface followed by thermal annealing leading to (2x2) overstructure with respect to W(110) in the low-energy electron diffraction pattern indicated formation of a structurally ordered YCo2(111) surface. While no clear spin asymmetry was observed for bulk-sensitive SRPES data taken at hnu=1253.6 eV, the more surface-sensitive SRPES data obtained at hnu=21.2 eV photon energy revealed a clear spin-asymmetry probing the validity of the recent theoretical prediction.

Magnetism on the surface of the bulk paramagnetic intermetallic compound YCo2.

Using full-potential electronic structure calculations, we predict that the (111) surface of the cubic Laves phase Pauli paramagnet YCo2 is ferromagnetic. The magnetism of the (111) surface is independent of the termination of the surface, does not extend beyond two Co layers, and is related to the field-induced metamagnetism of the bulk. YCo2 appears to be a prominent candidate to demonstrate the phenomenon of surface-induced itinerant magnetism localized in two dimensions.

Large negative magnetic contribution to the thermal expansion in iron-platinum alloys: quantitative theory of the Invar effect.

We show that the large negative magnetic contribution to the thermal expansion in disordered Fe-Pt alloys can be understood within the disordered local moment (DLM) approach. On the basis of first principles calculations we quantitatively describe the spontaneous volume magnetostriction for various Pt concentrations. It is found that the Invar effect in these alloys is entirely related to the state of thermal magnetic disorder modeled by the DLM states. We also show that the experimentally observed anomaly in the temperature dependence of the magnetization is due to a spontaneous reduction of the local magnetic moments rather than to "hidden excitations."

Defect-induced magnetic structure in (Ga(1)-(x)Mn(x))As.

We show that magnetic structures involving partial disorder of local magnetic moments on the Mn atoms in (Ga(1)-(x)Mn(x))As lower the total energy, compared to the case of perfect ferromagnetic ordering, when As defects on the Ga sublattice are present. Such magnetic structures are found to be stable for a range of concentrations of As antisites, and this result accounts for the observed magnetic moments and critical temperatures in (Ga(1)-(x)Mn(x))As. We propose an explanation for the stabilization of the partially disordered magnetic structures and conclude that the magnetization and critical temperatures should increase substantially by reducing the number of As antisite defects.

Correlation induced paramagnetic ground state in FeAl.

Experimentally the intermetallic compound FeAl is known to be nonmagnetic, whereas conventional density functional theory calculations within the local density approximation always yield a ferromagnetic ground state with a magnetic moment at the Fe site of about 0.7 mu(B). We show that a correlation correction within the LDA+U scheme yields a nonmagnetic ground state for U>or=3.7 eV using two different implementations. The disappearance of the magnetic ground state occurs since Fe-t(2g) and Fe-e(g) manifolds are affected differently by a common U. For large values of U a magnetic solution reappears as expected for strong correlation.