Spin-polarized electronic structure calculation

Finally, in Sect. E the optical and magnetic properties are considered. It is found experimentally that some Zintl phases are colored and in ternary systems the color changes continuously as a function of the composition. This change can be correlated to a shift in a maximum of the imaginary part 2 of the dielectric constant e, and 2 can be interpreted by electronic interband transitions ) The magnetic susceptibility and Knight shift are discussed on the basis of spin polarized band structure calculations . Spin and orbital contributions are also considered. 

In the present work electronic properties and the nature of chemical bonding in intermetallic B 32-type Zintl phases are discussed on the basis of relativistic and non-relativistic as well as spin polarized band structure calculations. 

The question of alternative structure can be answered by electronic-structure theory, and it turns out that a quantitative answer is slightly more complicated because different magnetic properties are calculated for the [NaCl] and [ZnS] types. Nonetheless, non-spin-polarized band-structure calculations are quite sufficient to supply us with a correct qualitative picture. This has been derived using the TB-LMTO-ASA method and the LDA functional, and they give the correct lattice parameters with lowest energies for both structure types [267], just as for the case of CaO. 

In contrast to the discussion above with amorphous barriers, it is possible to use first-principles electron-structure calculations to describe TMR with crystalline tunnel barriers. In the Julliere model the TMR is dependent only on the polarization of the electrodes, and not on the properties of the barrier. In contrast, theoretical work by Butler and coworkers showed that the transmission probability for the tunneling electrons depends on the symmetry of the barrier, which has a dramatic influence on the calculated TMR values [20]. In the case of Fe(100)/Mg0(100)/Fe (100) the majority of electrons in the Fe are spin-up. They are derived from a band of delta-symmetry. In 2004 these theoretical predictions were experimentally confirmed by Parkin et al. and Yusha et al. [21, 22]. Remarkably, by 2005 TMR read heads were introduced into commercial hard disk drives. 

Also pure density-functional methods combined with plane-wave basis sets and ultrasoft pseudopotentials [58] were used in our studies of extended systems [59]. The computational efficiency of these methods enables larger systems and to some extent dynamical processes to be studied. Generalized-gradient approximation (GGA) or spin-polarized GGA DFT functionals [60, 61] were employed in the electronic structure calculations. 

It is important to recognize the solid-state counterpart of the above observations. Consider a one-dimensional (ID) chain with one electron and one orbital per site (Fig. 26.5a). If electron-electron repulsion is neglected, the levels of the bottom half of the band are each doubly filled, thereby leading to a metallic state (Fig. 26.5b). Non-spin-polarized electronic band structure calculations predict that a system with a half-filled... 

Electronic structures of crystalline solids are mostly calculated on the basis of DFT. In this approach an open-shell system is described by spin polarized electronic band structures, in which the up-spin and down-spin bands are allowed to have different orbital... 

Now let us consider the effect of crystal environment on the magnetic moment of the lanthanides. In Table 10, we show the results of calculations of the magnetic moment of neodymium on several common crystal lattices. A trivalent Nd ion yields a spin moment of 3/lb and an orbital moment of 6/ib- In the final two columns of Table 10, we see that the SIC-LSD theory yields values slightly less than, but very close to, these numbers. This is independent of the crystal structure. The valence electron polarization varies markedly between different crystal structures from 0.34/ib on the fee structure to 0.90/Zb on the simple cubic structure. It is not at all surprising that the valence electron moments can differ so strongly between different crystal structures. The importance of symmetry in electronic structure calculations cannot be overestimated. Eor example, the hep lattice does not have a centre of inversion symmetry and this allows states with different parity to hybridize, so direct f-d hybridization is allowed. However, symmetry considerations forbid f-d hybridization in the cubic structures. Such differences in the way the valence electrons interact with the f-states will undoubtedly lead to strong variations in the valence band moments. 

Li, J. Noodleman, L. Electronic Structure Calculations Density Functional Methods for Spin Polarization, Charge Transfer and Solvent Effects in Transition Metal Complexes. In Solomon, E. I. Hodgson, K. O., Ed., ACS Symposium Series 692 Spectroscopic Methods in Bioinorganic Chemistry, American Chemical Society Washington, DC 1998, pp 179-197. 

The quality of the KS orbitals depends to a large part on the ability of a chosen density functional to correctly represent the groimd state density of a given molecule. In most cases, different density functionals produce qualitatively identical orbitals, which also agree with WFT orbitals. For molecules that might posses a spin-polarized ground state density, different methods of electronic structure calculation not only produce quantitatively different results, but also lead to qualitatively contrastive conclusions. One such case is illustrated in O Fig. 4-7. We leave it to the reader to decide whether or not chemically meaningful information can be extracted from the orbital picture as displayed in O Fig. 4-7. 

Optimize the structure of acetyl radical using the 6-31G(d) basis set at the HF, MP2, B3LYP and QCISD levels of theory. We chose to perform an Opt Freq calculation at the Flartree-Fock level in order to produce initial force constants for the later optimizations (retrieved from the checkpoint file via OptsReadFC). Compare the predicted spin polarizations (listed as part of the population analysis output) for the carbon and oxygen atoms for the various methods to one another and to the experimental values of 0.7 for the C2 carbon atom and 0.2 for the oxygen atom. Note that for the MP2 and QCISD calculations you will need to include the keyword Density=Current in the job s route section, which specifies that the population analysis be performed using the electron density computed by the current theoretical method (the default is to use the Hartree-Fock density). 

Though in this paper we have used the relativistic KKR wave functions ets betsis functions, the present approach may be easUy realized within any existing method for calculating the electron states. This will allow the electronic properties of materials with complex magnetic structure to be readily calculated without loss of accuracy. The present technique, being most eflicient for the SDW-type systems, can be also used for helical magnetic structures. In the latter case, however, the spin-polarizing part of potential (18) should be appropriately re-defined. 

The conclusion is that the effects of spin polarization on the total energy are very small. Spin-polarized calculations are still useful and necessary, however, because they produce spin densities, which contain valuable information about the electronic structure of the impurity at different sites. They also allow the calculation of hyperfine parameters, which can be compared directly with experiment (see Section IV.2). 

The impurity interacts with the band structure of the host crystal, modifying it, and often introducing new levels. An analysis of the band structure provides information about the electronic states of the system. Charge densities, and spin densities in the case of spin-polarized calculations, provide additional insight into the electronic structure of the defect, bonding mechansims, the degree of localization, etc. Spin densities also provide a direct link with quantities measured in EPR or pSR, which probe the interaction between electronic wavefunctions and nuclear spins. First-principles spin-density-functional calculations have recently been shown to yield reliable values for isotropic and anisotropic hyperfine parameters for hydrogen or muonium in Si (Van de Walle, 1990) results will be discussed in Section IV.2. 

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