Crystal matrix elements

In cesium chloride the main contribution to V2 comes from cesium ion states acting as intermediaries in a form that can be obtained from perturbation theory. We need not be further concerned here with the origin of Fj. (We shall discuss the ionic crystal matrix elements in Chapter 14.) For a particular value of J in Eq. (2-2), there are only seven values of i that contribute to the sum / = j numbered as 0, and the six nearest-neighbor chlorine s states. The solution (valid for any j) is... 

Under the assumption that the matrix elements can be treated as constants, they can be factored out of the integral. This is a good approximation for most crystals. By comparison with equation Al.3.84. it is possible to define a fiinction similar to the density of states. In this case, since both valence and conduction band states are included, the fiinction is called the joint density of states ... 

Inter-atomic two-centre matrix elements (cp the hopping of electrons from one site to another. They can be described [7] as linear combmations of so-called Slater-Koster elements [9], The coefficients depend only on the orientation of the atoms / and m. in the crystal. For elementary metals described with s, p, and d basis fiinctions there are ten independent Slater-Koster elements. In the traditional fonnulation, the orientation is neglected and the two-centre elements depend only on the distance between the atoms [6]. (In several models [6,... 

Here ak a ) is the annihilation (creation) operator of an exciton with the momentum k and energy Ek, operator an(a ) annihilates (creates) an exciton at the n-th site, 6,(6lt,) is the annihilation (creation) operator of a phonon with the momentum q and energy u) q), x q) is the exciton-phonon coupling function, N is the total number of crystal molecules. The exciton energy is Ek = fo + tfcj where eo is the change of the energy of a crystal molecule with excitation, and tk is the Fourier transform of the energy transfer matrix elements. 

Note in passing that the common model in the theory of diffusion of impurities in 3D Debye crystals is the so-called deformational potential approximation with C a>)ccco,p co)ccco and J o ) oc co, which, for a strictly symmetric potential, displays weakly damped oscillations and does not have a well defined rate constant. If the system permits definition of the rate constant at T = 0, the latter is proportional to the square of the tunneling matrix element times the Franck-Condon factor, whereas accurate determination of the prefactor requires specifying the particular spectrum of the bath. 

Table X gives an idea of the strength of the various expansion methods, and it shows that, by using the principal term only, one can hardly expect to reach even the above-mentioned chemical margin, even if the wave function W gO(D) is actually very close in the helium case. This means that one has to rely on expansions in complete sets, and the construction of the modern electronic computers has fortunately greatly facilitated the numerical solution of secular equations of high order and the calculation of the matrix elements involved. For atoms, the development will probably go very fast, but, for small molecules one has first to program the conventional Hartree-Fock scheme in a fully self-consistent way for the computers, before the next step can be taken. For large molecules and crystals, the entire situation is much more complicated, and it will hence probably take a rather long time before one can hope to get a detailed understanding of the correlation phenomena in these systems.

Mixing of LS-states by spin orbit coupling will be stronger with an increasing number of f-electrons. As a consequence, intermediate values of Lande g factor and reduced crystal field matrix elements must be used. 

Due to the intermediate coupling the sign of the crystal field matrix element 6 is reversed compared to the pure Russell-Saunders state. Thus for 8-fold cubic coordination a F7 ground state was found. From EPR measurements on Pu3"1" diluted in fluorite host lattices, a magnetic moment at T=0 K can be calculated, ranging from li ff = 1.333 (in Ce02) to y ff = 0.942 (in SrCl2) (24,... 

A sinusoidal plot of grf>2 vs.

crystal plane gives another set of Ks that depend on other combinations of the gy, eventually enough data are obtained to determine the six independent values of gy (g is a symmetric matrix so that gy = gy,). The g-matrix is then diagonalized to obtain the principal values and the transformation matrix, elements of which are the direction cosines of the g-matrix principal axes relative to the crystal axes. An analogous treatment of the effective hyperfine coupling constants leads to the principal values of the A2-matrix and the orientation of its principal axes in the crystal coordinate system. 

One immediate question appears why the wide range of isomer shifts for stannous compounds The tin ions cannot be in the ideal Sn (5s ) state. What is happening All of these compounds have complicated crystal structures, with tin located at a site which does not have inversion symmetry there is an electric field acting at the site of the tin. This electric field produces matrix elements between the 5s and the 5p states of the tin and therefore a mixing of the two states. The ground state under these circumstances is not a pure 5s state, but a mixture of 5s and 5p. This is confirmed by studying the quadrupole splitting of... 

Scattering media to which this matrix applies include randomly oriented anisotropic spheres of substances such as calcite or crystalline quartz (uniaxial) or olivine (biaxial). Also included are isotropic cylinders and ellipsoids of substances such as glass and cubic crystals. An example of an exactly soluble system to which (13.21) applies is scattering by randomly oriented isotropic spheroids (Asano and Sato, 1980). Elements of (13.21) off the block diagonal vanish. Some degree of alignment is implied, therefore, if these matrix elements... 

The above equations have been obtained on the assumption that no orbital states have energies close to that of the ground state. This means that they should be applicable to d3, d5, and d8 for crystal fields which are close to octahedral in symmetry. They should be applicable to d4 and d9 also, when the distortion from octahedral symmetry is tetragonal, since in this case matrix elements of are zero between the ground state and the nearby excited state, d2, d6, and d1 in octahedral symmetry must be treated in a manner similar to that used for dl in Sec. III.D. For other crystal-field symmetries, the treatment used depends on whether the crystal field gives low-lying excited states that have nonzero matrix elements of with the ground state. 

Entirely general analytical expressions for the matrix elements of equation (4) have been listed for the d-orbital case for an almost arbitrary assembly of charges surrounding a metal atom.5,38 They are reproduced in Appendix 1. By implementing these expressions as a computer program the problem of calculating the d-orbital energies in the crystal field model for any ordinary stereochemistry is made trivial. 

When the matrix elements are calculated for states built from /-electron configurations it is always found that the constants A% (these quantities are related to the strength of crystal field) always occur with (the sharp brackets denote integration with respect to 4/ radial function). A parameters play an important role in crystal field calculations and can be used as parameters in describing the crystal field. For the lowest L S J state they can easily be determined by using the operator equivalent technique of Elliott and Stevens [545—547] and with the help of existing tables of matrix elements. Wybotjbne [548], however, feels that a better approach is to expand Vc in terms of the tensor operators,, as... 

Based upon the method of calculation adopted, a complete computer programme consisting of three main parts can easily be written for support of such calculations. The three parts are as follows (a) the CNDO part or EHMO part with Madelung correction for calculation of the localized electron orbitals in the anionic group (b) the transition matrix element calculation part and (c) the second-order susceptibility part for the calculation of the microscopic susceptibility of the anionic group followed by the calculation of the macroscopic SHG coefficients of the crystal. 

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