Solids, lattice constants

Solid Lattice constant (nm) Cohesive energy (meV/atom) ... 

Our intention is to give a brief survey of advanced theoretical methods used to detennine the electronic and geometric stmcture of solids and surfaces. The electronic stmcture encompasses the energies and wavefunctions (and other properties derived from them) of the electronic states in solids, while the geometric stmcture refers to the equilibrium atomic positions. Quantities that can be derived from the electronic stmcture calculations include the electronic (electron energies, charge densities), vibrational (phonon spectra), stmctiiral (lattice constants, equilibrium stmctiires), mechanical (bulk moduli, elastic constants) and optical (absorption, transmission) properties of crystals. We will also report on teclmiques used to study solid surfaces, with particular examples drawn from chemisorption on transition metal surfaces. 

In the solid state, the Ceo molecules crystallize into a cubic structure with a lattice constant of 14.17A, a nearest neighbor Ceo-Ceo distance of 10.02A [41], and a mass density of 1.72 g/cm (corresponding to 1.44 Ceo... 

Below a temperature of Toi 260 K, the Ceo molecules completely lose two of their three degrees of rotational freedom, and the residual degree of freedom is a ratcheting rotational motion for each of the four molecules within the unit cell about a different (111) axis [43, 45, 46, 47]. The structure of solid Ceo below Tqi becomes simple cubic (space group Tji or PaS) with a lattice constant ao = 14.17A and four Ceo molecules per unit cell, as the four oriented molecules within the fee structure become inequivalent [see Fig. 2(a)] [43, 45]. Supporting evidence for the phase transition at Tqi 260 K is... 

Here Tq are coordinates in a reference volume Vq and r = potential energy of Ar crystals has been computed [288] as well as lattice constants, thermal expansion coefficients, and isotope effects in other Lennard-Jones solids. In Fig. 4 we show the kinetic and potential energy of an Ar crystal in the canonical ensemble versus temperature for different values of P we note that in the classical hmit (P = 1) the low temperature specific heat does not decrease to zero however, with increasing P values the quantum limit is approached. In Fig. 5 the isotope effect on the lattice constant (at / = 0) in a Lennard-Jones system with parameters suitable for Ne atoms is presented, and a comparison with experimental data is made. Please note that in a classical system no isotope effect can be observed, x "" and the deviations between simulations and experiments are mainly caused by non-optimized potential parameters. 

The effects due to the finite size of crystallites (in both lateral directions) and the resulting effects due to boundary fields have been studied by Patrykiejew [57], with help of Monte Carlo simulation. A solid surface has been modeled as a collection of finite, two-dimensional, homogeneous regions and each region has been assumed to be a square lattice of the size Lx L (measured in lattice constants). Patches of different size contribute to the total surface with different weights described by a certain size distribution function C L). Following the basic assumption of the patchwise model of surface heterogeneity [6], the patches have been assumed to be independent one of another. 

Fig. 5 shows data from a simulation of TIP4P water that is confined on both sides by a rhombohedral mercury crystal with (111) surface structure. Bosio et al. [135] deduce from their X-ray studies that a solid o-mercury lattice with a larger lattice constant in the z direction may be used as a good structural model for liquid mercury. Thus, the mercury phase was modeled as a rigid crystal in order to simplify the simulations. The surface of such a crystal shows rather low corrugation. 

It is not an easy task to develop computer codes which correctly treat the advancement of a folding interface as a boundary condition to a diffusion or flow field. In addition, the interface between a solid and a liquid, for example, is usually is not absolutely sharp on an atomic scale, but varies over a few lattice constants [32,33]. In these cases, it is sometimes convenient to treat the interface as having a finite non-zero thickness. An order parameter is then introduced, which for example varies from the value zero on one side of the interface to the value one on the other, representing a smooth transition from liquid to solid across the interface. This is called the phase-field... 

It is well established that GGA gives a better description of molecular systems, crystal surfaces and surface-molecule interactions. However, there are cases where the GGA results for solids are in much worse agreement with experiment than the LDA ones (e.g., 3-22 jj has been suggested that the effect of using GGA for solids is roughly equivalent to adding uniform tensile stress, and as a result lattice constants are frequently overestimated. 

Table 2 shows that in the case of ratile the GGA overestimation of lattice constants is less important in the present calculation than in Ref. 3. Most likely explanation is that the GGA functional is used here only for solid state calculations and not for the pseudopotential generation from the free atom. This procedure has been shown to give more accurate structural results than with the GGA applied both in the potential generation and solid state... 

The lattice enthalpy can be identified with the heat required to vaporize the solid at constant pressure. The greater the lattice enthalpy, the greater is the heat required. Heat equal to the lattice enthalpy is released when the solid forms from gaseous ions. In Section 2.4 we calculated the lattice energy and discussed how it depended on the attractions between the ions. The lattice enthalpy differs from the lattice energy by only a few kilojoules per mole and can be interpreted in a similar way. 

The Pyrex tube was suspended, with capillary down, in a small-holed rubber stopper which, in turn, was fastened to a goniometer head by a length of stout copper wire. The solid material within the capillary was photographed in a cold room (4°C.) using copper x-radiation, a camera with radius 5 cm., and oscillation range 30°. The effective camera radius was established by superimposing a powder spectrum of NaCl during an exposure of the sample the lattice constant for NaCl at 4°C. was taken to be 5.634 A. 

Alloys of lead and thallium have a structure based upon cubic closest packing from 0 to about 87-5 atomic percent thallium. The variation of the lattice constant with composition gives strong indication that ordered structures PbTl, and PbTl, exist. In the intermediate ranges, solid solutions of the types Pb(Pb,Tl)a and Pb(Pb,Tl)TlB exist. Interpretation of interatomic distances indicates that thallium atoms present in low concentration in lead assume the same valence as lead, about 2-14, and that the valence of thallium increases with increase in the mole fraction of thallium present, having the same value, about 2-50, in PbTls and PbTl, as in pure thallium. A theory of the structure of the alloys is presented which explains the observed phase diagram,... 

In connection with a discussion of alloys of aluminum and zinc (Pauling, 1949) it was pointed out that an element present in very small quantity in solid solution in another element would have a tendency to assume the valence of the second element. The upper straight line in Fig. 2 is drawn between the value of the lattice constant for pure lead and that calculated for thallium with valence 2-14, equal to that of lead in the state of the pure element. It is seen that it passes through the experimental values of aQ for the alloys with 4-9 and 11-2 atomic percent thallium, thus supporting the suggestion that in these dilute alloys thallium has assumed the same valence as its solvent, lead. 

Solid contacts are incommensurate in most cases, except for two crystals with the same lattice constant in perfect alignment. That is to say, a commensurate contact will become incommensurate if one of the objects is turned by a certain angle. This is illustrated in Fig. 30, where open and solid circles represent the top-layer atoms at the upper and lower solids, respectively. The left sector shows two surfaces in commensurate contact while the right one shows the same solids in contact but with the upper surface turned by 90 degrees. Since the lattice period on the two surfaces, when measured in the x direction, are 5 3 A and 5 A, respectively, which gives a ratio of irrational value, the contact becomes incommensurate. 

Numerous ternary systems are known for II-VI structures incorporating elements from other groups of the Periodic Table. One example is the Zn-Fe-S system Zn(II) and Fe(II) may substimte each other in chalcogenide structures as both are divalent and have similar radii. The cubic polymorphs of ZnS and FeS have almost identical lattice constant a = 5.3 A) and form solid solutions in the entire range of composition. The optical band gap of these alloys varies (rather anomalously) within the limits of the ZnS (3.6 eV) and FeS (0.95 eV) values. The properties of Zn Fei-xS are well suited for thin film heterojunction-based solar cells as well as for photoluminescent and electroluminescent devices. 

In general, we use only the lattice constants to define the solid structure (unless we are attempting to determine its S5nnmetry). We can then define a structure factor known as the translation vector. It is a element related to the unit cell and defines the basic unit of the structure. We will call it T. It is defined according to the following equation ... 

Fig. 38. Temperature dependence of the lattice constants a, b, c and the unit cell volume V of [Fe(2-pic)3]Cl2 CH3OH. The solid lines are calculated using the parameter values of Table 20. According to Ref. [39]...

Fig. 25. Limits of the miscibility gap in (O) homogeneous, ( ) two-phase Pd-Rh alloys calculated from lattice constants 151), solid line hydrogen solubilities at 760 Torr 152), dotted line 60).

The XRD analyses revealed presence of AEO and Nd203, SrC03 (about 62 wt%) in SrNd-SG sample, CaC03 and Ca(OH)2 (about 5 wt%) in CaNd-SG. Solid solutions of Nd in AEO and of AEE in Nd203 were observed in all samples. The calculation of lattice constants and unit cell volumes (UCV) showed modification of the oxide lattice by foreign cations. The formation of solid solutions obviously depended of the relative ionic radii of the elements equal to 0.0995 nm for Nd3+, 0.072 for Mg2+, 0.1 for Ca2+,... 

The muonium centers observed in the curpous halides (see Table II) are unusual in several respects compared with Mu in other semiconductors and insulators. Figure 12 shows the reduced hyperfine parameters for Mu in semiconductors and ionic insulators plotted as a function of the ionicity (Philips, 1970). The positive correlation is especially apparent for compounds composed of elements on the same row of the periodic table where the lattice constants and valence orbitals are similar (see solid points in Fig. 12). Note however that the Mu hyperfine parameters in cuprous halides lie well below the line and in fact are smaller than in any other semiconductor or insulator (Kiefl et al., 1986b). The reason for this unusual behaviour is still uncertain but may be related to other unusual properties of the cuprous halides. For example the upper valence band is believed... 

Figure 4.5 shows a conventional unit cell of an fee crystal. It consists of atoms at the eight edges of a cube and at the centers of the six sides. The length a of the side of the cube is the lattice constant-, for our present purpose we may assume that it is unity. The lattice of an infinite, perfect solid is obtained by repeating this cubic cell periodically in all three directions of space. 

It has been noted that the conductivity and activation energy can be correlated with the ionic radius of the dopant ions, with a minimum in activation energy occurring for those dopants whose radius most closely matches that of Ce4+. Kilner et al. [83] suggested that it would be more appropriate to evaluate the relative ion mismatch of dopant and host by comparing the cubic lattice parameter of the relevant rare-earth oxide. Kim [84] extended this approach by a systematic analysis of the effect of dopant ionic radius upon the relevant host lattice and gave the following empirical relation between the lattice constant of doped-ceria solid solutions and the ionic radius of the dopants. 

Figure 7 Projections of atoms from the bottom (solid circles) and top (open circles) surfaces into the plane of the walls. (A through C) The two walls have the same structure and lattice constant, but the top wall has been rotated by 0°, 11.6°, and 90°, respectively. (D) The walls are aligned, but the lattice constant of the top wall has been reduced by 12/13. The atoms can only achieve perfect registry in the commensurate case (A). Reprinted with permission from Ref. 14.

On the practical side, we note that nature provides a number of extended systems like solid metals [29, 30], metal clusters [31], and semiconductors [30, 32]. These systems have much in common with the uniform electron gas, and their ground-state properties (lattice constants [29, 30, 32], bulk moduli [29, 30, 32], cohesive energies [29], surface energies [30, 31], etc.) are typically described much better by functionals (including even LSD) which have the right uniform density limit than by those that do not. There is no sharp boundary between quantum chemistry and condensed matter physics. A good density functional should describe all the continuous gradations between localized and delocalized electron densities, and all the combinations of both (such as a molecule bound to a metal surface a situation important for catalysis). 

The atoms are stacked in three parallel planes (see Fig. 2) yielding a highly symmetric molecule which forms such a stable solid that the melting point is 148°C, i.e., almost 20° higher than that of orthorhombic cyclooctasulfur. Separation of from Sg is aided by the low solubility of the first S12 is about 150 times less soluble (93). The lattice constants are (57) ... 

The calculations above allowed the positions of atoms to change within a supercell while holding the size and shape of the supercell constant. But in the calculations we introduced in Chapter 2, we varied the size of the supercell to determine the lattice constant of several bulk solids. Hopefully you can see that the numerical optimization methods that allow us to optimize atomic positions can also be extended to optimize the size of a supercell. We will not delve into the details of these calculations—you should read the documentation of the DFT package you are using to find out how to use your package to do these types of calculations accurately. Instead, we will give an example. In Chapter 2 we attempted to find the lattice constant of Cu in the hep crystal structure by doing individual calculations for many different values of the lattice parameters a and c (you should look back at Fig. 2.4). A much easier way to tackle this task is to create an initial supercell of hep Cu with plausible values of a and c and to optimize the supercell volume and shape to minimize... 

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