This reverse type of structure makes its appearance in body-centered cubic crystal forms of Chromium and Iron which coexist with the regular positive hexagonal or face-centered cubic structures. Vanadium and Niobium, the first Division II elements of their respective groups, combine the positive and reverse orientations. Beyond Niobium the positive orientation does not appear in the common Division II forms of the elements, the structures to which the present discussion is limited, and all elements take the reverse orientation, except Europium and Ytterbium, which combine it with a unit-specific rotation; that is, no electric-rotational displacement at all, as in the inert gas elements.
On the basis of the considerations discussed in Chapter
1, the average effective specific rotation for such rotational combinations
has been taken as the geometric mean of the two components. Where the
orientations are the same, and the only difference is in the magnitude,
as in the 5-10 combination, and in the combinations of magnetic rotations
that we will encounter later, the equilibrium is reached in the normal
manner. If two different electric rotations are involved, the two-atom
pairs cannot attain spatial equilibrium individually, but they establish
a group equilibrium similar to that which is achieved where n atoms
of valence one each combine with one atom of valence n.
The Division II distances are shown in Table 3.
Because of the greater probability of the electropositive types of combinations, the characteristics of Division II carry over into the first elements of Division III, and these elements, Nickel, Palladium, and Lutetium, are included in the table. Some similar modifications of the normal division boundaries have already been noted in connection with other subjects.
The net total rotation of the material atom is a motion with positive displacement-that is, a speed less than unity-and as such it normally results in a change of position in space. Inside unit space, however, all motion is in time. The orientation of the atom for the purpose of the space-time equilibrium therefore exists in the three dimensions of time. As we saw in our examination of the inter-regional situation in Chapter12, Volume I, each of these dimensions contacts the space of the region outside unit distance individually. To the extent that the motion in a dimension of time acts along the line of this contact it is a motion in equivalent space. Otherwise it has no spatial effect beyond the unit boundary. Because of the independence of the three dimensions of motion in time the relative orientation of the electric rotation of any combination of atoms may be the same in all spatial dimensions, or there may be two or three different orientations.
In most of the elements that have been discussed thus far the orientation is the same in all spatial dimensions, and in the exceptions the alternate rotations are symmetrically distributed in the solid structure. The force system of an aggregate of such elements is isotropic. It follows that any aggregate of atoms of these elements has a structure in which the constituents are arranged in one of the Geometrical patterns possible for equal forces: an isometric crystal. All of the electropositive elements (Divisions I and II) crystallize in isometric forms, and, except for a few which apparently have quite complex structures, each of the crystal forms of these elements belongs to one or another of three types: the face-centered cube, the body-centered cube, or the hexagonal close-packed structure.
We now turn to the other major subdivision of the elements, the electronegative class, those whose normal electric displacement is negative. Here the force system is not necessarily isotropic, since the most probable arrangement in one or two dimensions may be the negative orientation, a direct combination of two ne-ative electric displacements, similar to the all-positive combinations. It is not possible to have negative orientation in all three dimensions, and wherever it does exist in one or two dimensions the rotational forces of the atoms are necessarily anisotropic. The controlling factor is the requirement that the net total rotational displacement of a material atom as a whole must be positive. Negative orientation in all three dimensions is obviously incompatible with this requirement, but if the negative displacement is restricted to one dimension the aggregate has fixed atomic positions in two dimensions, with a fixed average position in the third because of the positive displacement of the atom as a whole. This results in a crystal structure that is essentially equivalent to one with fixed positions in all dimensions. Such crystals are not usually isometric, as the inter-atomic distance in the odd dimension is generally different from that of the other two. Where the distances in all dimensions do happen to coincide, we will find on further investigation that the space symmetry is not an indication of force symmetry.
If the negative displacement is very small, as in the lower division IV elements, it is possible to have negative orientation in two dimensions if the positive displacement in the third dimension exceeds the sum of these two negative components, so that the net result is still positive. Here the relative positions of the atoms are fixed in one dimension only, but the average positions in the other two dimensions are constant by reason of the net positive displacement of the atoms. An aggregate of such atoms retains most of the external characteristics of a crystal, but when the internal structure is examined the atoms appear to be distributed at random, rather than in the orderly arrangement of the crystal. In reality there is just as much order as in the crystalline structure, but part of the order is in time rather than in space. This form of matter can be identified as the glassy, or vitreous, form, to distinguish it from the crystalline form.
The term state” is frequently used in this connection instead of form”, but the physical state of matter has an altogether different meaning based on other criteria, and it seems advisable'to confine the use of this term to the one application. Both glasses and crystals are in the solid state.
In beginning a consideration of the structures of the individual electronegative elements, we will start with Division III. The general situation in this division is similar to that in Division II, but the negativity of the normal electric displacement introduces a new factor into the determination of the orientation pattern, as the most probable orientation of an electronegative element may not be capable of existing in all three dimensions. As stated earlier, where two or more different orientations are possible in a given set of circumstances the relative probability is the deciding factor. Low displacements are more probable than high displacements. Simple orientations are more probable than combinations. Positive electric orientation is more probable than negative. In Division I all of these factors operate in the same direction. The positive orientation is simple, and it also has the lowest displacement value. All structures in this division are therefore formed on the basis of the positive orientation. In Division II the margin of probability is narrow. Here the positive displacement x is greater than the inverse displacement 8-x, and this operates against the greater inherent probability of a simple positive structure. As a result, both the positive and reverse types of structure are found in this division, together with a combination of the two.
In Division III the negative orientation has a status somewhat similar to that of the positive orientation in Division II. As a simple orientation, it has a relatively high probability. But it is limited to one dimension. The regular division III structures of Groups 3A and 3B are therefore anisotropic, with the reverse orientation in the other two dimensions. A combination of these two types of orientation is also possible, and in copper and silver, the first Division III elements of their respective groups, the crystals formed on the basis of this combination orientation have cubic symmetry. As in Division II, the elements of Division III in Groups 4A and 4B crystallize entirely on the basis of the reverse orientation. Table 4 lists what may be considered as the regular inter-atomic distances of the elements of Division III.
Although the probability of the negative orientation is greater in Division IV than in Division III, because of the smaller displacement values, this type of structure seldom appears in the crystals of the lower division. The reason is that where this orientation exists in the elements of the lower displacements, it exists in two dimensions, and this produces a glassy or vitreous aggregate rather than a crystal. The reverse orientation is not subject to any restrictive factor of this nature, but it is less probable at the lower displacements, and except in Group 4A, where it continues to predominate, this orientation appears less frequently as the displacement decreases. Where it does exist it is increasingly likely to combine with some other type of orientation. As a result of these limitations that are applicable to the inherently more probable types of orientation, many of the Division IV structures are formed on the basis of the secondary positive orientation, a combination of two 8-x displacements.
The secondary positive orientation is not possible in the electropositive divisions, as 8-x is negative in these divisions, and like the negative orientation itself, an 8-x negative combination would be confined to a subordinate role in one or two dimensions of an asymmetric structure. Such a crystal structure cannot compete with the high probability of the symmetrical electropositive crystals, and therefore does not exist. In the electronegative divisions, however, the 8-x displacement is positive, and there are no limitations on it, aside from those arising from the high displacement values.
The effective displacement of this secondary positive orientation is even greater than might be expected from the magnitude of the quantity 8-x, as the change of zero points for the two oppositely directed motions is also oppositely directed, and the new zero points are 16 displacement units apart. The resultant relative displacement is 16-2x, and the corresponding specific rotation is 18-2x. In Division IV the numerical values of the latter expression range from 10 to 16, and because of the low probability of such high rotations, the secondary positive orientation is limited to one or one and one-half dimensions in spite of its positive character. In Division III the 8-x displacements are lower, but in this case they are too low. A two-unit separation of the zero points (16 displacement units) cannot be maintained unless the effective displacement is at least 8 (one full three-dimensional unit). The secondary positive orientation is therefore confined to Division IV.
A special type of structure is possible only for those electronegative elements which have a rotational displacement of four units in the electric dimension. These elements are on the borderline between Divisions III and IV, where the secondary positive and reverse orientations are about equally probable. Under similar conditions other elements crystallize in hexagonal or tetragonal structures, utilizing the different orientations in the different dimensions. For these displacement 4 elements, however, the two orientations produce the same specific rotation: 10. The inter-atomic distance in these crystals is therefore the same in all dimensions, and the crystals are isometric, even though the rotational forces in the different dimensions are not of the same character. The molecular arrangement in this crystal pattern, the diamond structure, shows the true nature of the rotational forces. Outwardly this crystal cannot be distinguished from the isotropic cubic crystals, but the analogous body-centered cubic structure has an atom at each corner of the cube as well as one in the center, whereas the diamond structure leaves alternate corners open to accommodate the abnormal projection of forces in the secondary positive dimension.
In those of the lower elements of Division IV that are beyond the range of the inverse type of orientation, there is no available alternative for combination with the secondary positive orientation. The crystals of these elements therefore have no effective electric rotation in the remaining dimensions, and the relative specific rotation in these dimensions is unity, as in all dimensions of the inert gas elements. The most common distances in the aggregates of the Division IV elements are shown in Table 5.
Up to this point, no consideration has been given to the elements of atomic number below 10, as the rotational forces of these elements are subject to certain special influences which make it desirable to discuss them separately. One cause of deviation from the normal behavior is the small size of the rotational groups. In the larger groups the four divisions are distinct, and, except for some overlapping, each has its own characteristic force combinations, as we have seen in the preceding paragraphs. In an 8-element group, however, the second series of four elements, which would normally constitute Division III, is actually in the Division IV position. As a result, these four elements have, to a certain extent, the properties of both divisions. Similarly, the Division I elements of these groups may, in some cases, act as if they were members of Division III.
A second influence that affects the forces and the crystal structures of the lower group elements is the inactivity of the rotational forces in certain dimensions that was mentioned earlier. A specific rotation of two units produces no effect in the positive direction. The reason for this is revealed by equation 1-1. By applying this equation we find that the effective rotational force (ln t) for t = 2 is 0.693, which is less than the opposing space-time force 1.00. The net effective force of specific rotation 2 is therefore below the minimum value for action in the positive direction. In order to produce an active force the specific rotation must be high enough to make ln t greater than unity. This is accomplished at rotation 3.
The specific magnetic rotation of the 1B group, which includes only the two elements hydrogen and helium, and the 2A group of eight elements beginning with lithium, combines the values 3 and 2. Where the value 2 applies to the subordinate rotation (3-2), one dimension is inactive; where it applies to the principal rotation (2-3), two dimensions are inactive. This reduces the force exerted by each atom to 2/3 of the normal amount in the case of one inactive dimension, and to 1/3 for two inactive dimensions. The inter-atomic distance is proportional to the square root of the product of the two forces involved. Thus the reduction in distance is also 1/3 per inactive dimension.
Since the electric rotation is not a basic motion, but a reverse rotation of the magnetic rotational system, the limitations to which the basic rotation is subject are not applicable. The electric rotation merely modifies the magnetic rotation, and the low value of the force integral for specific rotation 2 makes itself apparent by an inter-atomic distance which is greater than that which would prevail if there were no electric displacement at all (unit specific rotation).
Theoretical values of the inter-atomic distances of the lower group elements are compared with measured values in Table 6
The figures in parentheses in column 4 of this table indicate the effective number of dimensions. Thus the notation 3(1) shown for hydrogen means that this element has a specific magnetic rotation of 3, effective in only one dimension.
Except where the crystals are isometric, there is still much uncertainty in the distance measurements on these lower group elements, and many other values have been reported in addition to those included in the table. This situation will be discussed at length in Chapter 3, where we will have the benefit of measurements of the distances between like atoms that are constituents of chemical compounds.
As indicated in the introductory paragraphs of this chapter, we are not yet in a position where we can determine specifically just what the inter-atomic distance will be for any given element under a given set of conditions. The theoretical considerations that have been discussed actually do lead to specific values in many cases, but in other instances there is an uncertainty as to which of two or more theoretically possible rotational arrangements corresponds to the observed crystal structure. Continuing progress is being made in both the experimental and the theoretical fields, and it can be expected that these uncertainties will gradually diminish toward the irreducible minimum that was mentioned earlier. In the course of this process there will necessarily be some changes in the identifications of the observed inter-atomic distances with the theoretically possible structures. A comparison of Tables 1 to 6 with the corresponding tabulations of the first edition should therefore be of interest as an indication of the nature and magnitude of the changes that have taken place in our view of this interatomic distance situation in the last twenty years, and by extension, an indication of the amount of change that can be expected in the future.
Such a comparison shows that the modifications of the original conclusions that now appear to be required, in the light of the additional information that has been made available, are confined almost entirely to those which have resulted from a better theoretical understanding of the behavior of the specific magnetic rotation above an effective value of 4. Few changes are required in either the magnetic or electric values in those rotational combinations where the specific magnetic rotation is 4-4 or less.
One of the puzzling features of the rotational situation as it appeared at the time of the original publication was the apparent retrograde progression of the specific magnetic rotation in Groups 4A and 4B. It was recognized at that time that both the 4˝ and 5 values of the specific rotation correspond to the same displacement, 4, the difference being that in the case of the 4˝ value the rotation extends to two units of vibration, and the last increment of specific rotation in this case is only half size. The next half unit increment, if such an increment were possible, would bring the 4˝ rotation back to the 5 value. It would therefore appear that the sequence of specific rotations beyond 4˝-4 should be 4˝-4˝, 5-4˝, 5-5, and so on. But the tendency is in the opposite direction. Instead of moving toward higher values as the atomic number increases, there is actually a decreasing trend. This was already evident at the time of publication of the first edition, as the low inter-atomic distances of the series of elements from Tungsten to Platinum could not be accounted for unless the specific magnetic rotation dropped back to 4-4˝ from the higher levels of the preceding elements of the 4A group. This decreasing trend has become even more prominent as distances have become available for additional elements of Group 4B, as some of these values indicate specific magnetic rotations of 4-4, or possibly even 4-3˝.
As it happens, the continuation of the trend toward lower values in the more recent data has had the effect of clarifying the situation. It is now evident that the 5-5 specific rotation is not reached within the accessible portion of Groups 4A and 4B. (Considerations that will be discussed later show that the specific rotation of 5-5 would be unstable.) The lower values in the 4A and 4B groups do not result from a decrease in the magnetic displacement, but from a shift of the existing displacement units from vibration one to vibration two, a process which reduces the specific rotation of the units by one half. On a vibration one basis, rotational displacements 4-3 correspond to specific rotations 5-4. Conversion of successive units of displacement to vibration two, without change in the number of displacement units, results in a series of specific rotations, 5-4, 4˝-4, 4-4˝, 4-4, and so on. A similar series with one additional displacement unit goes through the values 5-4˝, 4˝-5, 4˝-4˝, 4˝-4, and then follows the same route as the series with the lower displacement.
The modifications that have been made in the theoretical rotational values applicable to the elements of these two highest rotational groups since the publication of the first edition are the result of a review of the situation in the light of this new understanding of the trend of the specific rotation. The general pattern in group 4A is now seen to be that of the series from 5-4˝ to 4-4˝, with a return to 4˝-4˝ in the lower electronegative elements. So far as can be determined at this time, Group 4B follows the same pattern one step farther advanced; that is, it begins with 4˝-5 rather than 5-4˝.
The difference in the inter-atomic distance corresponding to one of the steps in this conversion process is relatively small, and in view of the substantial variation in the experimental values it has not appeared advisable to take into account the possibility of combinations such as 4˝-5 specific rotation of one atom of a pair and 4˝-4˝ in the other. It seems clear that such combinations do exist in some of the lower group elements, Sodium, for example, and they probably play some part in the higher groups. Most of the reported distances for Holmium and Erbium, for instance, agree more closely with a combination of 5-4˝ and 4˝-5 than with either individually. However, all of these values are theoretically possible, and the only question at issue in this and many other similar cases is which theoretical value corresponds to the observed distance. Definitive answers to identification questions of this kind will have to wait until the theoretical probabilities are specifically evaluated, or the experimental uncertainties are resolved.
Many questions concerning alternate crystal structures will also have to wait for more information from theory or experiment, particularly where crystal forms that exist only at high temperatures or pressures are involved. There is, however, a large body of information already available in this area, and it can be tied into the theoretical picture as soon as someone has the time and the inclination to undertake the task.