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5. F. A.

Kettle
The University Sheffield, S3 7HF, England

Crystal Field Potentials

Although it is now generally accepted that the ligand-field model of the electronic structure of trensition metal complexes is much more accurate than t,hnt provided by crystal field theory, the latter remains of paramount importance. There are two maiu reasons for this. I h t , if quantities which are well-defined in simple crystal field theory are allowed to becomc paramet,ers, theu the effects of covalency may he allowed for. The second reason for the continued interest in crystal field theory is that it may be used to predict &orbital splitting patterns which are useful in the interpretation of (1-l-d hands in electronic spectra. Examples of this are the spectra of complexes in which the coordination number of a transition metal ion is five or seven, a field in mhich there is much current interest. Despite the assumptions inherent in simple cryst,al field theory, it appears that it usually predicts correctly the relative energies of the &orbitals and, what is more, their relat,ive separations are also predicted fairly accurately. T h e calculation of a d-orhitial splitting pattern, within the crystal field approximation, falls into two parts (1). The first step is to obtain an expression for the electrostatic potential generated a t the metal ion by a suitable array of point charges (or dipoles) which represent the ligands. The second step is to use this potential field to determine the relative energies of the &orbitals. This second step has been discussed in THIS JOURNAL (I), and so in the present article we shall confine our discussion to a qualitative consideration of the form of the potential function. The problem we shall first consider is that of finding an expression for the crystal field potential around an atom mhich is a t the center of an octahedral arrangement of six identical ligands. Because me are interested in what happens around the metal atom it is convenient t o express the potential in terms of some function or functions which are centered on the metal atom. The most convenient functions are the spherical harmonics. Spherical harmonics are the functions that one usually draws when drawing a picture of a n orbital. As the reader may have discovered, there are several ways in which a p orbital, say, may be drawn. Two ways arc shown in I'igurc 1. Suppose that from the nuclcus of the adorn containing the p orbital we imagine that therc is a large numher of lines drawn radially outwards, so that the atom resembles a rolled-up hcdgchog or porcupine. Wc measure the amplitude of thc 71 orhitel along each of the lines and then mark off IL lcngt,h from ihc nuclcus proportional to this :~mplit.udc. l'hcsc marks would he found to define tho surr:~oosof t,wo sphcrcs i n contact, as shown in i A The ir, orbital shown in I'igure 1B is a

contour diagram in which points with the same 1 amplitudel are joined (only if it is the contour of zero amplitude should the two halves of the orbital touch). An important practical difference between Figures 1A and 1B is that the latter can only be drawn if a radial function is specified. The form of diagrams such as Figure 1A does not depend on the radial part of the orbital wavefunction. Of these two representations of p orbitals the former is equally valid as a picture of the spherical harmonic which is labelled To return to the crystal field potential. From the point of view of the metal ion the first, very crude, approximation to the six surrounding negative charges is to regard them as being uniformily smeared out over the surface of a sphere. That is, the first spherical harmonic in the expansion is that corresponding to a n s orbital (Yoo). This term is multiplied by a factor, k,, which, among other things, is proportional to the number of ligands ( e number of point charges). This is easily understood, for the charge density on our spherical shell will increase in direct proportion to the number of point charges. What of the spherical harmonics characteristic of p orbitals? As Figure 1A shows their presence would indicate that the potential along the +z axis differs from spherical symmetry (due to the Y o oterm that we already have) in the opposite way to the potential along the -z axis (and similarly +x and -x; +y and -y). But, by symmetry, for an octahedral complex the potential along the +z axis must equal that along -z (and that along x, -x, y, and -y). We conclude that there will be no p orbital spherical harmonic contribution to the potential. But exactly the same reasoning excludes all spherical harmonics corresponding to orbitals of u symmetry. This

-.

Y S -0 .

Figure 1.

Two representations of the somep orbital.

Volume 46, Number 6, June 1969

339

means that we may exclude j-, h-, j-, . . . , orbital spherical harmonics and confine our attention to those corresponding to d-, g-, i-, . . . , orbitals. Of the d orbitals we may at once exclude those spherical harmonics corresponding to the d,,, d,,, and dnE,, orbitals. There must be identical potentials a t corresponding points in the four quadrants of the xy plane, for example. The effect of a contribution from the d,, spherical harmonic, however, would be to increase the potential in two of these quadrants and decrease it in two others, and so this harmonic is excluded. The d,. and d+,. spherical harmonics may also be excluded. That corresponding to d,z would decrease the potential in the xy plane and increase it along the z axis (relative to the Yoo term). This, of itself, is not a valid reason for excluding it, for some other harmonic may be able to compensate for it and make the potentials at +x, -x, +y, and - y equal to Only the d,2-r. harmonic is availthat at +z and -2. able for this and, while able to compensate at +x and -x, only makes the discrepancy worse at +y and -y (Fig. 2). We conclude that none of the d-orbital harmonics will occur in the expansion. At this point is it worthwhile to stop and consider the form of the sort of spherical harmonic for which we are looking. It is one such that all corresponding points in the octahedron will experience the same potential. That is, all of those symmetry operations which turn an octahedron into itself will turn the spherical harmonic into itself. Evidently, no spherical harmonic corresponding to a degenerate set of orbitals will satisfy this condition for it is always the case that for such orbitals some symmetry operations will interconvert or mix them. What we need are orbitals of the same symmetry as a metal s orbital in an octahedral complex, that is, a l . . Suitable orbitals are to be found among g, i, k, and m orbitals (each of which provides one) and o orbitals (which provide two).

That is, we expect terms in Yp, Yo, Y8, YIO,Y12 (twice) and so on. Of these, only the first is of importance in the crystal field theory of d electrons and corresponds to the orbital g~.+~.+.. (Fig. 3). For f electrons the

Figure 3. (left) T h e " g d + .I+ .4"rpherical harmonic, Y4' 45/141~4'+ Y,-')I= 3/16& [ I 3 5 cor' 9 - 30 corn E 31 5 sin4 E cos' +]. There is only one negative lobe, consisting of eight interconnected pmtruberances, one in the center of each foce of the octahedron. Each protuberonce has of the lomplitudel of one of the lobes dong the coordinote ore%

+ +

'Ir6

Figure 4. (right) The " g , : E - 30 COO E 311.

spherical harmonic, Y<O

I=

a/r6&

(35 cod

second is also important and corresponds to the orbital i+++,.+,.. These orbitals correspond to linear combinations of spherical harmonics. So, g++,,+,, is a function of [YPo 45/14(y41 Y4c4)]and iz~+Y+zb is a function of [ Y ~ O - 47/z(y64 Y ~ - ~ ) ]~ . lthough they correspond to individual orbitals, it is instructive to consider these functions as made up of two "bits," the spherical harmonic term within round brackets 1/5/14(~<~ and that outside. Consider [Y4' Ya-3]. I n Figure 4 we show the YPo function. Its amplitude is positive along +z and -z and also along +x, -x, +y, and -y, although along this latter set it has only 0.375 of its amplitude along +a and -2. This defect may be remedied by adding some of the turns function (Y4( - Y4c4)to it (Fig. 5), and out to be the correct mixing coefficient. The arguY6c4). ment is slightly different for Y6" and (Ye4 The former has positive amplitnde along +z and -z but has a negative (and smaller) amplitude along the other axes. The combination (Ye4 Ye-') both offsets this negative amplitude and brings the potential along the x and y coordinate axes into equality with that along z. This explains why the (Ye4 Y6c4) term appears with a much larger mixing coefficient than does (Ya4 Ync4). We therefore conclude that the crystal field potential appropriate to an octahedral complex will be of the form

+ +

(0)
'/% 4 15 / 2 r

Figwe 2. A, The "d,? spherkol harmonic. YZ0 I= l/1457;;(3 cosPB 1 I, mgles being defined or g h o w n e insert. B, The " d A , ~ " spherical harmonic Ys2

+ Y2csI=

s i n 9 E cor 281.

I n the above discussion we have, for simplicity, talked

340 / Journal o f Chemical Education

by another set when moving to a lower-symmetry environment. We conclude that the crystal field potential function for a tetragonally elongated octahedral complex has the general form V' = k,'Y." - k,'Y," + k,'Y,' + k,'(Y,' + Y,c4)+ . . . where, for simplicity, we have only included terms that will cause splittings between d orbitals. This is also the general form of the potential for square planar complexes. I n general, terms will appear in the potential corresponding to all orbitals transforming as the totally symmetric representation of the corresponding point group. That is, orbitals which have symmetry a, al, a,', al. (as appropriate). These are usually listed in sets of character tables (for example in the convenient compilation by Cotton (4). Data for f orbitals (and hence the corresponding spherical harmonics) has recently been published (6). We note at this point that terms corresponding to p and f orbitals may only occur for complexes lacking a center of symmetry. No complete set of data is available for g orbitals, but a check to see whether any terms occur (other than those discussed above) is provided by the use of correlation tables (6) together with the information that the set of nine g orbitals transform as e, 11, tl, under the operations of the O h al, point group. In addition, some limited data is available on g orbitals in the literature (7).

of the ligands as being represented by point charges. Other models may be used (point dipoles, for example). The only difference would be to alter the numerical values of the 16's in the above expression. Since the Ic's are, in any case, best regarded as parameters, we shall not discuss t,hem further beyond noting that they are also functions of the metal-ligand separation. We now consider complexes of lower-than-octahedra1 symmetry. There are two ways by which we may proceed. Either we may appeal to a physical picture or use formal group theory. The former has conceptual advantages but the latter has a smaller probability of error. As in our discussion of octahedral complexes, we shall use the approaches successively. Consider a tetragonally elongated octahedral complex (Fig. 6). The potential is equal a t +x, -x, +y, and -y. Along the z axis the potential will be smaller than along x and y but that a t +z is still equal to that at -z. There are two ways in which we may adjust the expression given above for the octahedral case in order to adapt it to the present situation. The simplest is to recognize that if we add a spherical harmonic corresponding to -4% (Fig. 2 A ) we decrease the potential along +z and -z and increase it along +z, -x, +y, and -y. To compensate for this latter increase we must decrease the contribution of the Yoo term (that is, decrease k ~ ) . But we would expect to do this anyhow, for the tetragonal elongation would, in the limit, give us a square planar complex for which there would be four point charges instead of six, and we have already recognized that Ic, is proportional to the number of point charges. The second way of allowing for the elongation arises from our dissection of the [YdD -\/5/14(yp4 + Y4-"l term. If the mixing coefficientin this expression were greater than d2/i/14 the potential would be greater at +x, -x, +y, and -y than a t +z and -2. We conclude that the elongation will "unmix" the Ydo and (Y44 Y~F') terms. This separation is related to a feature which has been discussed in THIS JOURNAL in the context of Jorbitals (8,S) but which is a general feature of orbitals of high nodality. Namely, that a "cubic" set of orbital may have to be replaced

+ +

Literature Cited

(1) COMPINION, A. L., AND KOMABYNSKY, M. A., J. CHEM. E o u c , 41,257 (1964). (2) FRIEDMAN, H. G., CHOPPIN, G. It., AND FEUERBICHER, D.G. J. CHEM. EDUC., 41,354 (1964). EDUC., 41,358 (1964). (3) BECKICR, C., J. CHEM. (4) COTTON, F. A,, "Chemical Applications of Group Theory," Interscience, (division of John Wiley & Sons, Ino.) New York, 1963. ib) S. F. A,. AND SMITH, A. J.. J . Chem. Soc. (A), 688, , ~KETTLE. . (1967j. J. C., A N D CROSS, P. C., "Molecular (6) WILSON, E. B., DECIZTG, Vibrations," McGraw Hill, New Yorkfi955. Cambs. . Phil. SOC., 53, 343 (1957), and (7) ALTMANN, S. L.,P ~ O C references therein.

Figure

6. A tetragonolly extended octahedron.

Volume

46, Number 6,June 1969

341

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