Chemical Physics 14 (1976) 393-401 0 North-Holland Publishing Company

ON THE LIGAND-FIELD POTENTIALFOR f ELECTRONS IN THE ANGULAROVERLAPMODEL W.URLAND

Institut fir anorganische und analytische Chemie, Heinrich-Buff-Ring S, 63 Giessen, FRG

Received 5 December 1975 The angular overlap model is applied to f electrons. General relationships are evaluated to express the iigand-field potential in angular overlap parameters for arbitmry ligand-fields. Comparison with the electrostatic model is presented for a specitk example.

1.

Introduction

The interpretation of the spectra and magneticprop erties of some compounds of the trivalent lanthanide ions by applying the crystal-fieldpoint-chargemodel (electrostatic model) has been difficult because of their low co-ordination symmetry. For such systemsit is generally impossibleto derive from magnetic measurements unambiguousinformation about the crystal-field parameters [I 1. Easier to deal with because of the simple form of the crystal-fieldpotential are the compounds of high symmetry. So, if we consider f electrons, the mostextensive expansion of the crystal(hgand)-field potential V for the molecular symmetry C1 v = ROCOO Y;
+qc22y2 + R,(r,Y,4 2 + c*1 y; -I-c2& +c2_1 y ; + c2_2 q2>

contribution R c Y for sphericalsymmeO try has been omitted [l] $00 . To derive (1) we made use of the usual expansion of V:
where the

+ c43Y, t CLOYS t c41 Y; t c4,,Y;

tc&$ _-2Y~2+cq_3Y~3tcq-4y1;4) +cs4Y~+cs3Y~ +c61Yz

tc4_& +R&~Y~+c~~Y; +QY;

tc60Y~tc~_lY~ltc~_2Y~2

fc6_3~3+Cg_~Y~+Cg_5~5+Cs_6~6) (1) reduces for a cubic crystal-fieldin the point-charge model to:

radialfunction,ck4= expansion coefficient, Y{ = sphericalharmonic, k = quantum number I,4 = quantum number m; summation is over all possible functions which give non-vanishing matrix elements G,m I Vl3,m)). Apparently because of the above mentioned difticulties in the case of crystal-fieldswith low smetry magnetic properties only of lanthanide ions with high coordination symmetry have been studied so far [ 1,2] . For systems with low symmetry the application of the angular overlapmodel (AOM)of Schiffer and Jdrgensen [3] seems to be more adequate [4] The AOMand similarcovalent models have been applied to systemswith uncompleted d-shells14-71 as well as to systemswith uncompleted f-shells[S-14]. I3y employing the AOMwe derivein the following sections general relationshipswhich allowus to express the l&and-fieldpotential (1) in terms of angularoverlap parameters. As an example the ligand-fieldpotential of an octahedral complex is givenexplicitly. The expression for the potential in the AOMis compared with the one in the electrostatic model and the
tRk =

(2)

* In the first equation of ref. [l j

ChallgCd.

the signof Y? has to be

394

W.Urkmd/Ligand-field potential for f elechms

angularoverlapparameters are related to the crystalfield parameters.

2. ihe application of the AOMto f orbit& As the AOMhas been extensively reviewed 13-7, 121 only a short description of the model will be given here. The AOMmay be seen as a fmt-order perturbation approach to covalent bonding Beingbased on covalenkythe AOMis thus in contrast to the crystal-field model resting on electrostatic interaction. With the assumptionof weak covalency the perturbation energiesof the central orbitals are proportional to the squares of metal-ligandoverlap integrals.Like in crystal-field theory the AOMassumesthe effects of severailigandsbonded to the central metal to be additive what is equivalent to the assumptionof no ligandligand overlap.We can write the antibonding energy E* of a given f orbital as:
E* = k[&(A) F:"1*
k

Considerationof inequivalent A-bonding effects in two directions perpendicular to the metal-ligandaxis leads to the more general angular factors Dit, where Asnow represents u-, ns- and nobonding, see for example [5]. The D(I) form a matrix expressingthe rotation of a set of met$wavefunctions into the l&and axis frame (see fig. 1). The D(o matrix can be either constructured using euIerianangles(0, p, $) or direction cosinesas in (5). x yi 2

(9

=P_~(F~))~.

(4)

The direction cosinesgive the mutual orientation of the metal (x,y,z) and the l&and frame (xJJJ). In this paper the matrix for rotation of f orbitals Do is evaluated,using direction cosines.The real f-electron wavefunctions(7) are taken from ref. [15]. By replacingthe matrix (5) by the eulerian transformation (6) the FQ matrix for equivalent h-bonding may be constructed.

is a proportionality constant dependent on factors includingthe valence state ionization energiesof metal and ligand.h designatesthe bonding symmetry with respect to the metal-ligandaxis.S&Q.) is the maximal overlap integral for antibondinginteraction between metal and l&and functions of a given type u, x, etc., and given bond Iength.J+z),the angularoverlap integral, ls a property of the orientations of the overlapping orbitals and appliesto equivalent&bonding. The superscript labels the I quantum number of the metal functions. ek is the angularoverlapparameter for a particular bonding type.

;e

(6)

Thd matrix can be used generally for complexeswith axlally symmetric ligands.Here the mutual orientation of the metal and ligand frames is given completely by the eulerian rotations through 8, up and 0. The real f electron wavefunctions ]3,i\@are: 13,u) = la> =mr-31(2z2 13,ns)= Ins) = JijGr-3afiq4z2 ]3,ac)= Inc) = @zrr36<q422 )3,&S) = 18s)=@jGi3#4&(297), 13,Sc)= l&z)= JVG P33JEz(x2 13,@J= I& = *r-3&Ko(3xZy 13,+X) = I@= &-G-3:m(xS - y2), - y3), - 392). (7) -3X2 - 3y2)z, -x2 -JJ)y, -x2 - y2).X,

Fig.1.

The DQ matrix expressed in direction cosines is given in table 1. From table 1 wesee that u bonding involves

W.~Urhnd/Ligand-field potential

for f electrorls

39s

with I o>, with Ins), with Id, with I&), [lG7& [afi72(37; [M$(Y: - $11 S&,(o) with l&c),

To derive (9) the relationship

kq = (-l)qc;_g, (c* is complex conjugated to c) has been used. W!

Y~W&(O>with W, and
with I&*

- 37;Ns;&7)

Welike to express now the Rkck4 coefficients in angular overlap parameters. This can be achieved in three steps. (a) The Rkckq coefficients have to be expanded in one-electron matrix elements(3,m I Yl3,m). This may be done by applying the followingequation: (3,ml VI3,m) = k c QR kc&l)m~

The F(O matrix is givenin table 2. An equivalentmatrix is given in ref. [16]. The generalmatrix element of covalent interaction withligands between real f orbitab is [5] :
l&ads

(11)
which has been derived from (3) and (12) [17] :

where 13,u)and 13,~)are the realf orbitals 13,@and t is the runningindex for the bonding symmetry A$. I$ and $7 are the matrix elements of table 1. Eq. (8) contains (4) as a special case. From (8) we see that the covalent interaction between metal and l&andis separated into t = u, ns, nc, A$,6c, gs, and gc types. For each type the antibondmgmatrix elements are calculated by summingthe contributions from all ligands. Each contribation of a symmetry independent Iigand with the numberj is scaledwith the angularoverlap parameter eASfor the correspondingbonding type.

(3,mlYk4(3,m)=(-l)~(~

(12)
(b) The second step is to express the matrix elements in the complex I3,m l= Im ) basis in those in the real basis 13,u)= lu>. The bases are related as in (13):

3. The ligand-fieId potential The general expansion of the ligand-fieldpotential (3) for f electrons is:
B=ROcO,,Y;

-<II=

-L a (nsl - -Jfi (ncl,

<-II= -&,l+-&I, d y I-i=-;;:wt 3 IhA

-L 16s)+$ ISd, 12)= * 2I=-d -kSsl t &cl, d

_-iI@)_ 13)@ fi

t RZc2,,Y; + R2czl(Y; - y;) + Rzczz(Y; + 5) +R4q& +R&Y; - 5) + R4c42(Y; + Yi2)

t-21= -&&I+ -L&l, 4 4 -L Ilpc), l-3)= -2 Iid t+2 w, c-31= + Gpsl t~~cl. (13)

(31=

-&I fi

-+I,

+R4ca3(Yz -Y,-3)+R4c44(Y; +c4) t R6c60Y; + R6csl(Y; - Y;) +R6c62(Y; + q2) + R6cG30; - q31 +Q& + R6cas(Y; - ~s)fR6c66(Y; + yz;, + 5% (9)

With these relationshipsit is straightforward to deduce transformationslike (14): ~2}VIO~=-~~GslVlo~t~~SclVlo~. & fl (14)

396

W.UrlandfLignnd-field potentioi

forf electrons

Table 1

D(f)matrixin direction cosines

Lmd 10)
Metal
lo)

:7&--3)

-VT& M-1)
tazc57:-u+27*7B%
iI&-O+h383

&T24-&-1)
k~7$--lI~7*7m
4a*(5723-1147,73Q3 di%Qr7273+Q27173+Q37172)

J1sQhY3
J57zia383rz+o3738*+8373~2)

im,
I*8

Mmc4-1)
L/&I6Y&l)

~(Q3837l+Q373Pr+83Y3al) 01(8273+8372)+81@273+0372) +Yl(Q283+Q382)

16s)

@717273

~~,7273+&r7,73+837172)

16C)

$\/Isr3(7:-7;)

m(7:Bs-r:B3+2!3,7*73 -2827273)

&%:03-7:Q3+2Q,7O3 -&27273) idifQ2(7:-7:)++fi7,72Q~

3a38373t2Ql8l73thlrIP3 +28,7lQ3 ~(Q,p,72+p,r,s+cr~7~~2 -Q28272)

id&d37:-7;)

&i@217:-7$)+4fi7,72&

I@

w&1(7:-37:)

h/i58

1 (7:-7;,-4&,72192

dfiQ,&-7i)-t&ldQ2

di%Q,Lh7,-9827!-Q18272 -Q272Pd

From eq. (11) and transformations like (14) the coefficientsR c can be writtenin termsof one-electron k kq matrix elementsin the real basis.Weobtain the matrix of tabIe 3, (c) The final step is to relate the coefticientsRkckq to the angularoverlapparameterse, by meansof eq. (8). This cannot be done in general.Becauseof (8) the resultantrelationships are dependenton the particuiax Table 2 FCQ matrix in eulerian angles
Lignd
Mk?td

geomeuy, the nwnber of symmetry-independent ligands and the involvedbondingtypes and may be established by a computerprogramme. The case of octahedralsymmetry willbe treated in the next section.

IO)

Id)

Iid,

Iid,

W.Urklrtd/Ligand-fieId potential for f elecrrons

397

4. Application The relationships of sections 2 and 3 may be applied to a specific example. For convenience we choose for computation the l&and-field potential of an octahedron formed by six identical, axially symmetric ligands. The axis of quantization (z-axis) may lie along the threefold axis (see fig. 2).

The ligand-field potential VOhfor the octahedral ligand arrangement shown in fig. 2 is by symmetry arguments: VOh=ROcooY~ +R4c40Yt +R,cb3(Y,3 - q3) tRscsoY; t R&&Y; +R&(Y; + Ygd). - Yi3) (15)

16c)

Ilpb)

Ilpc)

Tablei. , The wcfficients expanded in one-electrok matrix elements

of the Rpkq

0
h

*
A 4 A

5Q 2L e
V
V

4 -8
V 2
t
8

P $c.
-

8 a
-

A 0
-

.J
Ji 0 Oi Ji
-

-0 .J -

-Gl

Gi -C
0

L -

3/f -

e d - -d --.Oi RI R -

R
Pi Vi *Ei $1 -

Ti __

VI If.

p Y

z -C -

i
z 3

> -

-li .

-t - .v - 2
-

ii

.A

-i, Ri

.. -

$ -

4 ,

ii1

*6 66

I
G=~fl,H=~

_i,

I 1 I I I I I I

1
. , 1.p

- _

W.Urland/Lt

pozenrkifor f electrons
CSclVW=

399

GislVl6s)=$(5ea + 5e, + e6 + 7e& + 25eJ,

Co-ordinates

af the figands

Gp~lVllpc1= ik(20e0 + 15en + *a GpslVlgs) = 1(5en + $ + 3eJ,

GcI@id = -@sl Vim)= h&e0

GpclVlu) = lfi(Jea = Gslv!7rc~

+ fen + es - ib$,

+ en - 4e6 + JeJ, = 4pwlu~ = C&%x~ = 0. (13

?
Fig. 2.

CScl~7rs)

From table 3 we obtain for the expansion coefficients: ROcOO = $&Wlo> + h.Wlnc~

The expressionsfor the diagonalone-electron matrix elements may be checked by a diagonalsum rule [3,12], saying that for each bonding type t and for each of the 2Z+lmetal orbitals the sum of the coefficients (Djo)2
of the angular overlap parameters er equals the number N of the Uganiis:
21+1
c 2lil @) = N,

+hlVlns) t GclV16c) + (6slVl6s) + (cpclPl$X) + (rpSlVl~S)), R,c,, = 3446Wla) + (nclVlnc)

t=1

(D$)2 = N.

(18)

+ (mlVjns> -7(6clv16c) - 7WVl6s) + 3GpClvl~C~ + 3Gpslyl@), R,c,, =&&-t/%tklVlnc) +i&GslVlnc) + ~Wlns) + (6/@)(~lvlu) - iW%Wlu)), R6cG0= 34%422(ul ?lu)- ;(~clVlnc) -$(nslVl?rss>+ ~Ciclv16c~ + &sslVl6s~ -i&ciVlW) - roGpslyllps~), R6ch3 = ~~(-&Sl~c~
+ #iGslVh> + @slVlns> - 44~1 Vllpd+ i@slVlu)),

For our example (18) becomes: 4 (F;9)2 = 6,

+ i&clVlns)

W?
Eqs. (15~(17) lead by substitution to the final expression for the ligand-fieldpotential: VOh = j$N12e0 + 24en + 24es + 24eV)Yi +Gt--2eo - se, + 9 e&- 2eV)Yi

t &Whd
7

Rscs6 = ~~(&Sl~c~ - :(&I~)).

- i&l iI&
(16)

+m(2eD

+ $e, - yes t BV)(Yz - Yi3) -&eV)Yi - kn + Be6 - G&Y, - G3)

+@(#e0-4en+Ses + 2$4W%9eo i & &ZS$%($ea

Application of (8) using the co-ordinatesof fe. 2 and the matrix elements of table 2 leads to the following expressionsfor the one-electron matrix elements WflU): (ffl?W = &Sea + 6en + 3Oc, + tip),

-4e, +le, -3eV)(Y, + Y$ (20)

bclVinc) = (nslVlns)=$(e, + 7en + 5e, + 5eP),

The above relationship for Vohin the AOMmay be compared with the one in the electrostatic model Cl81:

W.Urhd/&and-field

poten tip1 for

f electrons

+ (z&+41,5)r_y&Y~ + &/%$Y~ + (zi?r6&z7)~~~Y~ + yVZzqs(y66 where ~t&?~ + Jd2m(Y,3

C3)]
- Yi3, cm

+ -$,I,

are the usual constant expressionsand are defined for examplein ref. [18]*. Wesee that the appropriate ratios of the coefficients in (20) and (21) coincide:

Wegavea generalrecipe to compute the Iigand-field po; tential for arbitrary symmetry, any number of different ligandsand any bonding type. In the case of octahedral symmetry we gavedef&te expressionsForthe figandfield potential in the AOM.Wethen comparedwith the electrostaticmodei and related the angularoverlapparametersto the crystal-fieldparameters. Confmingourselvesto u bondingonly like in ref. [S], we reduce the number of ligand-field parametersfrom two b4 and p6 in ref. [ 181) to one, whichis eo. This can be done for all kindsof co-ordinationsymmetry, assuming identicalligandsand equal bond lengths. The
reduction of the number of ligand-field parameters is

From (20) and (21) we may expressthe crystaLfIeld parametersof ref. [18] in angularoverlapparameters. We obtain: po = ze2+$r = )(eo t 2eR+ 2es + 2eq), p4 = ze2(r4)/n5= -&(-2eo - $e, + Yes - 2eJ, pa =re2G6)1,7=j#e0 - 4eT + le, - &e,). (23)

due to the powerful feature of AOMto classifybonding interaction between ligandand metal. The other powerful feature whichmakes AOMsuperior to the electrostatic model is the fact that the angularoverlapparameter can be estimatedby approximateformulae [4,8]. We thus conclude that in future the applicationof AOMwill simplifythe interpretation of the magnetic properties and spectra of lanthanideions with low symmetry.

Also, we may reiate the angularoverlapparametersto the crystal-fieldparametersdF(r) of Elliott and Stevens Acknowledgement [19] usingthe appropriaterelationshipsgivenin ref. I thank ProfessorR. Hoppe for his support of this [181: work. For discussions I am grateful to Dr. M. Gerloch _4$~~,=6+., =$(e a t 2e If t2e 6 t2e ) from the University of Cambridge (England). Ip
Ai(r4) = -&p4 = &(-2eo - $en + ye, - 2e,), A;@) = h$ = &(teo - 4en + teg - fi$), = w(-2en = -+j&($e, - !e,, + lpeb - 2eg), - 4en + fe, - $eq),
- i%J.

References
(11 L.M. EngeIhardt and B.N. Figgis, J. Chem. Sot. A (1970)
415.

Ai(r4, = -&?!p4 A;(+, = &h,o, A6(+3 = 3~

6 6

= $j-#e ~ - 4,+%e6

[2] L.M. Engelhardt andB.N. F&is, J. Chem. Sot. A (1968)

1258.
13) C.E. Sch&Terand C.K. Jbrgensen, MoL Phys 9 (1965) 401. I41 M. Ge+xh and R.C. Slade. Ligand-field parameters (Cam-

(24)

Analogousexpressionslike (23) and (24) could be ob-tained for any kind df co-ordinationsymmetry using the generaIrelationshipsof sections2 and 3;

5. Conclusion
h this paper we have applied the AOMto f orbitals.
-Eq. (21) hai be& obtained from (5) in ref. [18] by gutting

bridge Univ. Press, 1973). CE. Sch%fer, Structure and Bonding 5 (1968) 68. C.E. Sctiffer, Proc. Roy. Sot. A297 (1967) 96. C.E. Sch&Ter,Pure and Applied Chem. 24 (1970) 361. CK. J&gensen, R. Pappalardo, and H.-H. Schmidtke, J. Chem. Phys. 39 (1963) 1422. [9] W.C. Perkins and C.A. Crosby, J. Chem. Phys 42 (1965) [5] [6] [7] [8]

. SO& = 4 and addingthe contribution @&)lZ&e for

sphes@alsymmetry.

407: [lo] J.D. Axe and C. Buns, Phys. Rev. 152 (1966) 331. [ 111 G. Bums, Phys Lett. 2SA (1967) 15. [ 121 C.K.J&men, godem Aspectsof LigandField Theory (Nor&-Ho&ml, Amsterdam,1971).

W.Urland/Ligand-field potential for f electrons [13] D. KuseandC.K. Jqkgensen, Chem.Phys Letters l(1967)

401

114. [ 141 H.-D.Ambqer, R.D. Fischer and B. Kanellakopulos,

Theor. Cbim. Acta 37 (1975) 105. [ISI S.E. Hamung and C.E. Schafer, Stiucture and Bonding 12 (1972) 201. [16] S.F.A. Kettle and A.J.P. Pioli, Inorg. Chim. Acta 1 (196?) 275.

[I?] M.Rotenberg, R. Bivins,N. Metropolis,J.K. Wooten Jr., The 3-j and sj Symbols (MIT Press, Cambridgs, Mass.,
1959). [lS] M. Gcrloch and D.J. Mackey, J. Chem. Sot. A (1970) 3030. [I91 RJ- Elliott and K.W.H.Stevens, Proc. Roy. Sec. 215 A (lY52)437,218 A(1953) 553,219 A (1953) 387.