A Simple Approach to the Jahn-Teller Effect

M. Bacci lstituto di Ricerca sulle Onde Eleitromagnetiche del C. N. R., Firenze, Italy
The importance of the Jahn-Teller effect (JTE) inthe interpretation of spectroscopic and structural properties of molecules and ions is now widely recognized (I). In spite of this, students, even in advanced courses, become little acquainted with the implications of such an effect, usually limiting themselves only to the enunciation of the theorem. The principal cause is due to a lack of proper exercises for a better understanding. Indeed, since the J T E has been evidenced both by an historical and a quantitative point of view in highly symmetric compounds (Oh or T d point groups), the straightest examples are drawn from these symmetries, although the mathematical treatment is generally complim tea ...
~

-- - -

In the present paper, in order to give a little more insight into the problems related to the JTE, we pruposexme simple calculations, which can be handled on a pocket calculator, concerning molecules with a fourfold symmetry axis. In this case the mathematical treatment is greatly simplified. vet it provides a situation quite analogous to that obtained inmore symmetric systems and allows a better visualization. On the other hand, to treat molecules with a C4 axis is not merely an academic exercise, because the JTE can be really effective there, as recent papers have shown (2-6). Theory and Background The theorem first described by Jahn and Teller in 1937 (7) affirms that, when an electronic degenerate level exists in a nonlinear molecule or ion, the nuclei displace themselves in order t o remove the electronic degeneracy. Let V be the electronic potential including electron-nuclei -interactions.If the electronic potential is expanded in a series of small displacements from the undistorted configuration:

Figure 1. Potential energy along a generic coordinate S ( r , ) . The solid line JTE. The COmSDondS to the harmonic aooroximation in the absence of me ~~.. presence of nonvan shing lonear terms t \lr I6 V / ~ ~ l ' , l l o\lr j ldashed I nel produces a disp acement of the m.n mum cooroinale (ooheo ine).
~~~ ~~ ~

Let us consider now amolecule of symmetry Dab (the same considerations are valid also for symmetries C4",04, DZd). In this symmetry the only degenerate electronic levels belong to the E, (or E,) representation and the symmetric square is given by:

[ERI2 = IEu12 = Als + Big + Bzg

it can be demonstrated that the symmetric nuclear configuration is stable onlv when all the matrix elements of the linear terms

(3)

In a square planar molecule (4 or 5 atoms) the Jahn-Teller active vibrations are the stretchingB1, and the bending BW The former distorts the square into a diamond, while the latter distorts it into a rectangle (8,9). Let us define the two different coupling constants as follows:

As a consequence, it follows from symmetry that vibrations are Jahn-Teller active if their irreducible representation r is contained in the svmmetric sauare . ll?;12 . . (7). . . Jahn and Teller showed that in all ihe nonlinear molecular point groups, where electronic degeneracy is allowed, there will exist a vibrational mode which ;emoves the degeneracy.
816

S(T'-). - ~-,,-

are zero, where 'Pi is an electronic wavefunction transforming as a component of the representation ri and S(r,) is a symmetry coordinate corresponding to the component y of the representation r. The J T E is present when, for some displacements S(r,) (Jahn-Teller active modes), the integral (2) does not vanish. In such case the nuclei displace themselves along the coordinates S ( r J so to reach a stable configuration (see Fig. 1). Since V is invariant under all the symmetry operations of the point group, aVlaS(r,) transforms in the same way as

The adiabatic potential energy surfaces (APES'S)can be easily evaluated by the secular eqn. (8):
E

I-

CISI

+V-6

c2Sz

ER(v) CZSZ

(5)

where we put for simplicity SI = S(B1) and SZ= S(B2) and V, the potential energy in the harmonic approximation, is given by: Here K I and KZare the force constants for the vibrations S, and Sz.

Journal of Chemical Education

From eqn. (5) the energies of the two APES's are ohtained:
r* = V + (c:S:

+ c;SP"

(7)

It can be demonstrated easily that only rhomhic distortions

are stable when

Teller distortions are gradually reduced by spin-orbit interaction until the system is not distorted for I A121 > cflKl(8); (b) the amplitude of the vibration becomes larger with increasing spin-orbit coupling; (c) the barrier between the equivalent minima is reduced by an increased spin-orbit coupling so that a dynamic situation is favored (by quantum mechanical tunneling or thermal activation over the harrier). Computation of the Band Shape for a Transition 2A 2E For the sake of simplicity, we will consider the coupling with the mode S1only and the same force constant K1 for both ground and excited levels. Within the semiclassical approximation the line shape of the optical absorption 2A 2E is given by (1, 11):

whereas rectangular distortions are stabilized in the opposite case:

In both cases the coordinates and the energies of the minima are given by:

where i = 1or 2, for rhombic and rectangular distortions, respectively. However, this dichotomy (no coexistence of rhombic and rectangular distortions) can he overcome if second-order terms are taken into account (9) so that the coexistence of minima of different symmetry may he allowed. Indeed as i t can be shown by symmetry arguments (1, 9), second-order nonvanishing terms in S,S1 and S,S2 are found in systems with a fourfold symmetry axis, it' the totally-symmetric n~ordinate S is considered. The APES'S still can be evaluated by the secular equation (5), adding the elastic term 1 ' 2 KmS: to V and substituting c, and cz with (c, c,lS,) and (cz + c,zS,), respectively, where c,i (i = 1,2) are the secondorder coupling constants.

were 0is the energy difference between the A and E states at SI = 0; hw, k , and T a r e the photon energy, the Boltzmann constant, and the absolute temperature, respectively. Recalling the properties of the Dirac &function (12) (see also Appendix), we obtain:

Examples The Role of the Spin-Orbit Coupling The spin-orbit coupling and the J T E are each other competitive. Indeed strong spin-orbit interactions tend to cancel the J T E and for sufficiently high spin-orbit constants A the minima coalesce a t Si = 0, that is a t the undistorted configuration. On the contrary, a large J T E quenches the spin-orbit splitting as well as other operator whose orbital part is offdiagonal in the representation in which the J T E is diagonal. This general quenching was first recognized by Ham (10) (Ham effect), and it has played a fundamental role in the interpretation of optical and epr spectra ( I ) . The simultaneous effects of the soin-orbit and the JahnTeller coupling are wel. and easily visualized considering a i in D svmmetrv. In such case we ohtain two level 'En (,,r -~ . 'E.. -. " similar secular equations instead of eqn. (5): clSl + V - c czSz f 1 ' %i X 0 (11) T I12 ih clSl + V - = Consequently, the energies of the two APES's are obtained modifying eqn. 7 as follows:
~~~ ~ ~ ~

Starting from eqn. 14 thecurves of Figure 3 can beohtained, where the Jahn-Teller energy was fixed still at 500 cm-', while the spin-orhit coupling wasvaried.' Figure 3 is particularly instructive, because i t shows that in the present case the JTE does not induce any splitting of the absorption band, although there is energy splitting at each moment. The splitting arises when the spin-orbit coupling is introduced, since the resulting two separated potential surfaces (see Fig. 2) lead to two intensity maxima. It could he interesting to compare the present result for A

2;:;

Note that each APES is twofold degenerate, because Kramer's degeneracy is not removed by the JTE. At this point, assuming for example the coupling with the vibrational modes B1 as prevalent, the cross-sections along S I , a t S2 = 0, can he drawn, as shown in Figure 2. The curves are computed fixing the Jahn-Teller energy (Em = 500 cm-I) and varying the spin-orbit coupling value. By an inspection of Figure 2 several observations can he made: (a) the Jahn1 When = , Ihw - c-1. .. . . XI2 . ~ " ,a. sinoularitv , is obtained. as it aooears .. looking at eqn. 14. Thls sd7gularftycan be removea ntroducing the h e resulting expression coupling woLh totally symmetric modes ( 1 n, but L is more difficult to handle and does not add new information
~~~ ~

o~

Figure 2,'Cross sections along the coordinate & computed at S2 = 0 with cj = lo4 cm-'/A and K, = lo5 cm-'/A2. (a) h = 0:(b) A = 400 cm-': (c)h = 800 cm-': (dl h = 2000 cm-'. Volume 59 Number 10 October 1982
817

and

1;-dz
6(r)
6(x

=1

(A2)

Moreover, if f(x) is a function continuous at x = xo, then

1+-f(*.) -rO)dx f(xd

=

(A3)

The integral in our eqn. (13) may be written in the f o m

11
'

f(r) WX)I

dx

(~4)

so we need another property in order to obtain eqn. (14). This relationship is

-1000

0
~ W -

10'00

~I~(x =) I

(cm-1) E ~

Figure 3. Computed abswption band shapes fw a transition 2A % in molecules with a fourfoldsymmetry axis, (a) = O:(b) A = 800 cm-': (c)A = 2000 cm-'. The omer parameter values are the same as in Figure 2. Arbitrary units in ordinate.

1 xa(z Ig'(xi)l
1

XJ

(A5)

whew ~ ' ( x , 8s ) rhc first derivative of gtx) rumpured ar x = I , and x , ore the r a m of [he equation gtx! = 11. Using relatiomhip (AS, and recalling rqn. (A3),the integrdl rA4! can be ;written
as:

= O (nosplittingj with thecase of the ahsorption band shape

for the transition A E in molwulrs with threefold svmmrtrv axis. T h e band shape is now given by (11):

h o k i n g at eqn. (13), it is easily seen that our functions g and f are given by

From an inspection of this relationship, it is easily seen that the corresponding band is constituted by two wings centered a t hw - 60 = 0. Such a different behavior depends upon the nature of the degenerate point Si = 0: there is splitting or not according as the point is a branch point or a crossing point, respectively ( I 1 ). Many other examples could he found which illustrate the J T E using the simpler expressions valid for molecules with a C4 axis. Here, I limit myself to signal the possibility of visualizing, by energy maps, the coexistence of different distortions without consuming too much computational time. T h e interested reader is referred to the example reported in Reference (9). Appendlx In order to obtain eqn. (14) from eqn. (13) it is useful to recall some properties of the Dirac &function (12). The Dirac 6-function is defined, in the one-dimensionalcase, as follows:

so that eqn. (14) can be obtained easily using relationship (A6).

Literature Cited

Reu., 14.357 (19f51. (2) Iijima, M.. Udagewa, Y., Ksys. K., and 110, M., Chem. Phys.. 7.229 (1975). (3) CantemG. W.,dansen,G.,Noort, M.andVander Waals. J. H.,J. Phys. Chem.,80,
e-c, \A>,",. ,>a.,c, &a"*

(4) Kielman-Val L ~ j i tE. . C. M.,Dekkers, H. P. J. M.,

noa,7a,e, """ ,..,",.

mdcanters,G. W.,Mol. Phys.,32,

(5) Shelnutt, J.A.,Cheuq.L. D..Chaq.L.C.C.. Nai-TengYu,mdFeltan.R. H.,J Chem. Phys.. 66,3387 (1977). (6) Baaei, M., J. Chem. Phya.,68,4907 (1978). (7) Jshn,H. A,, and Teller, E.,Proc.Roy. Soc. A , 161.220(1937). (8) Bsllhsusen. C. J., Theorel. Chim. Acto, 3,368 (1965).

rad;mic Press, New York. 1978;~ppendir 8.

818

Journal of Chemical Education