# K S Krishnan and the early experimental evidences for the Jahn-Teller Theorem

## Abstract

Jahn-Teller theorem, proposed in 1937, predicts a distortional instability for a molecule that has symmetry based degenerate electronic states. In 1939 Krishnan emphasized the importance of this theorem for the arrangement of water molecules around the transition metal or rare earth ions in aqueous solutions and hydrated saltes, in a short and interesting paper published in Nature by pointing out atleast four existing experimental results in support of the theorem. This paper of Krishnan has remained essentially unknown to the practitioners of Jahn-Teller effect, eventhough it pointed to the best experimental results that were available, in the 30’s and 40’s, in support of Jahn-Teller theorem. Some of the modern day experiments are also in conformity with some specific suggestions of Krishnan.

Jahn-Teller effect<sup>1</sup> is a beautiful and simple quantum phenomenon that occurs in molecules, transition metal complexes as well as solids containing transition metal or rare earth ions. It states roughly that ‘a localized electronic system that has a symmetry based orbital degeneracy, will tend to lift the degeneracy by a distortion that results in the reduction of the symmetry on which the degeneracy is based.’ In isolated systems such as a molecule or a transition metal complex it is a dynamical or quasi static phenomenon. They are called dynamic and static Jahn-Teller effects<sup>2</sup>. When it occurs co-operatively in crystals it is a spontaneous symmetry breaking phenomenon and a crystal structure change. This is called a co-operative Jahn-Teller effect.

Even before Jahn-Teller theorem appeared, Krishnan and collaborators<sup>3</sup> performed a series of pioneering magneto crystalline anisotropy study of families of paramagnetic salts containing transition metal and rare earth ions lending good support to various new quantum mechanical ideas including those of Bethe, Kramers and Van Vleck on crystal field splitting and magneto crystalline anisotropy. In the biographical Memoirs of the Royal Society of London, K. Lonsdale and H.J. Bhaba<sup>4</sup> wrote: ‘The papers published by Krishnan during this period (30’s) in collaboration with B C Guha, S Banerjee and N C Chakravarty were the foundation stones of the modern fields of crystal magnetism and magnetochemistry’.

In the paramagnetic salts that Krishnan and collaborators studied the magnetic ions are well separated from each other by the intervening water molecules and also anion groups. As a result any direct or superexchange or dipolar interactions between the magnetic moments are weak; consequently any co-operative magnetic order such as antiferrmomagnetic order is pushed down to very low temperatures below 1 K. This enabled Krishnan and others to study in detail the magnetic properties of essentially isolated paramagnetic ions in various crystal field environments.

Jahn-Teller theorem and its experimental consequences has been studied in great detail in chemistry and physics particularly in the context of electron spin resonance experiments<sup>5</sup>. In the simplest of transition metal complexes there is a cubic (octahedral) environment around the transition metal ion such as $`Cu^{2+}`$. The octahedral environment leads to a crystal field splitting of the five fold degenerate d level into an orbital doublet ($`e_g`$) and a triplet ($`t_{2g}`$).

In Krishnan and collaborator’s work one notices repeated reference to deviation from cubic electric field at the center of rare earth ions in several cases and transition metal ions in some cases as inferred from their own anisotropic magnetic susceptibility measurements. The most obvious causes for departure from regular cubic symmetry of the coordination clusters are inequivalence of the ligand atoms in the first or second co-ordination shell and forces of crystal packing. No one suspected that electronic orbital degeneracy can lead to an asymmetry such as a distortion of the octahedra with equivalent ligand atoms.

It is at this juncture the theoretical papers of Jahn and Teller appeared, which suggested another important cause for molecular asymmetry. And Krishnan readily appreciated the importance of this theorem for crystal field splitting and arrangement of water molecules around paramagnetic ions in aqueous solutions and wrote an interesting short paper in Nature<sup>6</sup> in 1939 that we reproduce here. It is interesting that Van Vleck<sup>7</sup>, who very much admired<sup>8</sup> K S Krishnan, also developed his theory of Jahn-Teller effect for orbital doublets in paramagnetic ions in the same year.

In his paper KSK quotes at least four existing experimental results that support the Jahn-Teller theorem: i) x-ray data that is consistant with a small deviation of the perfect $`H_2O`$ octahedra around the paramagnetic ion in hydrated salts ii) magnetic data, mostly from his group, that exhibits strong magnetic anisotropy that is similar in magnitudes in various salts suggesting that the cause for any distortion arises from the electronic state of the paramagnetic ions rather than the surrounding atoms iii) asymmetry inferred from electronic absorption spectra of cation surrounded by water molecules in aqueous solutions studied by Freed et al. iv) magnetic double refraction exhibited by the aqueous solution of these salts, as observed experimentally by Raman and Chinchalkar and Haenny and v) the experimental observation of Chinchalkar that double refraction is absent experimentally when the paramagnetic ion is in an S-state (for example $`Gd^{3+}`$ or $`Mn^{2+}`$ which are orbital singlets)

Krishnan’s paper contained important suggestions and also looked at a slightly more complex system namely rare earth ions in aqueous solutions than the relatively simpler case of transition metal ions in solids. What Krishnan was looking for was perhaps static Jahn-Teller distortion at room temperature. The issue of timescale associated with the distortion dynamics and the nature of the experimental probe becomes important here. The Jahn-Teller cluster being a finite system, will either quantum mechanically tunnel among equivalent distorted configurations in a phase coherent manner with a short time period , or will hop to various equivalent distorted configurations incoherently through thermal fluctuations. Optical absorption, for example, is a short time scale measurement: it will see even dynamic distortions as a static one. The static susceptibility measurememt on the other hand is a low frequency probe. Any indication of distortion through this experiment will mean a nearly frozen distortion.

The choice of paramagnetic salts dissolved in water offers some special advantage too. A paramagnetic ion is typically surrounded by six water molecules forming a rigid octahedral complex. A coordination complex such as $`[Cu(H_2O)_6]^{2+}`$, is loosely coupled to the environment namely water. This makes the restoring force against the Jahn-Teller distortion weaker, making a nearly static Jahn-Teller distortion feasible even at room temperatures. On the other hand, In the case of a solids, the Jahn-Teller distortion has to work against the packing forces of the crystal thereby reducing the Jahn-Teller stabilisation energy.

Many of Krishnan’s experiments involved rare earth ions. In view of the larger degeneracy and also the compactness of the f-orbitals, rare earth ions have some advantages as well as disadvantages. The compactness of the wave functions make the crystal field splitting smaller and also the quenching of angular momentum less important. On the other hand the spin orbit coupling, which can make the magnetic anisotropy stronger, is larger in the rare earth case. The larger degeneracy of the f-orbitals also leads to a proliferation of low lying multiplets making the theory as well the interpretations of the spectra hard. Perhaps because of these difficulties most of the classic studies of Jahn Teller effect seems to be confined to transition metal ion systems.

I will try to put some of Krishnan’s suggestions in the modern context. Now it is well known that the dynamic to static Jahn-Teller distortion cross over temperature, as measured by ESR measurements, ranges from 1K to more than 300K in a variety of systems<sup>10</sup>. Some of these room temperature systems include $`Cu^{2+}`$ ion that Krishnan was referring to based preseumably on room temperature measurements. What I mean to say is that static Jahn-Teller distortion is not a very low temperature luxury that Krishan could have missed. Secondly, Krishnan was referring to some x-ray structural data as evidence for octahedral distortion. some modern EXAFS measurements<sup>11</sup> on $`Cu^{2+}`$ and $`Cr^{2+}`$ ions in aqueous solutions at room temperatures show the presence of a distorted octahedra with two copper-oxygen distances of about 2.00 Au and 2.3 Au.

Krishnan’s suggestion that the large magnetic double refraction observed by Raman and Chinchalkar and Haenny in aqueous solutions of paramagnetic ions is very interesting. This seems to be a compelling evidence for the Jahn-Teller distortion, as explained by Krishnan: the distorted octahedral complex, inview of the magnetic anisotropy arising from the large spin-orbit coupling, tend to align themselves in water along the magnetic fields causing double refraction. The absence of solid state effects and diluteness of the paramagnetc ions makes this argument very important: the system resembles somewhat an ideal gas of ‘octahedral molecules’ as far as the double refraction is concerned. I should also point out that I have not been able to find out in my short literature survey any later study of Jahn-Teller effect in aqueous solutions using the magnetic double refraction as a proble.

After this one paper on Jahn-Teller effect, Krishnan essentially left the field of crystal paramagnetism. Further he also never wrote any paper on the issue of Jahn-Teller effect.

The insightful suggestions of Krishnan, that came soon after the Jahn-Teller theorem, was never taken up for further study as far as I can see in the literature. This paper has remained unknown. One wonders why. One possible reason is the choice of rare earth ions, which as we mentioned earlier is complicated theoretically and also hard when it comes to interpretation of the experimental spectra. Another possible non scientific reason is as follows: a detailed followup paper or some further works by Krishnan<sup>9</sup> could have made Krishnan’s work known more and opened up the field of Jahn-Teller effect much earlier, making Krishnan a pioneer in one more beautiful field.

Detailed experimental confirmation of Jahn-Teller theorem became possible only after the ESR experiments of Bleaney and Bowers<sup>12</sup> in 1952 in $`CuSiF_6.6H_2O`$ and related family of paramagnetic salts, about 15 years after the enunciation of the theorem and Krishnan‘s supporting suggestions. The milestones included careful observation of the split ESR line below about 50K (indicating frozen distortion in the ESR time scales) and motional narrowed unsplit line above about 50K (indicating a dynamic distortion) for the copper salts.

Narly half a decade of experimental work on Jahn-Teller effect in the modern era is broadly consistant with the sixty year old suggestion of Krishnan. The practically unknown suggestions of Krishnan , however, remains as the only experimental support for the Jahn-Teller theorem covering a period of more than ten years, before the beginning of the modern era. As I mentioned earlier, the suggestion of magnetic double refraction by Krishnan may be still be useful in the modern context for Jahn-Teller effect study in the rich variety of new and old coordination complexes involving transition metal and rare earth metal ions.

Acknowledgement

I wish to thank Dr Tapan Kumar Kundu (RSIC, IIT Madras) for an informative discussion.

References   
1) H.A. Jahn and E. Teller, Proc. Roy. Soc. A161 220 (1937)   
2) M.D. Sturge, in Solid State Physics, Eds. Seitz and Turnbull, vol. 20 page 91 (Academic Press, New Yor, 1967); I.B. Bersuker, Jahn-Teller effect and vibronic interactions in Modern Chemistry (Plenum, NY, 1984)   
3) Starting from 1933 Krishnan and collaborators wrote more than a dozen important papers on exhaustive study of magneto crystalline anisotropy in paramagnetic salts   
4) K Lonsdale and H J Bhabha in Biographical Memoirs of the Royal Society of London, 1962   
5) A. Abragam and B. Bleaney, Electron Paramagnetic Rosonance of transition metal ions (Clarendon Press, Oxford 1970)   
6) K. S. Krishnan, Nature, 143 600 (1939)   
7) J. H. Van Vleck, J. Chem. Phys. 7 72 (1039)   
8) P.W. Anderson, in his K.S. Krishnan Memorian Lecture devivered at NPL, Delhi in 12th January 1987, recalls warmly Van Vleck’s (Ph.D. supervisor of P W Anderson) admiration for K.S. Krishnan. Another such instance involving Van Vleck is quoted in the article by K.Lonsdale and H.J. Bhaba (ref. 4)   
9) A close look at K.S. Krishnan’s style of paper writing shows that typically he starts with a short letter style paper and ends with a series of long papers presenting the details of his experimental investigations. Roughly in each five, six years he goes for new pastures.   
10) T.K. Kundu and P.T. Manoharan, Chem. Phys. Lett. 241 627 (1997); 264 338 (1997); T.K. Kundu, Ph.D. Thesis (Chemistry Department, IIT, Madras 1997); Kundu notes that in solutions the counter ions can affect (renormalise) the cross over temperature considerably in some cases   
11) T.K. Sham, Chem. Phys. Lett. 83 391 (1981); B. Beagley et al. J. Phys.: Conens. Matter, 1 2395 (1989); A recent paper, Ralf Akesson et al., J. Phys. Chem. 96 150 (1992), refers to some modern EXAFS measurements by I. Watanabe and N. Matsubayashi (Osaka) on the two copper-oxygen distances in the octahedra.   
12) B. Bleaney and K.D. Bowers, Proc. Phys. Soc. (London) A65 667 (1952)