Computational quantum chemistry has made fantastic strides in the last 30 years. Often deep insight into all sorts of questions regarding reactions and structures of molecules has become possible. But sometimes the simplest of questions can prove incredibly difficult to answer. One such is how accurately can the boiling point of water be predicted from first principles? Or its melting point? Another classic case is why mercury is a liquid at room temperatures? The answer to that question (along with another, why is gold the colour it is?) is often anecdotally attributed to Einstein. More accurately, to his special theory of relativity.[1] But finally in 2013 a computational proof of this was demonstrated for mercury.[2] The proof was built up in three stages.
What I did not get from this article is why mercury is such a very special case (i.e. why neither gold, m.p. 1337K nor thallium, m.p. 577K, are liquids at room temperature). No doubt someone will explain. In the past, gold and mercury were said to be the only two visual manifestations of Einstein’s special theory in every-day objects. I say the past, because mercury is now rarely seen in any every-day objects (digital thermometers have taken over, and the mercury barometer has long since gone). If anyone knows of other examples, do let us know.
Note added in 2019: Similar calculations have now been performed on Copernicium[3] predicting it too is a liquid (MP 283 ± 11K) and has noble gas character (group 18) due to both relativistic and dispersion effects. Without those, it would simply be a common group 12 element.
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Nice post.
Spin-orbit coupling is a purely relativistic effect.
It gives rise to magnetic anisotropy and hysteresis in ferromagnets.
They are "everyday" phenomena.
A colleague has kindly brought to our attention the observation that whilst mercury is unusual amongst the elemental metals, there exists a class of non-relativistic molecular metal, of which a member Li(NH3)4 is even odder (DOI: 10.1021/ja109397k) in melting at 89K! These are described as expanded metals, since "the distance between the molecular bearers of the eventually itinerant electrons becomes large".
There can be (much) more to the term metal than meets the eye.
In the last week, the first example of a relativistic effect on the properties of a molecule (as opposed to an element) has been published, DOI: 10.1126/science.1255720. The molecule in question is Sg(CO)6. I quote here a pertinent passage from the article itself:
because of the relativistic contraction of s and p1/2 orbitals, the d-orbitals are better shielded from the atomic nucleus and expand. The overlap with the LUMO of the CO ligand becomes stronger. This may lead to a stronger contribution of π-back-donation relative to σ-donation in comparison with the corresponding ratio in the complexes of the lighter members of group 6.
Only by including full relativistic effects can quantum mechanics predict the hexacarbonyl to be both stable and volatile, which was indeed verified by experiments. Presumably without relativistic effects, the hexacarbonyl would have been predicted to be unstable, easily dissociating to a lower-coordination carbonyl and CO gas.
Someone correct me who has a better understanding, but gold is not liquid because its 6s valence shell is not filled and is therefore more susceptible to valence bonding (the single electron has a higher energy to allow overlap with other atoms while at the same time the atom is accepting of another electron to fill the electron pair). Thallium has an unfilled p-orbital, which has a very different shape than the s orbitals of the valence electrons for gold and mercury. It's shape reduces the exposure of the electron to the effects of the heavy nucleus and frees it up valence bonding with neighbors. In thallium's case, this bond does not fulfilll any specific electon pair, so it is not as strong as the valence bonds found in gold. This at least superficially explains why gold has a higher melting point than thallium.