I have now read on the Wikipedia pages for unbihexium, unbinilium, and copernicium that these elements will not behave similarly to their forebears because of “relativistic effects”. When I read about rutherfordium, it too brings up the relativistic effects, but only to say that it compared well with its predecessors, despite some calculations indicating it would behave differently, due to relativistic effects.
The dubnium page on Wikipedia says that dubnium breaks periodic trends, because of relativistic effects. The Wikipedia page on seaborgium doesn't even mention relativistic effects, only stating that it behaves as the heavier homologue to tungsten. Bohrium's Wikipedia page says it's a heavier homologue to rhenium.
So, what are these relativistic effects and why do they only take effect in superheavy nuclei? When I think of relativistic effects, I think speeds at or above $.9 c$ or near incredibly powerful gravitational forces. So, I fail to see how it comes into play here. Is it because the electrons have to travel at higher speeds due to larger orbits?
Best Answer
When quantum mechanics was initially being developed, it was done so without taking into account Einstein's special theory of relativity. This meant that the chemical properties of elements were understood from a purely quantum mechanical description i.e., by solving the Schrödinger equation.
The more accurate models following that time, that do use special relativity, were found to be more consistent with experiment than compared with the ones that were used without special relativity.
So when they quote "relativistic effects" they are referring to chemical properties for elements calculated using special relativity.
Changes to chemical properties of elements due to relativistic effects are more pronounced for the heavier elements in the periodic table because in these elements, electrons have speeds worthy of relativistic corrections. These corrections show properties that are more consistent with reality, than with those where a non-relativistic treatment is given.
A very good example of this would be the consideration of the color of the element gold, Au.
Physicist Arnold Sommerfeld calculated that, for an electron in a hydrogenic atom, its speed is given by $$v \approx (Zc)\alpha$$ where $Z$ is the atomic number, $c$ is the speed of light, and $$\alpha\approx\frac{1}{137}$$ is a (dimensionless) number called the fine structure constant or Sommerfeld's constant. For Au, since $Z= 79$, its outer shell electrons would be moving$^1$ at about $0.58c$. This means that relativistic effects will be pretty noticeable for gold$^2$, and these effects actually contribute to gold's color.
Interestingly, we also note from the above equation, that if $Z\gt 137$ then $v\gt c$ which would violate one of the postulates of special relativity, namely that no object can have a velocity greater than that for light. But it is also well known that no element can have atomic number $Z\gt 137$.
$^1$Electrons are not "moving around" a nucleus, but they are instead probability clouds surrounding the nucleus. So "most likely distances of electrons" would be a better term.
$^2$In the example of the element Gold, which has an electron configuration $$\bf \small 1s^2 \ 2s^2\ 2p^6\ 3s^2\ 3p^6\ 4s^2\ 3d^{10}\ 4p^6\ 5s^2\ 4d^{10}\ 5p^6\ 6s^1\ 4f^{14}\ 5d^{10}$$ relativistic affects will increase the $\bf \small 5d$ orbital distance from the nucleus, and also decrease the $\bf \small 6s$ orbital distance from the nucleus.