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Why is Thorium (At. no. 90) an f-block element at all?

Chemistry Asked by user82401 on October 5, 2021

Being an exception of the Aufbau principle, Thorium has an electronic configuration of $ce{[Rn]}mathrm{7s^25f^06d^2}$ instead of the expected $ce{[Rn]}mathrm{7s^2 5f^2 6d^0}$.

Two other elements, Lanthanum and Actinium, also showed such an anomaly as $mathrm{6s^2 4f^0 5d^1}$ and $mathrm{7s^2 5f^0 6d^1}$, respectively. But we placed them both in the d-block of the periodic table.

Since, even in Thorium, the last electrons occupied d-orbitals only (disobeying Aufbau), then why is it placed in the f-block of the periodic table. I mean, it should be placed in the d-block, shouldn’t it?

Edit: Note that here, I don’t intend to ask or know how or why the 2 electrons disobeyed the Aufbau, and occupied the higher energy 5d instead of lower energy 4f.

Rather, I want to know only that why it is kept in the f-block when the last orbitals which the electrons occupied were of d-subshell.

One Answer

The bulk metal actually does involve the $f$ orbitals, distinguishing it from what would be its congeners in Group 4 of the $d$ block. From Wikipedia:

Despite the anomalous electron configuration for gaseous thorium atoms, metallic thorium shows significant 5f involvement. A hypothetical metallic state of thorium that had the [Rn]6d27s2 configuration with the 5f orbitals above the Fermi level should be hexagonal close packed like the group 4 elements titanium, zirconium, and hafnium, and not face-centred cubic as it actually is. The actual crystal structure can only be explained when the 5f states are invoked, proving that thorium, and not protactinium, acts as the first actinide metallurgically.[1]

Cited reference

1. Johansson, B.; Abuja, R.; Eriksson, O.; et al. (1995). "Anomalous fcc crystal structure of thorium metal". Physical Review Letters 75 (2): 280–283. https://doi.org/10.1103/PhysRevLett.75.280, erratum at https://doi.org/10.1103/PhysRevLett.75.3968

Answered by Oscar Lanzi on October 5, 2021

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