The electrical conductivity of metals is a physical property of these materials. Much of the theory used to explain the electrical conductivity of metals is also based on physics understanding. However, I would like to ask if it is possible to incorporate some chemistry, from concepts in atomic structure or chemical bonding of metals, into explaining the variation of electrical conductivity across periods and down groups.

Based on chemistry alone, we would obviously expect predicted trends to be inaccurate. The chemistry reasoning would need to be complemented by physical theories to give a complete and accurate prediction of such a property. Recently, I have seen an over-simplistic explanation based on the number of valence electrons the metal atoms possess, equating more valence electrons to higher electrical conductivity. This was used to explain the higher electrical conductivity of $\ce {Cu}$, compared to $\ce {Ca}$, and it was clearly wrongly used.

On this note, I would like to ask, what are the factors, in terms of electronic structure of metals or their chemical bonding behaviour, that influence the electrical conductivity of metals?

Mott (1936) informs that for most of the first-row transition metals, it is the $\ce {4s}$ electrons which are delocalised and thus, contribute to the conductivity. Of course, in metallic bonding of these metals, both $\ce {3d}$ and $\ce {4s}$ orbitals overlap significantly and they should both be considered but Mott says that the $\ce {3d}$ electrons move much more slowly, due to their higher effective mass, thus contributing less to conductivity.

Mott, N. F. The electrical conductivity of transition metals. Proc. Royal Soc. Lond. 1936, 153, 699-717.

  • $\begingroup$ I might suggest starting through Ashcroft & Mermin's excellent Solid State Physics book - it is a big topic. But, in general, trying to directly compare chemistry (atoms and molecules) with solid state physics (crystal properties) rapidly leads to cognitive dissonance - there is just too much changing. The simple picture of atomic orbitals smoothly merging into energy bands in solids just doesn't work out most of the time. $\endgroup$ – Jon Custer Jul 9 '19 at 14:06
  • $\begingroup$ chemistry.stackexchange.com/questions/57484/… may also be of interest (full disclosure - my answer). Similarly chemistry.stackexchange.com/questions/58847/…. $\endgroup$ – Jon Custer Jul 9 '19 at 14:19
  • $\begingroup$ @JonCuster Thank you for your insights. Your answer in the linked post was helpful. I may explore the references/textbooks you have suggested in future. $\endgroup$ – Tan Yong Boon Jul 9 '19 at 22:54

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