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How can one explain niobium’s weird electronic configuration?

Asked 10 years, 6 months ago Modified 3 years, 8 months ago Viewed 57k times

As cited in an answer to this question, the ground state electronic configuration of niobium is:

64 Nb : [Kr] 5s1 4d4

Why is that so? What factors stabilize this configuration, compared to the obvious 5s2 4d3 (Aufbau principle), or the otherwise
possible 5s0 4d5 (half-filled shell)?

electronic-configuration transition-metals

Share Improve this question Follow edited Mar 31, 2018 at 12:47 asked Oct 29, 2012 at 15:11
Gaurang Tandon F'x
9,575 10 62 115 23.4k 8 94 150

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There is an explanation to this that can be generalized, which dips a little into quantum chemistry, which is known as the idea of
pairing energy. I'm sure you can look up the specifics, but basically in comparing the possible configurations of Nb , we see the
44 choice of either pairing electrons at a lower energy, or of separating them at higher energy, as seen below:

d: ↿ ↿ ↿ _ _ ↿ ↿ ↿ ↿ _ ↿ ↿ ↿ ↿ ↿ ^
OR OR |
s: ⥮ ↿ _ Energy gap (E)

The top row is for the d-orbitals, which are higher in energy, and the bottom row is for the s-orbital, which is lower in energy. There
is a quantifiable energy gap between the two as denoted on the side (unique for every element). As you may know, electrons like to
get in the configuration that is lowest in energy. At first glance, that might suggest putting as many electrons in the s-orbital (lower
energy) as possible, and then filling the rest in the d-orbital. This is known as the Aufbau principle and is widely taught in
chemistry classes. It's not wrong, and works most of the time, but the story doesn't end there. There is a cost to pairing the
electrons in the lower orbital, two costs actually, which I will define now:

Repulsion energy: Pretty simple, the idea that e- repel, and having two of them in the same orbital will cost some energy.
Normally counted as 1 C for every pair of electrons.

Exchange energy: This is a little tricky, and probably the main reason this isn't taught until later in your chemistry education.
Basically (due to quantum chemistry which I won't bore you with), there is a beneficial energy associated with having pairs of like
energy, like spin electrons. Basically, for every pair of electrons at the same energy level (or same orbital shell in this case) and
same spin (so, if you had 2 e- in the same orbital, no dice, since they have to be opposite spin), you accrue 1 K exchange energy,
which is a stabilizing energy. (This is very simplified, but really "stabilizing energy" is nothing more than negative energy. I hope
your thermodynamics is in good shape!) The thing with exchange (or K) energy is that you get one for every pair, so in the case:

↿ ↿ ↿

from say a p-subshell, you would get 3 K, for each pair, while from this example:

⥮ ↿ ↿ ↿ ↿

from a d6 , you would get 10 K (for each unique pair, and none for the opposite spin e-)

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from a d , you would get 10 K (for each unique pair, and none for the opposite spin e-)

This K is quantifiable as well (and like the repulsion energy is unique for each atom).

Thus, the combination of these two energies when compared to the band gap determines the state of the electron
configuration. Using the example we started with:

d: ↿ ↿ ↿ _ _ ↿ ↿ ↿ ↿ _ ↿ ↿ ↿ ↿ ↿ ^
s: ⥮ OR ↿ OR _ |
PE: 3K + 1C 6K + 0C 10K + 0C Energy gap (E)

You can see from the example that shoving 1 e- up from the s to the d-subshell results in a loss of 1C (losing positive or
"destabilizing" repulsive energy) and gaining 3K (gaining negative or "stabilizing" exchange energy). Therefore, if the sum of these
two is greater than the energy gap (i.e. 3K - 1C > E) then the electron will indeed be found in the d shell in Nb 's ground state.
Which is indeed the case for Nb .

Next, lets look at perhaps exciting the second s e- up to the d-subshell. We gain 4 additional K but don't lose any C, and we must
again overcome the energy gap for this electron to be found in the d-subshell.

It turns out that for Nb : 4K + 0C < E (remember that C is considered a negative value, which we're not losing any of), so Nb is
ultimately found in the 5s1 4d4 configuration.

Share Improve this answer Follow edited Mar 31, 2018 at 12:37 answered Jun 7, 2013 at 18:23
Gaurang Tandon Gavin Kramar
9,575 10 62 115 1,624 14 7

2 Just in case it wasn't obvious for any reader: "from say a p-subshell, you would get 3 K" that's because there are 3 C2 = 3 electron pairs. Similarly,
"from a d6 , you would get 10 K" that's because there are 5 C2 = 10 electron pairs. The author calculated this by simple combinatorics ;)
– Gaurang Tandon Mar 31, 2018 at 12:39

Well it turns out Atoms are a way more scientific than all best scientist put together, lol so much complexity just to be in low energy state. Great
answer at @Gavin kramar , could have added the actual figures for (E) i.e the energy gap – DJphy Feb 8, 2020 at 18:10

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