Why Do 4s Orbitals Fill Before 3d as Atomic Number Increases?

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SUMMARY

The discussion centers on the filling order of 4s and 3d orbitals as atomic number increases, specifically addressing why 4s orbitals are filled before 3d orbitals. It is established that this occurs due to the lower energy state of 4s orbitals when lower energy levels are filled. Key concepts such as electron penetration and shielding are highlighted, with emphasis on the radial distribution of electrons in these states. The Schrödinger Equation's applicability to multi-electron systems is also acknowledged, providing a framework for understanding energy levels.

PREREQUISITES
  • Understanding of atomic orbitals and their energy levels
  • Familiarity with concepts of electron penetration and shielding
  • Basic knowledge of the Schrödinger Equation
  • Awareness of radial distribution functions in quantum mechanics
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  • Study the radial distribution of 4s and 3d orbitals
  • Research the effects of electron shielding on atomic energy levels
  • Explore the implications of angular momentum on energy levels
  • Review the Schrödinger Equation in the context of multi-electron atoms
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Students of quantum mechanics, chemistry enthusiasts, and educators seeking to deepen their understanding of atomic structure and electron configurations.

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Homework Statement


Explain why, as the atomic number increases, the 4s electronic states fill before the 3d states. The fact that they fill first means they are lower energy. You must explain why they are lower energy.


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The Attempt at a Solution


First, I'm aware that 4s is not always lower energy than 3d and they are only asking about the case where previous orbitals have been filled.

Everything I've dug up so far has been kinda vague, mentioning things like penetration and shielding. That doesn't sound like a good answer. More specifically, I've seen penetration described as the electron spending more time closer to the nucleus, however, the electron is really a standing wave, so that doesn't make sense to me.

We've only really discussed the Schrödinger Equation for the hydrogen atom, so that doesn't seem applicable here, but any reasonably simple explanation involving it would be very welcome. Thanks.
 
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Habeebe said:
First, I'm aware that 4s is not always lower energy than 3d and they are only asking about the case where previous orbitals have been filled.
What's special about having the lower states filled?

Everything I've dug up so far has been kinda vague, mentioning things like penetration and shielding. That doesn't sound like a good answer.
Why not?

More specifically, I've seen penetration described as the electron spending more time closer to the nucleus, however, the electron is really a standing wave, so that doesn't make sense to me.
Where did you get the idea that the electron is "really" a standing wave?
It is the wavefunction that forms a stationary state - not the electron. "Spending more time close to the nucleus" means more likely to be detected close to the nucleus than far away from it ...

Compare the radial distribution of the 4s and 3d states.
What is the average distance of the electron from the nucleus in these states?

Have you had a look at what shielding may be doing?

What happens to the spacing of atomic energy levels as you increase n?
What does angular momentum do to each energy level?

We've only really discussed the Schrödinger Equation for the hydrogen atom, so that doesn't seem applicable here, but any reasonably simple explanation involving it would be very welcome.
It is, sort-of, applicable.
The pattern of energy levels for atoms in general is similar to that for hydrogen.
 
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I discussed it with my professor, and in conjunction with your replies it makes a lot more sense now. Thanks.
 

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