Do Quantum Orbitals in the Atom Overlap at Different Energy Levels?

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Discussion Overview

The discussion revolves around the nature of quantum orbitals in atoms, specifically whether orbitals of different energy levels can overlap and how this relates to electron transitions between these orbitals. The scope includes conceptual understanding and the implications of quantum mechanics in atomic structure.

Discussion Character

  • Conceptual clarification
  • Debate/contested
  • Technical explanation

Main Points Raised

  • One participant questions whether higher orbitals (like d orbitals) can overlap with lower orbitals (like s or p orbitals) given that orbitals are associated with quantized energy levels.
  • Another participant suggests that while orbital functions can mathematically overlap, the probability of finding an electron in a different energy eigenstate is zero due to orthogonality of these states.
  • A later reply clarifies that in unperturbed systems, electrons in different orbitals do not overlap, but perturbations can allow for transitions between states, leading to a mixture of orbital probabilities.
  • One participant expresses confusion about the concept of overlap, seeking clarification on whether an electron in a higher orbital can be found in a lower orbital without transitioning to that state.
  • Another participant explains that in perturbed systems, overlap can occur, allowing for energy transitions, and emphasizes that understanding this requires familiarity with quantum mechanics mathematics.
  • A participant raises a question about the behavior of electrons when a gas is heated and photons are emitted, inquiring about the energy transfer involved in electron transitions.
  • Another participant responds by discussing collision excitation and the conditions under which electrons can be excited to higher energy states, noting that occupied states cannot be excited to certain lower states.

Areas of Agreement / Disagreement

Participants express differing views on the concept of overlap between orbitals, with some asserting that overlap is not possible in unperturbed systems, while others acknowledge that perturbations can lead to overlap and transitions. The discussion remains unresolved regarding the precise nature of overlap and its implications for electron behavior.

Contextual Notes

Limitations include the participants' varying levels of understanding of quantum mechanics, which affects the clarity of the discussion. The mathematical formalism of quantum mechanics is referenced but not fully explored, leaving some assumptions and definitions unaddressed.

Who May Find This Useful

This discussion may be of interest to students and individuals seeking to understand the behavior of electrons in atomic orbitals, particularly in the context of quantum mechanics and atomic transitions.

Quantom
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My question concerns the orbitals in the atom (s,p,d, and f.) I know that each orbital shell is a probability density that has a quantized energy. My question is, do the orbitals touch, or rather do higher orbitals like say a d have a probability density that overlaps a p or s orbital in a lower shell. Considering that the orbitals are quantized I am assuming that they do not overlap because any overlap would mean that the electrons have the same energy and because they are quantized this can't happen...but I am not sure...thanks in advance for your responses.
 
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I think you are mixing different concepts here.

All these orbital functions extend from 0 to infinite radius, compare with sin(x) and cos(x), you can see that they "overlap".

But the probability for a genera state [itex]\psi[/itex] to be in the energy-eigenstate [itex]\phi _E[/itex] is:

[tex]\int d\vec{x}\, \phi _E^*(\vec{x}\, ) \psi (\vec{x}\,) = P[/tex]

And different energy-eigenstates are orthogonal:

[tex]\int d\vec{x} \, \phi _E^*(\vec{x}\, ) \phi _{\epsilon} (\vec{x}\,) = \delta _{E,\epsilon}[/tex]

So you have to think for yourself what you mean by "overlap", the function cos(x) and sin(x) does are overlapping each other as graphs, but their integral:

[tex]\int _0^{2\pi} dx \, \cos (x) \sin (x) = 0[/tex]
 
I appreciate the reply, but I am afraid that i have very little clue what that meant considering i am a high school student who is not well versed in the mathematics for quantum mechanics. When i say overlap i mean can an electron in a higher orbital have a probability of existing in a lower orbital like the s, but does not jump to that orbital. My understanding is that electrons can jump to different orbitals i just want to know if electrons that exist in a higher orbital can be found in lower orbitals even though their energy exceeds that of the lower orbital. Hopefully that clears my definition of overlap up, but perhaps not.
 
You are then talking about the "integral overlap"´and then the answer is "yes" and "no".

No is that the Energy eigenfunctions are orthogonal, if your electron is state 2p, then it has no probability to be in the state 1s, 2s etc.

But that is for unperturbed systems, in reality, we can perturb the system (atom) to make transitions of between these states.

Considering the electron in its ground state, 1s, if it is not perturbed it will stay there for ever. But if we perturb it, with an external source (a photon as an example) its probability density function will become a mixture of 1s, 2s, 2p etc, and you will have a probability to find it in an excited state. And the opposite situation when the electron is in an excited state. This is called perturbation theory.

So let me summarize:
i) In the unperturbed system, atom, you will not have any overlap between different orbital functions.
ii) In perturbed systems, you can have it, and this can induce transitions in energy (jumps)

You will understand more when you learn more about the mathematical formalism of QM, I promise, since QM is basically a mathematical way to describe nature.
 
thanks that was much more understandable
 
Quantom said:
thanks that was much more understandable

It is hard to know at what level one should answer when the person who asked does not give any clue at what level of understand he is at. Remember that next time to tell that you are a high school student :-)
 
so what occurs with electrons in the orbitals of an atom when a gas is heated and a photon is emitted? My understanding is that an electron from a lower orbital rises and then falls back down. How does the electron get energy to jump up if it is a higher orbital electron that is being effected? Does the overlap increase thereby giving the lower orbital electron enough energy to jump up?
 
There you have collision excitation, atoms will 'collide' more often (since you will increase the average kinetic energy of the atoms in the gas. thus resulting in a higher probability per unit time to excite an atom).

You can only excite electron in an atom to a non occupied state. e.g if the all the states up to 3d are occupied, you can't excite a 1s electron to a 2p state, etc.
 
thank you very much for your help.
 

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