Why is the energy of two ions bonded lower than two ions separated?

  • Thread starter Thread starter rokku
  • Start date Start date
  • Tags Tags
    Energy Ions
Click For Summary

Discussion Overview

The discussion revolves around the question of why the energy of two ions bonded together is lower than that of two separated ions. Participants explore concepts related to covalent bonding, quantum mechanics, and the interplay of forces such as attraction and repulsion between charged particles.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested
  • Mathematical reasoning

Main Points Raised

  • One participant questions how bonding lowers the overall energy despite repulsive forces between protons and electrons.
  • Another participant suggests that covalent bonding is a consequence of particle indistinguishability, referencing Griffiths' work on quantum mechanics.
  • There is a challenge regarding the classification of nuclei as fermions or bosons, with a later reply emphasizing the importance of electron positioning in bonding.
  • Some participants argue that indistinguishability is not the crucial factor in covalent bonding, noting that bonding occurs even in systems with a single electron, such as H2+.
  • One participant discusses the quantum mechanical nature of bonding, highlighting how electron positional uncertainty contributes to lower kinetic energy.
  • Another participant mentions the "exchange force" and its minimal role in bonding, while also questioning the implications of electron pairing in different spin states (singlet vs. triplet) on bonding outcomes.
  • A crude model involving positive and negative charges is proposed to illustrate binding energy, suggesting that quantum chemistry would provide a more accurate description involving various energy components.

Areas of Agreement / Disagreement

Participants express differing views on the significance of indistinguishability in bonding and the effects of electron spin states on covalent bonding. The discussion remains unresolved regarding the implications of these factors on the overall understanding of bonding energy.

Contextual Notes

Some claims rely on specific interpretations of quantum mechanics and may depend on definitions of terms like "indistinguishability" and "bonding." The discussion includes references to advanced concepts that may not be universally accepted or understood.

rokku
Messages
7
Reaction score
0
How does forming a bond between two ions lower the overall energy of the system? Also how would two hydrogen atoms form if there is proton-proton repulsion and electron-electron repulsion and only proton-electron attraction?
 
Chemistry news on Phys.org
In the case of covalent bonding, it's a consequence of the indistinguishability of particles! Griffiths talks about this at the end of his Intro to Quantum book in Chapter 5. Essentially, the superposition that results from treating identical particles (they are treated as distinguishable classically) results in bosons being closer together and fermions (like electrons) being farther apart and once you consider spin, the electrons are able to occupy the "singlet" state where they are more likely to be in between the two nuclei, attracting them towards the center.
 
Last edited:
Pythagorean said:
In the case of covalent bonding, it's a consequence of the indistinguishability of particles! Griffiths talks about this at the end of his Intro to Quantum book in Chapter 5. Essentially, the superposition that results from treating identical particles (they are treated as distinguishable classically) results in bosons (nucleus) being closer together and fermions (like electrons) being farther apart and once you consider spin, the electrons are able to occupy the "singlet" state where they are more likely to be in between the two nuclei, attracting them towards the center.

Aren't most nuclei fermions, not bosons?
 
Ah yes, good point. Removed the reference to the nucleus. The electrons concentrating in the middle and attracting the protons is really the key point, I think.
 
Indistinguishability is not the crucial point, given that you observe covalent bonding already for molecules containing only one electron, namely ##\mathrm{H}_2^+##.
Classically you won't expect a big effect, as nuclear-nuclear repulsion and electron-electron repulsion is made up at bonding distances by electron nuclear attraction.
In fact, covalent bonding is an essentially quantum mechanical effect. In the molecule, the electron can move in the potential throughs of two nuclei as compared to only one in the case of a single atom. This increases its positional uncertainty ##\Delta x## along the bond axis and by the uncertainty principle lowers its momentum uncertainty ##\Delta p=\hbar/\Delta x##.
Hence also its kinetic energy gets lower although the story doesn't end here.
There is an excellent article by Kutzelnigg, a quantum chemist, on the principle behind bonding:
http://onlinelibrary.wiley.com/doi/10.1002/anie.197305461/abstract
 
DrDu said:
Indistinguishability is not the crucial point, given that you observe covalent bonding already for molecules containing only one electron, namely ##\mathrm{H}_2^+##.
Classically you won't expect a big effect, as nuclear-nuclear repulsion and electron-electron repulsion is made up at bonding distances by electron nuclear attraction.
In fact, covalent bonding is an essentially quantum mechanical effect. In the molecule, the electron can move in the potential throughs of two nuclei as compared to only one in the case of a single atom. This increases its positional uncertainty ##\Delta x## along the bond axis and by the uncertainty principle lowers its momentum uncertainty ##\Delta p=\hbar/\Delta x##.
Hence also its kinetic energy gets lower although the story doesn't end here.
There is an excellent article by Kutzelnigg, a quantum chemist, on the principle behind bonding:
http://onlinelibrary.wiley.com/doi/10.1002/anie.197305461/abstract

Huh. I never knew that. Thanks Dru.
 
DrDu said:
Indistinguishability is not the crucial point, given that you observe covalent bonding already for molecules containing only one electron, namely ##\mathrm{H}_2^+##.
Classically you won't expect a big effect, as nuclear-nuclear repulsion and electron-electron repulsion is made up at bonding distances by electron nuclear attraction.
In fact, covalent bonding is an essentially quantum mechanical effect. In the molecule, the electron can move in the potential throughs of two nuclei as compared to only one in the case of a single atom. This increases its positional uncertainty ##\Delta x## along the bond axis and by the uncertainty principle lowers its momentum uncertainty ##\Delta p=\hbar/\Delta x##.
Hence also its kinetic energy gets lower although the story doesn't end here.
There is an excellent article by Kutzelnigg, a quantum chemist, on the principle behind bonding:
http://onlinelibrary.wiley.com/doi/10.1002/anie.197305461/abstract

Interesting read. They explicitly demonstrate how little the "exchange force" plays. I'll note that identical particles is a quantum mechanical effect, not a classical one.

So the next claim Griffiths makes is that in the triplet state, the electron pair are "antibonding" which implies to me that they will prevent covalent bonding in that case. Is that true?
 
Pythagorean said:
So the next claim Griffiths makes is that in the triplet state, the electron pair are "antibonding" which implies to me that they will prevent covalent bonding in that case. Is that true?

The problem is that e.g. in H_2, starting from the 1s orbitals, you can only form one bounding and one anti-bounding orbital as in H2+. With singlet pairing both electrons can fill the same bounding orbital, while with triplet pairing, one has to be in the anti-bonding orbital, so that no net bond results.
 
  • Like
Likes   Reactions: 1 person
The answer to the original question is much simpler than the above. You can construct a very crude model of 2 positive and 2 negative charges which is bound. Take a square ABCD of side a, with protons at A and C and electrons B and D. The energy is (-4+2sqrt(2))/a, which means binding.
Quantum chemistry will give an accurate number involving e kinetic energy, ep potential energy, e-e repulsion mitigated by e-e correlation. To become more precise you have to use Dirac theory, finite nuclear size, nuclear motion, radiative correction. But that was not the question.
 

Similar threads

  • · Replies 4 ·
Replies
4
Views
2K
  • · Replies 0 ·
Replies
0
Views
2K
  • · Replies 1 ·
Replies
1
Views
2K
Replies
1
Views
2K
Replies
3
Views
2K
Replies
3
Views
2K
Replies
32
Views
5K
  • · Replies 4 ·
Replies
4
Views
3K
Replies
4
Views
2K
  • · Replies 5 ·
Replies
5
Views
6K