Many body wavefunction and exchange correlation

In summary, the conversation discusses the term "exchange correlation functional" in relation to Hartree-Fock (HF) and Density Functional Theory (DFT). The first fundamental question is about the claim that the exchange term is accounted for exactly in the HF energy, which may not be accurate due to the use of approximate single electron wavefunctions. The second question is about the difficulty in calculating the exact electron-electron repulsion term, which can only be expressed in terms of the two-particle density. The third question ponders whether the challenge in finding the correct exchange-correlation functional is related to the non-existence of single body wavefunctions in a many body system or the inability to mathematically combine N single body wavefunctions into one many
  • #1
askhetan
35
2
Everywhere I ready about HF or DFT the term exchange correlation functional comes up. I have a couple of fundamental questions about these:

1) Books say that the correlation energy is the difference between the exact energy (lets say we've found that somehow) and the hartree-fock energy and that the exchange term is accounted for exactly in the hartree-fock energy. While these claims depend on what exactly you include in the correlation energy, isn't the second part on getting the exact exchange totally wrong?? This is because the wave functions that are used to construct/evaluate the hartree fock energy are not the "exact" single electron wavefunctions to begin with so whatever mathematical construct we use to get the exchange energy term can only yield us a false answer. We don't know if there are things called single electron wavefunctions! Or am I wrong? I mean let's say we got the "exact" single electron wavefunctions from somehwhere. Then can we calculate the exchange energy the way its been calculated in hartree-fock method ? Is there a fundamental way to combine all the "exact" single electron wavefunctions to give us the total wavefunction?

2) Likewise, all books say that when we take into account coulombic repulsion, only using the composite wave function can only give us the same exact repulsion. If we use individual electron wavefunctions or densities, then this becomes a mean field approximation. I really do not understand this. In the end an electron is particle at least to the extent that it cannot feel repulsion from itself. So if it feels the repulsion from other charge densities (given we know what they are), why should this be a problem ?. I put forward the same proposal again - if i can get the "exact" single electronic wavefunctions from somewhere, then wouldn't it feel the repulsion of other electrons in the way this normal "averaged" coulomb term describes.
To be more specific, I provide this document http://www.physics.metu.edu.tr/~hande/teaching/741-lectures/lecture-05.pdf where on page 2, Eq. (11) the real accurate term has been described for calculating the exact repulsion from the many-body density. It says there "It can be proven that this (electron electron repulsion) term cannot be written in terms of the single-particle density but instead only in terms of the two-particle density". Can someone please direct me to the proof?

3) Are we in the end saying that there is no rule of physics which can tell how one exact single many body wavefunction for N electrons can be decomposed into N exact 1-body wavefunctions or vice versa. Is this really the challenge that we haven't been able to solve in order to get to the correct exchange-correlation functional? If yes please explain a bit further. Also, has this all got to do anything with the second quantization, whatever that means.

Thanks a lot for your attention.
 
  • #3
To reword it and shorten it I'd say this:

Every text I read says we do not know the exact exchange-correlation functional. Is this related to the non-existence of single body wavefunctions in a many body system? or is it related to the lack of our knowledge of being able to mathematically combine N single body wavefuntions into one many body wavefunction (or the vice versa - deconstruct the many body wavefuntion into N single body wavefunctions.)?
 

1. What is a many body wavefunction?

A many body wavefunction is a mathematical representation of the quantum state of a system composed of multiple particles. It describes the position, momentum, and other properties of all the particles in the system.

2. What is exchange correlation in the context of many body wavefunction?

Exchange correlation refers to the effects of the interactions between particles on the overall wavefunction of a many body system. This includes the exchange of particles between different states and the correlation of their positions and movements.

3. How is the exchange correlation term incorporated into the Schrödinger equation?

The exchange correlation term is included in the Schrödinger equation through the use of density functional theory (DFT). This allows for the calculation of the total energy of a many body system by considering the interactions between particles.

4. What is the significance of the exchange correlation term in electronic structure calculations?

The exchange correlation term is crucial in accurately predicting the behavior and properties of materials at the atomic and molecular level. It accounts for the quantum mechanical effects of electron-electron interactions, which are essential for understanding and predicting the behavior of matter.

5. How is the exchange correlation term treated in different theoretical models?

The exchange correlation term is treated differently in different theoretical models, such as Hartree-Fock theory, DFT, and many-body perturbation theory. Each model takes into account different aspects of the exchange and correlation effects, and the choice of model depends on the specific system being studied and the desired level of accuracy.

Similar threads

  • Atomic and Condensed Matter
Replies
0
Views
486
  • Atomic and Condensed Matter
Replies
4
Views
1K
  • Quantum Physics
2
Replies
44
Views
2K
  • Atomic and Condensed Matter
Replies
1
Views
827
  • Atomic and Condensed Matter
Replies
0
Views
40
  • Atomic and Condensed Matter
Replies
3
Views
2K
  • Quantum Physics
Replies
2
Views
766
  • Atomic and Condensed Matter
Replies
1
Views
811
  • High Energy, Nuclear, Particle Physics
Replies
12
Views
2K
  • Atomic and Condensed Matter
Replies
3
Views
10K
Back
Top