Help with Hohenberg-Kohn Theorem

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In summary, the conversation discusses the proof for the first Hohenberg-Kohn theorem, noting a statement that may not be obvious. The conversation then goes on to explain how this statement can be proven and how it relates to partial differential operators. It is concluded that for a potential to differ, it must be by a constant, and examples are given to illustrate this concept.
  • #1
TeethWhitener
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Hi everyone, I was going through the derivation of the first Hohenberg-Kohn theorem (see here under eqn 1.31 for reference) when I noticed a once-obvious statement that didn't seem so obvious anymore. Namely, the proof requires that if you have two Hamiltonians ##H_1 \neq H_2##, then their ground states are not equal ##\Psi_1 \neq \Psi_2##. Maybe this statement is just completely obvious and I'm missing some PDE or linear algebra uniqueness theorem that I should have remembered from college, but for the life of me, I can't prove it. I know that 2nd order ODE's have unique solutions (given the proper assumptions), but why can't we have:
$$H_1\Psi = E_1\Psi$$
$$H_2\Psi = E_2\Psi$$
where ##H_i## is a partial differential operator?
 
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  • #2
Nevermind, I think I figured it out. Let:
$$H_1 = -\frac{\hbar^2}{2m}\nabla^2+V_1(\mathbf{r})$$
$$H_2 = -\frac{\hbar^2}{2m}\nabla^2+V_2(\mathbf{r})$$
Then subtracting ##(H_2-E_2)\Psi=0## from ##(H_1-E_1)\Psi=0## gives
$$V_1(\mathbf{r})-V_2(\mathbf{r}) = E_1-E_2$$
So the potentials are only allowed to differ by a constant.
 
  • #3
Note that here it's assumed that ##\Psi \neq 0##. If you have a potential like ##V(x) = \frac{1}{2}kx^2## for some dimensionless position coordinate ##x## (with the unit of ##x## being same order of magnitude as the std. dev. of the ground state probability distribution) and then change it to something like

##V(x) = \left\{\begin{smallmatrix}\frac{1}{2}kx^2 ,\hspace{20pt}x<1000\\ 10kx^2 ,\hspace{20pt}x\geq 1000\end{smallmatrix}\right.##

the change doesn't really affect the ground state, as the wave function will be practically zero for values of ##x## larger than 1000 anyway.
 

FAQ: Help with Hohenberg-Kohn Theorem

1. What is the Hohenberg-Kohn Theorem?

The Hohenberg-Kohn Theorem is a fundamental theorem in quantum mechanics that provides a connection between the external potential of a system and its electron density. It states that the ground-state electron density uniquely determines the external potential, thus determining the total energy of the system.

2. What is the significance of the Hohenberg-Kohn Theorem?

The Hohenberg-Kohn Theorem is significant because it provides a mathematical basis for density functional theory (DFT), a widely used approach in quantum mechanics for studying the electronic structure of many-body systems. It also simplifies calculations by reducing the dimensionality of the problem from the 3D space of the wavefunction to the 3D space of the electron density.

3. How does the Hohenberg-Kohn Theorem relate to the Schrödinger equation?

The Hohenberg-Kohn Theorem is closely related to the Schrödinger equation, which is the fundamental equation governing the behavior of quantum systems. The theorem provides a way to calculate the ground-state energy and wavefunction without explicitly solving the Schrödinger equation.

4. Can the Hohenberg-Kohn Theorem be extended to excited states?

No, the Hohenberg-Kohn Theorem only applies to the ground state of a system. However, there are extensions of the theorem that can be used to calculate excited states, such as the Kohn-Sham equations in DFT.

5. Are there any limitations to the Hohenberg-Kohn Theorem?

Yes, there are some limitations to the Hohenberg-Kohn Theorem. It assumes that the system is in its ground state and that the electron-electron interactions are described by a local potential. It also does not take into account relativistic effects or correlation between electrons, which can be important in certain systems.

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