Quantum Chemistry and ground-state energy

In summary: So the actual ground state is a linear combination of two states:$$\Psi_{He}(\mathbf{r}_1,\mathbf{r}_2)\propto \Psi_H(\mathbf{r}_1)\Psi_H(\mathbf{r}_2)-\Psi_H(\mathbf{r}_1)\Psi_H(\mathbf{r}_2)$$In summary, we can calculate the ground state energy and wave function of helium by ignoring the electron-electron repulsion term and treating each electron as if it were in an isolated hydrogen atom. This gives a ground state energy of 8 times the ground state energy of a single hydrogen atom, and a wave function that is a linear combination of two states
  • #1
Blamo_slamo
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Homework Statement


If we were to ignore the interelectronic repulsion in helium, what would be it's ground state energy and wave function?


Homework Equations


I have created my ground state wave function [tex]\psi[/tex] for 1s:

[tex]\psi[/tex] = (1/[tex]\sqrt{}\pi[/tex])(z/a)3/2(e-zr/a)

The operator is the laplacian, in spherical polar coordinates.

The Attempt at a Solution



So the energy of the two particles is the hamiltonian operating on [tex]\psi[/tex],
and I should get an eigen function out which would be the energy for one of the two particles.
Using the laplacian operator I got:

E = [(-[tex]\hbar[/tex] 2/2m)(1/[tex]\sqrt{}\pi[/tex])(z/a)3/2](z2/a2 e-zr/a - 2z/ar e-zr/a) + V(r)[tex]\psi[/tex]

For the energy of the one particle. My problem is,
that this isn't an eigen function of the laplacian, and I've managed to hit a brick wall.
I'm completely stumped on what I could do, any help would be greatly appreciated!
 
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  • #2
Blamo_slamo said:
If we were to ignore the interelectronic repulsion in helium, what would be it's ground state energy and wave function?
It might help to start by writing out the Hamiltonian. Ignoring the electron-electron repulsion term gives:
$$H = -\frac{\hbar^2}{2m}(\nabla^2_{\mathbf{r}_1}+\nabla^2_{\mathbf{r}_2}) -\frac{Ze^2}{4\pi \varepsilon_0 |\mathbf{r}_1-\mathbf{R}|}-\frac{Ze^2}{4\pi \varepsilon_0 |\mathbf{r}_2-\mathbf{R}|}$$
But hopefully you'll see this is just a Hamiltonian for two isolated hydrogen atoms. Couple that with the fact that ##Z_{He}=2Z_{H}## and you get that the ground state energy for each electron is ##E_{He} = 4E_H##. So the total ground state energy (for 2 electrons) is ##E_{He} = 8E_H## and the wavefunction is just ##\Psi_{He}(\mathbf{r}_1,\mathbf{r}_2) = \Psi_H(\mathbf{r}_1)\Psi_H(\mathbf{r}_2)##, where ##\Psi_H## is the ground state wavefunction for the hydrogen atom.

EDIT: one quick note, since the electrons are fermions, the total wavefunction must be antisymmetric with respect to exchange of ##\mathbf{r}_1## and ##\mathbf{r}_2##. Obviously, our ground state helium wavefunction above is not. However, if we attach spin labels to the electrons, then we can get back antisymmetry as long as the electrons have opposite spins.
 
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FAQ: Quantum Chemistry and ground-state energy

1. What is quantum chemistry?

Quantum chemistry is a branch of chemistry that uses principles from quantum mechanics to study the behavior and properties of atoms and molecules. It provides a more accurate understanding of the chemical bonding and interactions between particles at the atomic level.

2. What is the ground-state energy?

The ground-state energy is the lowest possible energy level that an atom or molecule can have in its stable, lowest energy state. It is the starting point for calculating other energy levels and properties of the system.

3. How is the ground-state energy calculated?

The ground-state energy is calculated using quantum mechanical equations, such as the Schrödinger equation, which take into account the positions and interactions of all the particles in the system. These equations are solved using computational methods, such as the Hartree-Fock method, to determine the lowest energy state.

4. What factors affect the ground-state energy?

The ground-state energy of an atom or molecule is influenced by various factors, including the number of electrons, the nuclear charge, and the distance between atoms. The electron configuration and the atomic or molecular geometry also play a role in determining the ground-state energy.

5. Why is the ground-state energy important in chemistry?

The ground-state energy is important in chemistry because it provides information about the stability and reactivity of atoms and molecules. It also helps in predicting and understanding various chemical properties, such as bond strengths, ionization energies, and electronic spectra, which are crucial in many chemical reactions.

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