Hydrogen Atom

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Quantum Mechanics A
Schrödinger Equation
The most fundamental equation of quantum mechanics; given a Hamiltonian \mathcal{H}, it describes how a state |\Psi\rangle evolves in time.
Basic Concepts and Theory of Motion
UV Catastrophe (Black-Body Radiation)
Photoelectric Effect
Stability of Matter
Double Slit Experiment
Stern-Gerlach Experiment
The Principle of Complementarity
The Correspondence Principle
The Philosophy of Quantum Theory
Brief Derivation of Schrödinger Equation
Relation Between the Wave Function and Probability Density
Stationary States
Heisenberg Uncertainty Principle
Some Consequences of the Uncertainty Principle
Linear Vector Spaces and Operators
Commutation Relations and Simultaneous Eigenvalues
The Schrödinger Equation in Dirac Notation
Transformations of Operators and Symmetry
Time Evolution of Expectation Values and Ehrenfest's Theorem
One-Dimensional Bound States
Oscillation Theorem
The Dirac Delta Function Potential
Scattering States, Transmission and Reflection
Motion in a Periodic Potential
Summary of One-Dimensional Systems
Harmonic Oscillator Spectrum and Eigenstates
Analytical Method for Solving the Simple Harmonic Oscillator
Coherent States
Charged Particles in an Electromagnetic Field
WKB Approximation
The Heisenberg Picture: Equations of Motion for Operators
The Interaction Picture
The Virial Theorem
Commutation Relations
Angular Momentum as a Generator of Rotations in 3D
Spherical Coordinates
Eigenvalue Quantization
Orbital Angular Momentum Eigenfunctions
General Formalism
Free Particle in Spherical Coordinates
Spherical Well
Isotropic Harmonic Oscillator
Hydrogen Atom
WKB in Spherical Coordinates
Feynman Path Integrals
The Free-Particle Propagator
Propagator for the Harmonic Oscillator
Differential Cross Section and the Green's Function Formulation of Scattering
Central Potential Scattering and Phase Shifts
Coulomb Potential Scattering
Illustration of the hydrogen atom.

We now discuss the solution of the Schrödinger equation for the hydrogen atom. We are especially interested in this system because it is of direct physical interest and because it is possible to solve it exactly.

The effective one-dimensional problem for this system is

\left[ -\frac{\hbar^2}{2\mu}\frac{d^2}{dr^2}+\frac{\hbar^2}{2\mu}\frac{l(l+1)}{r^2}-\frac{Ze^2}{r}\right] u_{nl}=Eu_{nl},

where Z=1\! represents the hydrogen atom, Z=2\! represents the helium ion, He^+,\! and so on. Here, \mu\! is the effective mass of the atom.

We will focus on the bound states here. To solve the above equation, let us begin by writing down its solutions in the limits of small and large r\!.

In the limit of small r;\! i.e., r \to 0, the equation becomes

\left[ -\frac{\hbar^2}{2\mu}\frac{d^2}{dr^2}+\frac{\hbar^2}{2\mu}\frac{l(l+1)}{r^2}\right] u_{nl}=0.

The only solution to this equation that is not divergent as r\to 0 is u_{nl}(r)\sim r^{l+1}.\!

In the opposite limit, r \to \infty, we obtain

\frac{d^2 u_{nl}}{dr^2}+\frac{2\mu E}{\hbar^2}u_{nl}=0.

The only solution to this equation that does not diverge as r\to\infty is u_{nl}(r)\sim e^{-r/a},\! where a=\sqrt{\frac{-\hbar^2}{2\mu E}}.

Let us now define \kappa=a^{-1}.\! The above asymptotic limit for large r\! can now be written as

u_{nl}(r)\sim e^{-\kappa r}.\!

We now assume that the full expression for u_{nl}(r)\! has the form, u_{nl}(r)=(\kappa r)^{l+1}e^{-\kappa r}W(\kappa r).\!

To simplify the equation, let us introduce the dimensionless radial coordinate, \rho=\kappa r,\! so that u_{nl}(r)\! may now be written as u_{nl}(\rho)=\rho^{l+1}e^{-\rho}W(\rho).\!

Substituting this into the effective Schrödinger equation and simplifying, it becomes


where \rho_{0}=Ze^{2}\sqrt{\frac{2\mu }{\hbar^{2}E}}.

Let us now try a series solution for W(\rho):\!

W(\rho)=a_0+a_1 \rho+a_2\rho^2+...=\sum_{k=0}^\infty a_k \rho^k

Our equation now becomes

\sum_{k=0}^\infty (a_{k}k(k-1)\rho^{k-2}+2(l+1)k\rho^{k-2}a_k-2\rho^{k-1}a_k k)+\sum_{k=0}^\infty(\rho_0 a_k\rho^{k-1}-2(l+1)a_k\rho^{k-1})=0,

or, upon simplification,

\sum_{k=0}^\infty (a_{k+1}(k+1)k\rho^{k-1}+2(l+1)(k+1)\rho^{k-1}a_{k+1}-2\rho^{k-1}a_k k+(\rho_0-2(l+1))a_k\rho^{k-1})=0.

Setting the coefficients of all powers of \rho\! to zero, we obtain




In the limit of large k,\! the recursion relation becomes




These are the coefficients of the series for e^{2\rho}.\! We therefore see that, unless we terminate the series at a finite order (i.e., we make W(\rho)\! a polynomial), the wave function will diverge as r\to\infty. If we wish to terminate the series at N^{\text{th}}\! order, we set a_{N+1}=0.\! This yields the condition,


If we now solve this for the energy, we obtain the energy eigenvalues of the system,

E_{Nl}=-\frac{Z^2\mu e^4}{2\hbar^2(N+l+1)^2}.

The recursion relation now becomes


The function, W(\rho),\! can be expressed in terms of the confluent hypergeometric function,

_1F_1(a,c,z)=1+\frac{a}{c}\frac{z}{1!}+\frac{a(a+1)}{c(c+1)}\frac{z^2}{2!}+...=\sum_{k=0}^\infty a_k z^k,

which is a solution of Kummer's equation,

z\frac{d^2w}{dz^2} + (b-z)\frac{dw}{dz} - aw = 0.\,\!

If we assume a power series solution as before, then the recursion relations are


Comparing this form to the recursion relations for our solution for W(\rho),\! we see that





Therefore, we may write W(\rho)\! as

W(\rho)=C _1F_1(-N,2(l+1),2\rho),\!

where \rho=\kappa r=\sqrt{\frac{-2\mu E}{\hbar^2}}r.

The full normalized wave function is given by

\psi_{n,l,m}(r,\theta,\phi)=\frac{e^{-\kappa r}(2\kappa r)^l}{(2l+1)!}\sqrt{\frac{(2\kappa)^3(n+l)!}{2n(n-l+1)}}\  _1F_1(-n+l+1,2(l+1),2\kappa r)Y_{l}^m(\theta,\phi),

where we have introduced the more commonly-used principal quantum number n=N+l+1.\!

The first few normalized wave functions for the hydrogen atom are as follows

\psi_{100}= \dfrac{e^{-r/a}}{\sqrt{\pi a^3}}

\psi_{200}= \dfrac{e^{-r/2a}}{\sqrt{32\pi a^3}} \left( 2-\dfrac{r}{a} \right)

\psi_{210}= \dfrac{e^{-r/2a}}{\sqrt{32\pi a^3}} \left( \dfrac{r}{a} \right) \cos(\theta)

\psi_{2 \pm 10}= \dfrac{e^{-r/2a}}{ \sqrt{64\pi a^3}} \left( \dfrac{r}{a} \right) \sin(\theta) e^{\pm i \phi}

The energy may be written as

E=-\frac{Z^2\mu e^4}{2\hbar^2 n^2}=-\frac{Z^2}{n^2}\,\text{Ry},

where the Rydberg \text{Ry}=13.6\,\text{eV}\! for the hydrogen atom and n=1,2,3,...\! The degeneracy of each energy level is n^2.\!

To the side is a chart that depicts the energy levels for the hydrogen atom graphically for n=1,2,3\! in units of \text{Ry}\!. The parenthesis indicates the degeneracy due to possibile values of the magnetic quantum number m from l to + l.


(1) (N. Zettili, Quantum Mechanics: Concepts and Applications, Exercise 6.3)

An electron in a hydrogen atom is in the energy eigenstate, \psi_{2,1,-1} \left(r, \theta, \phi \right) = Nre^{-r/2a}Y_1^{-1}\left(\theta, \phi \right).

(a) Find the normalization constant, N.\!

(b) What is the probability per unit volume of finding the electron at r = a,\! \theta = 45^{\circ},\! and \phi = 60^{\circ}?\!

(c) What is the probability per unit radial interval dr\! of finding the electron at r = a?

(d) What are the expectation values of \hat{\mathbf{L}}^2 and \hat{L}_{z}?


(2) (Griffiths, Quantum Mechanics, Problems 4.13 and 4.14)

(a) Find \langle r\rangle and \langle r^2\rangle for an electron in the ground state of hydrogen. Express your answers in terms of the Bohr radius a.\!

(b) What is the most probable value of r\! in the ground state of hydrogen?


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