Lecture 20

Spherical Harmonics

http://www.hep.shef.ac.uk/phy226/

Introduction
We can all imagine the ground state of a particle in an infinite quantum well in 1D

X Or the 2D representation of 2 harmonics of a wave distribution in x and y interacting on a plate

Y X
www.falstad.com/mathphysics.html

Visualisation of the spherical harmonics in a 3D spherical potential well is more tricky !!!!!

Introduction
Lets think about the Laplace equation in 3D In 3D Cartesian coordinates we write:

" 2 #(x, y, z) = 0

In spherical polar coordinates we stated that:

1 #$ 2 #' 1 # $ #' 1 #2 " = 2 &r )+ 2 &sin * ) + 2 #* ( r sin 2 * #+ 2 r #r % #r ! r sin * #* % (

2

and so the Laplace equation in spherical polar coordinates is:

" 2 #(r, $ , % ) = 0

Comparing the Cartesian case with the spherical polar case, it is not difficult to believe that the solution will be made up of three separate functions, each comprising an integer variable to define the specific harmonic solution.

! "(x, y, z) = X (x)Y ( y)Z(z)

e.g.

"(r, # , $ ) = R(r)P(# )F($ )

"(r, # , $ ) = Are%r 2a 0 (sin # )e i$

"(x, y, z) = Asin k x x sin k y y sin k z z

Schrdinger equation in 3D coordinates

Lets consider now the Schrdinger equation in 3D. In 3D Cartesian coordinates we write:

!2 2 " # $ + V (x, y, z)$(x, y, z) = E$(x, y, z) 2m

In spherical polar coordinates we stated that:

1 #$ 2 #' 1 # $ #' 1 #2 " = 2 &r )+ 2 &sin * ) + 2 !r #r #* ( r sin 2 * #+ 2 % #r ( r sin * #* %

2

and so the Schrdinger equation in spherical polar coordinates is:

!2 2 " # $(r, % , & ) + V (r)$(r, % , & ) = E$(r, % , & ) 2m

Here again the solution can be factorised, i.e. the solution is the product of three separate functions, each comprising an integer variable to define the specific harmonic solution. !

"(r, # , $ ) = R(r)P(# )F($ )

Electron orbitals for the Hydrogen atom

This topic underlies the whole of atomic and nuclear physics. Next semester in atomic physics you will cover in more detail the spherical polar solutions of the Schrdinger equation for the hydrogen atom. Bohr and Schrdinger predicted the energy levels of the H atom to be:

En = "

13.6eV n2

This means that the energy of an electron in any excited orbital depends purely on the energy level in which it resides. From your knowledge of chemistry, you will know ! that each energy level can contain more than one electron. These electrons must therefore have the same energy. We say that there exists more than one quantum state corresponding to each energy level of the H atom. (Actually there are 2n2 different quantum states for the nth level). For the 1D case it was sufficient to define a quantum state fully using just one quantum number, e.g. n = 2, because our well extended only along the x axis. In 3D we have to consider multiple axes within a 3D potential well, and since the probability density functions corresponding to the electron probability clouds (EPCs) are mostly not radially symmetric, we must represent wavefunctions with the same energy but different eigenfunctions, using a unique set of quantum numbers. The quantum numbers for polar coordinates corresponding to (r, " , # ) are (n,l, m)

Electron orbitals for the Hydrogen atom

An electron probability cloud (EPC) is a schematic representation of the likely position of an electron at any time. This figure shows the EPCs corresponding to the ground state and some excited states of the hydrogen atom. For each energy level there are several different EPC distributions corresponding to the different 3D harmonic solutions for that energy level.

The quantum numbers for polar coordinates corresponding to (r , " , ! ) are (n, l , m)

Electron orbitals for the Hydrogen atom

n is defined as the principal quantum number (and sets the value of the energy level of the wave). For each wave with quantum number n, there exist quantum states of l from l = 0 to l = (n - 1) where l is defined as the orbital quantum number. So for example an electron in the 2nd excited state can be in (n=3, l=0), or (n=3, l=1) or (n=3, l=2) quantum states. Each one of these states has further states represented by quantum number m defined as the magnetic quantum number, a positive or negative integer where |m| " l .

Electron orbitals for the Hydrogen atom

The full solution "(r, # , $ ) = R(r)P(# )F ($ ) , for the ground state and first few excited states corresponding to each specific combination of quantum numbers is shown below. a0 is the Bohr radius corresponding to the ground state of the H atom ..
Quantum numbers for 3D spatial ! geometry n l m 1 2 2 2 3 3 3 3 0 0 1 1 0 1 1 2 Normalised solution of the TISE for Hydrogen atom P( ) 1 2 1 2
6 cos 2 3 sin 2 1 2 6 cos 2 3 sin 2 10 2 3cos 1 4

R (r ) 2 r a0 e 0 3 a0 2 1 r r 2a 0 0 2 e 3 a0 2 2a0 2 r r 2a 1 0 0 e 3 2 6a0 2 a0 r r 2a 1 0 1 e 3 2 2 6a0 a0 2 r r 2 r 3a 0 0 27 18 + 2 2 e 3 a0 a 0 81 3a0 2 4 r r r 3a 0 0 6 e 3 a0 a0 81 6a0 2 4 r r r 3a 0 1 6 e 3 2 a0 a0 81 6a0 4 r 2 r 3a 0 e 0 2 3 81 30a0 2 a0

F( ) 1 2 1 2
1 2 1 2 1 2 1 2 1 2 1 2 e i e i

Electron orbitals for the Hydrogen atom

Once we have the solution to the Schrdinger equation in 3D spherical polar coordinates we can deduce the probability function. For example the probability density function in 3D for ground state (1,0,0) can be calculated using the wavefunction for this state:

2 ! r a0 1 # (r , " , ! ) = R (r ) P (" ) F (! ) = 3 2 e a0 2

1 1 = e !r a 3 " a0 2 2!

The radial probability density for the hydrogen ground state is obtained by multiplying the square of the wavefunction by a spherical shell volume element.

' 1 *2 2 1 &2r a 0 &r a 0 "(r, # , $ ) = ) e , = 3e ) , %a 32 % a0 ( + 0

$

So

1 #2r a 0 dP = 3 e 4 "r 2 dr "a0

$

If we integrate over all space P =

%
0

1 #2r a 0 e 4 "r 2 dr = 3 "a0

%
0

!
we can show that the total probability is 1.

4r 2 #2r a 0 e dr 3 a0
/

2 3 4 ) "2r a 0 # "a0r 2 a0 r a0 &, P = 3 +e " " (. = 1 % 2 2 4 '-0 a0 * $

Electron orbitals for the Hydrogen atom

Probability density function in 3D for ground state (1,0,0) is

1 #2r a 0 dP = 3 e 4 "r 2 dr "a0

Electron orbitals for the Hydrogen atom

It would be very interesting to plot the full 3D probability density distributions for each combination of quantum states. Unfortunately, distributions for non spherically symmetric solutions (i.e. p and d quantum states) are functions of and as well as of radius r making them exceedingly difficult to plot.

Electron orbitals for the Hydrogen atom

If we were to plot only the probability density functions for spherically symmetric solutions (i.e. s quantum states) for each quantum state n we would find the following distributions corresponding to the EPCs shown earlier for hydrogen.

Electron orbitals for the Hydrogen atom

Spherical Harmonics The solution of a PDE in spherical polar coordinates is

"(r , # , $ ) = R(r)P(# )F($ )

We can say that the solution is comprised of a radially dependent function R(r) and two angular dependent terms P(" )F(# ) which can be grouped together to form specific spherical harmonic solutions Yl m! , # ) . ("
!

!
m Formally the spherical harmonics Yl (" , # ) are the angular portion of the solution to Laplace equation in spherical coordinates derived in the notes (see Appendix).

! The spherical harmonics Yl m (" , # ) can be directly compared to the P(" ) and F(" )

solutions for the wavefunction describing the electron orbitals of the hydrogen atom.
!
!

Electron orbitals for the Hydrogen atom

Spherical Harmonics Spherical harmonics are useful in an enormous range of applications, not just the solving of PDEs. They allow complicated functions of and to be parameterised in terms of a set of solutions. For example a summed series of specific harmonics as a Fourier series can be used to describe the earth (nearly but not exactly spherical). Summing harmonics can produce some really pretty shapes
http://www.lifesmith.com/spharmin.html

Oil droplets or soap bubbles oscillating

m Spherical Harmonics Yl (" , # ) also describe the wobbling deformations of an

oscillating, elastic sphere. What sine and cosine are for a one-dimensional, ! linear string, the spherical harmonics are for the surface of a sphere. A tiny oil droplet is placed on an oil bath which is set into vertical vibrations to prevent coalescence of the droplet with the bath. The droplet, which at rest would have spherical form due to surface tension, bounces periodically on the bath. A movie shows the oscillations of the drop and the corresponding calculations using spherical harmonics Yl m (" , # ) with = 2, 3, 4 and m = 0. The magnetic quantum number m determines rotational symmetry of the wobbling around the ! vertical axis. For m 0, deformations are not symmetric with respect to the vertical, and in this case, the droplet starts to move around on the oil bath. This can be seen in a second movie.

Oil droplets or soap bubbles oscillating

Oil droplets or soap bubbles oscillating