VISUALIZING

Eigenfunctions, Wave Functions and

Orbitals

Excel to understand what we are plotting

3D (GeoWall) to explore the plots
 Outline
Background (the math, physics, and chemistry
perspectives on )
Some questions
connections btwn chem and phys views?
Getting at some answers
Using Excel
Using 3D visualization
 What are we visualizing
Math: Eigenfunctions to the Separable Partial
Differential Equation.
Physics: Wavefunctions of the Hydrogen Atom
with Definite Energy, Angular Momentum,
and z-component of Angular Momentum.
Chemistry: Orbitals of Hydrogen-like Atoms
key to bonding.
 What are we visualizing?
The probability that an electron will be found at
a particular location.
The electron is bound to a nucleus (charge Z).
Assume no effect from other electrons! (and
this is ok!)
The wave function
 The wave function z

=R(r)()() y
| |2 (= *) tells us probability x

Rn,l(r) tells us how it varies with distance

(constant direction)
l,m () tells us how it varies with angle to z axis
along an arc
m () tells us how it varies with angle along a
circle centered on z axis.
 Specific case: What do the angular
solutions for n=3, l=2, m=1 look like?

Math and physics say:

From Mathematica

Chemistry says:
From Orbital Viewer
 WHAT ARE WE PLOTTING???

Using Excel to visualize the solutions

The Excel spreadsheet has macros for creating

the n=3, l=2, m=1 solutions.
 Using Excel to understand the plots
Use ctrl-s to calculate the values of at points in the
y-z plane for (nlm)=(3,2,1)
The size of the bubbles is proportional to the value of

Use ctrl-b to highlight the points along an arc or a
radius.
Observe the shape of the plot of vs. r for various angles,
or vs. for various r.
Can you see what R, , are doing, individually? What
does separable mean?
 What do these mean? Where do they
come from?
Now, you need to know what the functions
are!
You can find the PDE (Schrodingers equation,
with the Coulomb potential) HERE
YIKES!!!
 solutions
They worked out the solutions for some values
of n, l, and m.
Dont worry about the constants. Do note:
R is exponentials times Laguerre polynomials
(Mathematica knows about these)
is Legendre Polynomials of cos() (Mathematica
knows about these, too)
m ()=eim which has magnitude 1!
 N=3, l=2, m=1
Can you tell from the mathematical solutions
how each part (R, , ) behaves?
Does the Excel plot match your
understanding?
Can you explain in physics terms what the
picture show?
 Alt-F11 opens the macro window.
Manually change the function for . We have n=3,
l=2, m=1. What does n=3, l=2, m=-1 look like?

What should these look like in 3D?

{Mathematica or MathCad might be nicer!}

These know about complex numbers (a+ib).
Try plotting | *| using the math equations.
Create and plot linear combinations.
 Orbitals vs. Wavefunctions
The orbital viewer (http://www.orbitals.com/)
orbitals dont look like that. Why????
The solutions you have seen are complex.
Orbital Viewer plots a real function that is a
linear superposition of two complex solutions.
What does that mean mathematically?
What does that mean physically?
 m
Are the physics ms the same as the chemistry
ms? (NO!)
What is the relationship???
What does m tell us in physics? What does it
tell us in chemistry?
 3D visualization
Now that we understand something about what the
plots represent and
We have some questions
Lets explore some 3D pictures!
Revisit the questions:
What does m tell us in physics? How does that show up in
the pictures?
What does m tell us in Chemistry? How does that show up
in the pictures?
How can we construct an orbital picture (chem) in Excel or
the 3D visualization using the math/physics wave function
data?
 Questions to explore
Math: What is an eigen-function? What is an
eigenvalue? What are the properties of nth-order
polynomials? What is linear superposition?
Physics: What do the solutions look like? How does
the physics of angular momentum relate to the plots?
What is linear superposition?
Chemistry: What do the orbitals mean??? What
about more than one atom?
 Useful links
http://chemviz.ncsa.uiuc.edu/content/demo-waltz3.html
http://www.chm.davidson.edu/ChemistryApplets/AtomicOrbitals/d-orbitals.html has the fuzzy cloud pictures of
orbitals
http://mathworld.wolfram.com/SphericalHarmonic.html has the mathematica functions and output for
eigenfunctions of the angular PDE
http://www.orbitals.com/ Has a nice orbital rendering program for download. It draws the orbitals (as used in
chemistry) for one or more atoms. The orbital is the region where the probability is greater than a specified
value. Phase (+ or -) is indicated by color.
Useful features:
Can choose any n<30, and any l, m for these ns
Can visualize wavefunction for superposition of more than one atom. By placing two atoms in same location,
can create superpositions of the wavefunction.
3D features:
Can set transparency of rendering so that can look through the drawing for 3D information
Can watch as orbital is constructed to see inside before the surface gets covered
Can set probability for outer surface, and can animate sequence for drawing surfaces of decreasing probability
(slice in probability space)
Can render drawings for stereoscopic viewing
Caveat:
The orbitals are NOT the eigenfunctions of the Lz operator. The orbital for m is actually the superposition
for the two real-valued linear superpositions of the +m and m solutions.
http://www.orbitals.com/orb/ov.pdf pdf file explaining orbial drawing software.
 Non sequitur
Is there quasidiffusion in biological systems?

Quasidiffusion = the random walk, but time dependent

mean free path.
In physics (e.g. phonons in crystal) mean free path and
life time both depend on energy. As phonons decay,
step size gets longer, but rate of decay also slows
down.
See: J. P. Wolfe or M. Msall or H. J. Maris, etc (phonon
quasidiffusion)
In biology ?