Linearity, Symmetry, and Prediction

David Ding
February 3, 2012
Abstract
These are my notes from the book Linearity, Symmetry, and Prediction in the Hydrogen Atom
1 The setting: Hilbert space
In quantum theory, the wave function is an element of the Hilbert space L
2
(R
3
), which consists of all
measurable functions from R
3
to C such that

R
3
[f[
2

We dene the inner product of two functions and as
, =

R
3

,
and two functions
1
and
2
are dened as equivalent if [,
1
[ = [,
2
[ for all functions . Technically,
we ought to work with the projective space PL
2
since we only care about normalized wave-functions up to
a phase, so a function and a are identical.
Denition 1. Let B be an arbitrary subset of V , a complex inner-product space. Then, the perpendicular
space of B is
B

= x V : y B, x, y = 0.
We say that a subset B of V spans V if B

= 0; this denition is equivalent to the standard denition

for nite-dimensional vector spaces V .
Denition 2. Let / be a set of complex-valued functions on a set S, and let f : S C. Then, f can
be uniformly approximated by elements of / if and only if, for every > 0, there exists / such that
[f(x) (x)[ < for all x S.
Theorem 1 (Stone-Weierstrass). Let / be a subalgebra of the algebra of all complex-valued functions on
a compact set S. Suppose
1. / is closed under complex conjugation: if f /, then f

/, where f

(x) = (f(x))

,
1
2. / separates points in S: if x, y S with x ,= y, then there is a f / such that f(x) ,= f(y),
3. For every x S, there is a f / such that f(x) ,= 0.
Then, any continuous function on S can be uniformly approximated by functions in /.
In particular, the algebra of polynomials satisfy the above conditions, and so any continuous function
can be approximated by polynomials (the Bernstein polynomials). Note that this does not imply every
continuous function can be approximated by a power series; the coecients of a Bernstein approximations
do not necessarily converge, even though the polynomials approximate better and better.
1.1 Important Vector Spaces
In non-relativistic quantum theory, R
3
is the ambient physical space. Quantum states are described
by vectors in the Hilbert space L
2
(R

). When using spherical coordinates, it often suces to consider

the Hilbert space L
2
(S
2
), where S
2
is the 2-sphere. We are also interested in the space T
l
n
, the space of
homogeneous polynomials in n variables of degree l. Finally, we are interested in the space H
l
, the subspace
of T
l
3
whose vectors/functions satisfy the Laplace equation:
H
l
= f T
l
3
:
2
f = 0,
and the restriction to S
2
, }
l
. The space }
l
is equal to the space spanned by spherical-harmonics of order
l. The space } is the direct sum of all }
l
.
2 Important Groups and Representations
In the quantum mechanics of the hydrogen atom, the Lie groups SO(3), SO(4), and SU(2) are critical.
The Lie group SO(3) arises as the rotational symmetry of the ambient space. It has a natural repre-
sentation over R
3
, which induces the representation over L
2
(R

): if g SO(3), L
2
(R

), and x R

is any variable, then

(g)(x) := (g
1
x).
Recall that irreducible representations of SO(3) are given by V
n
, where n is the highest weight. The
dimension of V
n
is 2n + 1.
Theorem 2. The space H
l
is an irreducible subrepresentation of L
2
(R
3
) isomorphic to V
l
.
3 Physical importance of representations
As mentioned before, in quantum mechanics, the state of a system is determined by a function in the
Hilbert space R
3
. When we measure a system for any observable (such as momentum, position, energy,
and angular momentum), the result usually cannot be deterministically predicted; rather, the best we can
do is to predict the probabilities of measuring a specic value. There are certain states

, called base
states, that do have a well-dened value for a certain observable. For instance, there might be a state
E
for
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energy, such that every measurement of an object in the state
E
will return E for the energy. These base
states are the eigenvectors of some hermitian linear operator, which are associated with some observable.
Linear algebra gives that the eigenvalues of a hermitian linear operators are real, and the eigenvectors
could be normalized to be orthonormal. Physicists also assume that these eigenvectors always form a basis
for the Hilbert space. Given an arbitrary state , the only possible values of energy (respectively, position,
momentum, angular momentum) that can be measured are the eigenvalues of the energy operator. If E
1
is an eigenvalue, then the probability of measuring E
1
for the energy is given by [
E
1
, [
2
. In addition,
Paulis Exclusion Principle states that no two fermions (which include electrons) can occupy the same
quantum state. Since for complex represent the same physical state, Paulis exclusion principle
states that no more than n particles can occupy an n-dimensional subspace of L
2
(R
3
).
Suppose we are measuring the state of a hydrogen atom in a laboratory. Hydrogen atoms are rotationally
symmetric under the group SO(3) of rotations of the ambient physical space. If we have an observer at
a certain location, and we apply the rotation g SO(3) to him, he should measure the same properties
of the hydrogen atom; however, to him, the state of the hydrogen atom changes from to (g), where
is the induced representation on L
2
(R
3
). Thus, the only physically meaningful subspaces of L
2
(R
3
)
correspond to representations of SO(3), since (g) is equivalent to for all g SO(3). Moreover, we can
break each subspace into irreducible representations, which represent the elementary states. All vectors in
an elementary state must be physically equivalent, since each vector can be transformed into every other
vector.
4 Prediction in the Hydrogen Atom
Theorem 3. The induced representation of SO(3) on T
l
3
of homogeneous polynomials of degree l in three
variables is isomorphic to
H
l
H
l2
H
0 or 1
under the mapping
(p
l
, . . . , p
0 or 1
) p
l
+r
2
p
l2
+r
4
p
l4
+ +r
l0 or 1
p
0 or 1
,
where r
2
= x
2
+y
2
+z
2
.
Thus, any polynomial on S
2
can be written as a sum of harmonic polynomials, and thus, by the
Stone-Weierstrass theorem, any function in L
2
(S
2
) can be uniformly approximated by a sum of harmonic
polynomials. The analogous theorem, regarding the span of L
2
(R
3
) by harmonic polynomials, is given by
the below theorem:
Theorem 4. Let J be the functions in L
2
(R
3
) that are invariant under SO(3); that is, J is the subalgebra
of functions of only r, the radial coordinate. Then, J } spans L
2
(R
3
).
Now, if f J and F is the one-dimensional subspace of J spanned by f, then F }
l
is an irre-
ducible representation of SO(3) (isomorphic to }
l
, of course). Moreover, it is clear that these are the only
irreducible subrepresentations of L
2
(R
3
).
Therefore, we can predict that every elementary state of the hydrogen atom (or any other spherically
symmetric system) has either 1, 3, 5, ... dimensions. Let us call the rst elementary state the s-shell,
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the second the p-shell, the third the d-shell, and the fourth the f-shell. Any two electrons in the same
shell should have the same energy distribution, same momentum distribution, or the same distribution for
any observable, since by rotating the atom (or the laboratory), we can rotate the state of one electron
to another. By Paulis exclusion principle, the s-shell can only hold one electron; the p only three, the
d only ve, and the fourth only seven. This is actually incorrect, since we forgot to account for spin; by
accounting for spin, we predicted, using only the assumption of spherical symmetry, that the s-shell has
two electrons, the p six, the d ten, and the f fourteen, a result well known to physicists and chemists.
References
[1] Stephanie Frank Singer, Linearity, Symmetry, and Prediction in the Hydrogen Atom. Springer, New
York, 2005.
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