1.

Review of Basic Quantum Mechanics

Contents

Review quantum mechanics postulates, angular momentum theory and hydrogen atom
electronic structure.

Notes

Review1: Postulates of Quantum Mechanics

Postulate 1. The state of a quantum mechanical system is completely

specified by a function that depends on the coordinates of the

particle(s) and on time. This function, called the wave function or

state function, has the important property that is the

probability that the particle lies in the volume element located at

at time .
The wavefunction must satisfy certain mathematical conditions
because of this probabilistic interpretation. For the case of a single
particle, the probability of finding it somewhere is 1, so that we have
the normalization condition

(1.1)

It is customary to also normalize many-particle wavefunctions to 1.

The wavefunction must also be single-valued, continuous, and finite.
Postulate 2. In any measurement of the observable associated with
operator ,the only values that will ever be observed are the
eigenvalues , which satisfy the eigenvalue equation

(1.2)

This postulate captures the central point of quantum mechanics--the values of

 dynamical variables can be quantized (although it is still possible to have a continuum
of eigenvalues in the case of unbound states). If the system is in an eigenstate of
with eigenvalue , then any measurement of the quantity will yield .
Although measurements must always yield an eigenvalue, the state
does not have to be an eigenstate of . An arbitrary state can be

expanded in the complete set of eigenvectors of ( as

(1.3)

where may go to infinity. In this case we only know that the

measurement of will yield one of the values , but we don't know

which one. However, we do know the probability that eigenvalue

will occur--it is the absolute value squared of the coefficient, .

This leads to our third postulate.

Postulate 3. If a system is in a state described by a normalized wave
function ,then the average value of the observable corresponding to
is given by

(1.4)

Postulate 4. To every observable in classical mechanics there

corresponds a linear, Hermitian operator in quantum mechanics.
This postulate comes about because if we require that the expectation value of an
operator is real, then must be a Hermitian operator. Some common operators
occuring in quantum mechanics are collected in Table 1:

Table 1: Physical observables and their corresponding quantum operators (single particle)

Observable Observable Operator Operator

Name Symbol Symbol Operation

Position Multiply by
Momentum

Kinetic energy

Potential energy
Multiply by

Total energy

Angular momentum

Postulate 5. The wavefunction or state function of a system evolves in

time according to the time-dependent Schrdinger equation

(1.5)

The central equation of quantum mechanics must be accepted as a postulate.

Postulate 6. The total wavefunction must be antisymmetric with
respect to the interchange of all coordinates of one fermion with those
of another. Electronic spin must be included in this set of coordinates.

[To be studied in the next lecture].

Review 2: The Angular Momentum Operators

We start from the classical expression for angular momentum,

, to obtain the quantum mechanical version ,

where , , and are all three-dimensional vectors. This

definition leads immediately to expressions for the three

components of L:
 = (2.1)

= (2.2)

= (2.3)

From these definitions, we may easily derive the following commutators

= (2.4)

= (2.5)

= (2.6)

where the indices i,j,k can be x, y, or z, and where the coefficient is unity if i,j,k

form a cyclic permutation of x,y,z[i.e., (x,y,z), (y,z,x), or (z,x,y)] and -1 for a reverse
cyclic permutation [(z,y,x), (x,z,y), or (y,x,z)]. The final commutator indicates that we
cannot generally know Lx, Ly, and Lzsimultaneously except if we have an eigenstate
with eigenvalue 0 for each of these.
Classically, any component of the angular momentum must be less
than or equal to the magnitude of the overall angular momentum
vector. Quantum mechanically, the average value of any component
of the angular momentum must be less than or equal to the square

root of the expectation value of dotted with itself:

(2.7)

is simply .
Since commutes with any component , we can have

simultaneous eigenfunctions of and a given component . We

usually pick the z axis, since the expression for is the easiest of

the three when we work in spherical polar coordinates:

= (2.8)

= (2.9)

= (2.10)

Of course it is also possible to express in terms of the unit vectors

for spherical polar coordinates,

= (2.11)

= (2.12)

= (2.13)

Here,

(2.14)

and
 =

= (2.15)

The simultaneous eigenfunctions of and are called the

spherical harmonics, , where lis the total angular

momentum quantum number, and m is the so-called magnetic

quantum number. The spherical harmonics are defined as

(2.16)

where Plm are the associated Legendre polynomials. We require that ,

and spherical harmonics with m<0 are defined in terms of the spherical harmonics
with m>0 according to Ylm = (-1)m [ Yl-m]*. The spherical harmonics are normalized
over integration of angular coordinates such that

(2.17)

and they have the following special properties:

= (2.18)

= (2.19)
It can be useful to define ladder operators for angular momentum.
The following ladder operators work not only for straight angular

momentum , but also for combined angular momenta such

as . If

(2.20)

then

(2.21)

We can see that these ladder operators raise or lower the magnetic quantum number m
but leave l alone.
One can also show that in spherical polar coordinates

(2.22)

By comparing this expression with that for in spherical polar coordinates,

(2.23)

we can see that the Hamiltonian can be written as

= (2.24)
Clearly commutes with the kinetic energy term, has no r dependence.

Likewise, if , then commutes with the whole Hamiltonian. Hence, for

problems where the potential depends only on r (central force problems), we can find

simultaneous eigenfunctions of , , and .

The most important property for an angular momentum operator is eq.

(2.6) from which almost all other properties can be derived. For the
electron, the spin is just a form of angular momentum, but it is
intrinsic meaning it cannot be expressed into the form like eqs.(2.1-3)
or eqs.(2.15,22). However, we can still find out the eigenvalues of the
spin angular momentum operators of the electron. [To be studied in
the next lecture].

Review 3. Hydrogen Atom

Finally, consider the hydrogen atom as a proton fixed at the origin, orbited by an

electron of reduced mass . The potential due to electrostatic attraction is

(3.1)

in SI units. The kinetic energy term in the Hamiltonian is

(3.2)

so we write out the Schrdinger equation in spherical polar coordinates as

(3.3)

It happens that we can factor into , where are

again the spherical harmonics. The radial part then can be shown to obey the

equation

(3.4)
which is called the radial equation for the hydrogen atom. Its (messy) solutions are

(3.5)

where , and is the Bohr radius, . The functions

are the associated Laguerre functions. The hydrogen atom

eigenvalues are

(3.6)

There are relatively few other interesting problems that can be

solved analytically. For molecular systems, one must resort to
approximate solutions.
When the electron spin is considered, to a good approximation,
the Hamiltonian of hydrogen atom will be the same if there is
no magnetic field applied to it. Therefore the energy
eigenequation will be the same except the eigenfunctions are
modified so that the spin wavefunctions are taken into account:

(r,)
nlm nlm(r,) g(ms) (3.7)

where g(ms) is the spin state which is generally a linear combination of

and : g(ms)=c1+c2. There are two choices for c1 and c2. Therefore,
the degeneracy of hydrogen atom eigenstate is changed into 2n2.

[To be studied in the next lecture].

References

Textbook pp.1-282.

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