Elements of Quantum Mechanics

and the H Atom 2

Quantum mechanics provides the tools for a quantitative

understanding of atoms and molecules. The reader is expected
to be familiar at least with the main concepts. Here we want to
repeat and refurbish the most important notions and methods so
that we can work with them directly in the following chapters.

Overview
If the reader is already familiar with quantum mechanics he may just want
to browse this chapter and return later if necessary. However, readers who
have experienced quantum mechanics up to now only as compulsory math-
ematical exercise may perhaps read this chapter with advantage and find it
helpful to approach the indispensable instruments without big formal hurdles.
In Sects. 2.12.3 we summarize a minimum of formalism. Section 2.4 treats
as a first example the well known particle in a box and the free electron gas
which in atomic and solid state physics is an important elementary model.
Section 2.5 gives an overview of how to treat angular momenta, needed in
all following text, specified in Sect. 2.5.4 for the electron spin s = 1/2. Sec-
tion 2.6 offers a crash course in nonrelativistic quantum mechanics of the
H atom essential knowledge for all the following chapters. We refrain here
from formal derivations in favour of a plausible, possibly somewhat hand wav-
ing introduction. Finally, Sect. 2.7 presents a first, elementary approach to in-
teractions of atomic electrons with external fields, which will be extended and
deepened in Chap. 8. Clearly, such a brief introduction into quantum mechan-
ics cannot substitute a profound study of the formal theory. It should, however,
facilitate the access to it and make the reader fit for the following chapters.

2.1 Matter Waves

2.1.1 Limits of Classical Theory

The classical picture of a well defined trajectory with known coordinate x(t) and
momentum p(t) looses its validity in quantum mechanics, as sketched in the phase

Springer-Verlag Berlin Heidelberg 2015 87

I.V. Hertel, C.-P. Schulz, Atoms, Molecules and Optical Physics 1,
Graduate Texts in Physics, DOI 10.1007/978-3-642-54322-7_2
88 2 Elements of Quantum Mechanics and the H Atom

diagram Fig. 2.1: position and momentum cannot be measured simultaneously. They
may only be determined with an accuracy in accordance with the uncertainty rela-
tion pi xi h/2 . Quantum mechanics only makes statements about probability
amplitudes (r, t). These may assume the form of so called Wave-packets which
localize particles in space and time as well as the uncertainty relation allows it. One
finds a particle at position r and time t with the probability
 2
w(r, t) =  (r, t) . (2.1)

This is the key assumption of the statistical interpretation of quantum mechanics

as formulated by Max B ORN (1927) in the early days of quantum mechanics, for
which he received the N OBEL prize in physics in 1954. Quantum mechanics allows
to describe the evolution of a wave packet quantitatively. If formed at time t = 0
with widths in momentum and space, pi (0) and xi (0), respectively, one finds for
larger times t > 0 always pi (t)xi (t) > pi (0)xi (0): the wave packed diverges
as indicated in Fig. 2.1.

2.1.2 Probability Amplitudes in Optics

One may easily visualize the concept of a probability amplitude for the example
of photons in a YOUNGs double slit experiment. The probability to find a photon
at position r and time t is proportional to the intensity I (r, t) of the light, and the
latter is proportional to the square of the field amplitude. Let us consider only one
component of polarization, say Ex . The dependence of the intensity on position may
then be written as
 2  2
I (r) Ex (r) = (r) = w(r).
The last two equalities can help us to get used to quantum mechanical terminology:
we call the quantity (r) now the (position dependent) probability amplitude or
wave function. In the case of light, it is simply represented by the electric field
component Ex . One determines it according to the laws of optics as solution of the
corresponding wave equation

(r) + k 2 (r) = 0 (2.2)

Fig. 2.1 Classical trajectory p

(red line) and quantum
mechanical probability (grey
shaded) in phase space. Note: ics
also at the beginning of a echan
mm
quantum mechanical ntu
trajectory, i.e. a qua
wave-packet, its position and
momentum are not precisely
defined corresponding to classical
the uncertainty relation x
2.1 Matter Waves 89

(with  = 2 /x 2 + 2 /y 2 + 2 /z2 ) for given boundary conditions. For optical

applications a variety of approximations may be used such as H UYGENS -F RESNEL
principle or the diffractions theory of K IRCHHOFF. As the wave function is derived
from a linear partial differential equation (PDE), we may use the linear superposition
principle to describe the interference of waves. For diffraction by two slits we thus
have
(r) = 1 (r) + 2 (r), (2.3)
if 1 and 2 each describe the wave from one or the other slit. With these ampli-
tudes, the probability to find an atom at the detector positions r is given by:
 2  2
w = (r) = 1 (r) + 2 (r) .

This expression contains interference terms 1 2 and is not simply a superposition

of probabilities but rather (we omit here the r):
 
w = |1 |2 + |2 |2 + 2 Re 1 2 . (2.4)

We may see this expression as a reinterpretation of the classical YOUNG double slit
experiment in terms of quantum mechanical probability amplitudes.
In an actual experiment one may now reduce the light intensity such that only
one single photon at a time is near the double slits and participates to the observed
interference pattern. One may easily verify such a setup with a particle counter
detecting single photons one may even hear the individual photons click.1 If a
sufficient number of such single photon events are recorded and added up, one finds
quite counter intuitively that the classical diffraction pattern known from optics
is recovered! Thus, the probability distribution of each individual photon behind the
double slit is determined by the wave amplitudes = 1 + 2 and it is impossible
to say through which slit the particle has passed (see Fig. 1.31). One also says that
one photon always interferes only with itself. We shall discuss this statement in some
detail in Chap. 2, Vol. 2 and quantify it statistically.

2.1.3 Probability Amplitudes and Matter Waves

From the perspective just discussed let us have a look at the matter waves intro-
duced in Sect. 1.7.1. We have already familiarized ourselves with the relation be-
tween momentum and wavelength as postulated by DE B ROGLIE. Matter waves are

1 For the experts: One may invest a lot of thought and substantial experimental efforts to make

absolutely sure that only isolated photons reach the double slit setup (for a recent review on single
photon sources see E ISAMAN et al. 2011). In the present context we shall be content if the average
time tav between each interference event (photon counted) is long compared to the coherence time
of the photon source c = 1/  tav , with  being the bandwidth of the source (see Sect. 2.1.4,
Vol. 2).
90 2 Elements of Quantum Mechanics and the H Atom

also characterized by an amplitude (r), determining the probability for finding a

particle at position r in a volume element d3 r:
 2
dw(r) = w(r)d3 r = (r) d3 r. (2.5)

And as in optics, diffraction and interference occurs, e.g. at a double slit for which
(2.4) describes the experimentally observable signal of particles.
However, in contrast to electromagnetic radiation, where was identified with
the electric (or magnetic) field, for matter waves (r) cannot be attributed to any
directly measurable physical quantity: the observable physics is described by the
probability w(r). So we call (r) simply the probability amplitude for finding a
particle at position r.
Otherwise, analogue considerations are valid for photons and particles of matter.
If e.g. we try to localize them on their pathways, we loose the interference patterns!
One important general rule holds: interference phenomena are observed if differ-
ent but indistinguishable pathways exist on which the particles may proceed toward
the detector. In contrast, no interference is observed if the two pathways may in
principle be distinguished even when no distinction is made in the actual experi-
ment.

Section summary
In classical mechanics well defined trajectories in position r(t) and mo-
mentum p(t) space describe the motion of particles. In contrast, quantum
mechanics describes probability amplitudes (r) and probabilities dw(r) =
|(r)|2 d3 r for finding a particle at a certain position r in a volume element
d3 r.
Diffraction and interference of matter waves can be described by concepts in
analogy to those used in wave optics. The big difference is that for photons
the probability amplitude is also a directly measurable quantity (electric or
magnetic field) while for matter waves (r) cannot be measured directly
only probabilities |(r)|2 refer to the real world.

2.2 SCHRDINGER Equation

Wave equations for matter waves were derived independently by Erwin

S CHRDINGER and PAUL D IRAC who in 1933 jointly received the N OBEL prize in
physics for their ground breaking work. The nonrelativistic S CHRDINGER equa-
tion is most commonly used in AMO physics and will briefly be introduced here.
As we shall see in Chap. 6, the relativistically correct D IRAC equation, valid for
fermions, is significantly more complex and describes inherently also the elec-
tron spin. Its key results may, however, also be introduced as perturbations into
the S CHRDINGER equation which then leads to sufficiently accurate results in the
non relativistic energy regime.
2.2 SCHRDINGER Equation 91

2.2.1 Stationary SCHRDINGER Equation

In contrast to photons, particles of matter may be exposed to external forces which

change their momentum and hence their wavelength. One may start from the wave
equation (2.2) and try to guess, how to modify it for matter waves. Consider-
ing a particle of mass m with a total energy W moving in a conservative poten-
tial V (r), we simply use the (nonrelativistic) energy conservation law of classi-
cal mechanics W = Wkin + V to determine its momentum from the kinetic en-
ergy Wkin :
 
p 2 = 2mWkin = 2m W V (r) .
With W being a constant of motion we derive from this and (1.118) the absolute
value of the wave vector k = p/ and insert it into (2.2):

p2 2m(W V (r))
(r) + (r) = (r) + (r) = 0.
2 2
Rewritten, this is already the stationary S CHRDINGER equation

2
(r) + V (r)(r) = W (r), (2.6)
2m
or somewhat more compact

(r) = W (r)
H (2.7)


with the eigenfunction (r) and the eigenenergy W . The H AMILTON operator H
represents the total energy (briefly just Hamiltonian):

 =   + V (r).
2
H (2.8)
2m
In the often encountered one-dimensional case the S CHRDINGER equation (2.6) is
further simplified:

2 d2 (x)
+ V (x)(x) = W (x). (2.9)
2m dx 2

2.2.2 HAMILTON and Momentum Operators

We may write the H AMILTON operator (2.8) even more suggestive:

 =  2 + V (r) = 
p2
2
H + V (r). (2.10)
2m 2m
Here we have introduced the momentum operator (a vector operator)
92 2 Elements of Quantum Mechanics and the H Atom

/x
p = i = i /y
 (2.11)
/z

so that


2 2 2

p2 = 
p 
p = 2 2 = 2  = 2 + + . (2.12)
x 2 y 2 z2
Thus, (2.10) is the operator form of the classical energy conservation law

p2
W = Wkin + V = + V (r).
2m

2.2.3 Time Dependent SCHRDINGER Equation

So far we have discussed probability amplitudes only as a function of r, the par-

ticles position in space. For many problems in AMO physics such a description
of quantum systems by stationary states is fully sufficient. However, often time de-
pendence is equally important. In respect of photons we know, that electromagnetic
waves follow a time dependent wave equation, which is a 2nd order partial differ-
ential equation (PDE) in space and time derived from the M AXWELL equations. In
contrast, for matter waves the time dependent S CHRDINGER equation holds:

 (r, t) = i (r, t)
H (2.13)
t
2 (r, t)
or more explicitly:  (r, t) + V (r) (r, t) = i .
2m t
It cannot be derived, and we just communicate it here as it was found by Erwin
S CHRDINGER in the beginning of 1926 by the way: during a winter ski holiday
in the Swiss Alps. We point out some key aspects:

The S CHRDINGER equation is a linear PDE of 2nd order in space and 1st order
in time! As a consequence, time dependence of stationary states is truly complex.
The linear superposition principle may be applied to the solutions.
The statistical interpretation of quantum mechanics understands solutions
(r, t) of this PDE as probability amplitudes for finding a particle at a posi-
tion r in space at time t according to (2.1).
Although the S CHRDINGER equation cannot be derived, it is able to describe
a wealth of atomic phenomena and to predict observables quantitatively (under
nonrelativistic conditions) with excellent accuracy: we emphasize that is this very
fact which defines the validity of a physical theory.
Equivalently, formal (algebraic) quantum mechanics can be deduced from a con-
sistent set of axioms, which are, however, also heuristically assumed.
2.2 SCHRDINGER Equation 93

Consistent alternatives of wave equations for matter waves are the D IRAC equa-
tion for fermions, a multi component spinor equation and the K LEIN -G ORDON
equation, a single component PDE of 2nd order in time, which turns out to be
valid for bosons both are relativistically correct.

(r, t) = H
If the Hamiltonian itself does not depend on time, H (r), the time depen-
dence of the wave function may be factored by a product ansatz:

(r, t) = (r)(t) (2.14)

 (r, t) = i (r, t)
H (r)(t) = i (r)(t)
H
t t

H (r) i (t)
= W.
(r) (t) t

The last identity (with the constant W which has to be determined) must hold so
that the former equality can be valid for all values of r and t. One thus has to
solve id(t)/dt = W (t) and H (r) = W (r). In this case, the time dependent
equation leads to the trivial solution


W
(t) exp i t . (2.15)


The position dependent part is nothing but the stationary S CHRDINGER equation
(2.6) and the parameter W introduced is the total energy of the system. The overall
wave function is given by


W
(r, t) = (r) exp i t . (2.16)


Note: The time dependence is truly complex and the imaginary unit i in the prefactor
 = H
is needed for the solution! In the present case, however, with H (t) the time
dependence is trivial in the sense that only
 2  2
w(r, t) =  (r, t) = (r) (2.17)

can be measured, which contains only information about the stationary state.
In order to find these stationary atomic states for a given potential V (r)
which are the equivalent to B OHRs stationary orbits one has to solve the station-
ary S CHRDINGER equation (2.6) under suitably chosen boundary conditions. For
bound states this typically leads to a whole series of discrete total energies W < 0
with a set of quantum numbers characterizing the states. The corresponding series
of wave functions for individual electrons called orbitals describe the probability
of finding the particles at a given position in space.
94 2 Elements of Quantum Mechanics and the H Atom

2.2.4 Freely Moving Particle The Most Simple Example

As the most simple example we consider now a freely moving particle with mass m,
(kinetic) energy W and momentum p. The relevant stationary S CHRDINGER equa-
tion (2.6) reads
2
(r) = W (r) and has solutions (r) = C exp(ikr). (2.18)
2m
As one verifies by inserting the solution with wave vector k = p/ into the equation,
the total energy is given by W = 2 k 2 /(2m) = p 2 /(2m) = Wkin . With the time
dependence (2.16) the whole probability amplitude for this free particle is simply a
plane wave:

2 
 k
(r, t) = C exp i(t kr) = C exp i t kr (2.19)
2m


W pr
= C exp i t .
 
With this we obtain the important dispersion relation for free matter waves:

W p2 k 2 2 2
= = = = (k) or W = k . (2.20)
 2m 2m 2m
Note: The probability to find this particle, w(r, t) = | (r, t)|2 = |C|2 , is indepen-
dent of position and time as expected for an infinitely extended plane wave. In
other words, a particle with well defined momentum may not be localized at all as
expected according to the uncertainty relation (1.123).

Section summary
The stationary S CHRDINGER equation (2.6) may be gleaned from the classi-
cal wave equation combined with a free interpretation of the DE B ROGLIE
wavelength in a conservative potential. It is validated by the excellent
agreement of its predictions with experimentally observed data in the sub-
microscopic world at nonrelativistic energies.
In its most compact form it reads H = W , where the H AMILTON operator
(2.10), also called Hamiltonian, is constructed in full analogy to its classical
counterpart, just replacing the momentum by the quantum mechanical mo-
mentum operator  p = i.
The time dependence of the wave function is described by the time dependent
S CHRDINGER equation (2.13). In the case that the Hamiltonian itself is not
time dependent, the (stationary) solutions are given by the product of the solu-
tions (r) of the stationary equation (2.6) and a simple exponential function
exp(i(W/)t).
The most simple solution of the time dependent S CHRDINGER equation is a
plane wave exp[i((W/)t kr)], with the energy W = k 2 /(2m).
2.3 Basics and Denitions of Quantum Mechanics 95

2.3 Basics and Denitions of Quantum Mechanics

2.3.1 Axioms, Terminology and Rules

Here we summarize briefly the fundamental axioms of quantum mechanics and re-
call some terminology and rules which we shall use later on:

Quantum States and Wave Functions

States of quantum systems (in the world, in atomic physics . . . ) are described by
state vectors for which we introduce here the bra and ket notation of D IRAC,
| and |
, respectively. Typically, states may be expressed in terms of basis states,
or basis vectors, say |f1
, |f2
, |f3
, . . . , |fn
, . . . . We speak about a complete basis
set, if each state of a system can be written as ket vector



|
= ci |fi
, alternatively as bra vector | = ci fi |. (2.21)
i=1 i=1

Note: the sum includes all bound (discrete) and free (continuum) states.
One calls a basis orthonormal if

fk |fi
= ki , (2.22)

where |
is the scalar product of two state vectors |
and |
. With this, the
projection of the state |
onto the basis vector |fk
is


fk |
= ci fi |fk
= ck . (2.23)
i=1

Wave functions, the most commonly used representation of states, are formally
obtained by expanding |
in a continuous position basis {|r
} where r extends
over all points in 3D position space. We write (2.21) as ket
 
     
|
= d r r  r 
3 
or as bra | = d 3 r  r  r  . (2.24)

Per definition we have, in analogy to (2.22),

    
r r = r r  , (2.25)

and obtain from (2.24) the definition of a wave function in position space,

   
r|
= |r
= d3 r  r  r r  = (r), (2.26)
96 2 Elements of Quantum Mechanics and the H Atom

and (r) = |r
. In practice, wave functions are determined by solving the sta-
tionary S CHRDINGER equation. With (2.24) and (2.25) we derive (after one 3D
integration) the scalar product in terms of wave functions:2

|
= (r)(r)d3 r = |
. (2.27)

For the eigenstates |k

of the S CHRDINGER equation the orthonormality relation
(2.22) thus reads:

i |k
= i (r)k (r)d3 r = ik . (2.28)

We finally note that, equivalent to the state expansion in position space, one may
define wave functions (p) in momentum space by

  
|
= d3 p  p p and

   
p|
= d3 p  p pp  = (p).

Operators
Linear operators play a key role in quantum mechanics: in general an operator
changes an object onto which it acts (e.g. a state vector, a wave function, another
 and let it act on a ket
operator) into something different. Let us call the operator A
vector |
:

A|
= |
.
Linearity implies that for a superposition of states |
= c1 |1
+ c2 |2
+
 
 c1 |1
+ c2 |2
+ = c1 A|
A  1
+ c2 A|
 2
+ .

B
The product of two operators A  is defined by
 
B)|

(A   B|

=A  . (2.29)

B
Operator multiplication is distributive, i.e. A C
 = (A
B)
C = A(
B C)
 but not neces-
  
sarily commutative. In general AB = B A and one defines a commutator

 B]
[A,  =A
B B
A (2.30)

2 We shall use the bra| and |ket

symbols rather loosely. In particular, we shall often write wave

functions simply as |
, |k
, etc.
2.3 Basics and Denitions of Quantum Mechanics 97

which only in special cases may vanish (see Sect. 2.3.3). With |
and |
being
two state vectors or wave functions one defines as matrix element of A  between

states |
and |
(which may or may not be basis states of an operator A:

 = (A)d
A = |A
 3 r. (2.31)

Without going into details we define the so called adjoint (or Hermitian conjugate)
 by
operator A
     
  = |A

A  or A  = |A
 (2.32)
 
  3
or  d r = (A)d
A  3 r. (2.33)


Of particular importance are the so called Hermitian operators, let us call them O.
They are self-adjoint:
O 
 O. (2.34)
By this definition and with (2.31)(2.33) the matrix elements
 

O|
 = (O)
= |O
 d3 r = (O)d 3r (2.35)

 = |O

= |O
 (2.36)

are all equivalent for Hermitian operators.3

Observables
Observables are all physical quantities which can in principle be measured (ob-
served). Every quantity which is observable in classical physics is represented quan-
tum mechanically by a linear Hermitian operator, let us call it O.  A quantum sys-
tems can be characterized by a set of eigenstates (eigenvectors) |fk
of an observable
O which it may in principle assume. From the eigenvalue equation

 k
= k |fk

O|f (2.37)

one determines the eigenvalues k of the observable O  for the eigenvectors |fk
. In
any individual physical measurement of the observable O  only one of its eigenvalues
k can be observed.
From (2.37) and the orthonormality of the |fk
basis one sees that the matrix
 in the basis of its eigenstates between |fi
and |fk
are
elements of O

 k
= k ik ,
Oik = fi |Of (2.38)

3 To verify these relations one simply expands |

and |
in a basis of eigenvectors (eigenfunc-

tions) of O.
98 2 Elements of Quantum Mechanics and the H Atom

ik is diagonal and because of (2.36) the eigenvalues k must be real

i.e. the matrix O
as one has to demand for measurable quantities!

Superposition and Expectation Values

In general, a quantum systems to be investigated may be found in a state |
which
 Let the state |
be a linear superposition of
is not an eigenstate of the operator O.

eigenstates |fi
of the operator O with eigenvalues i according to (2.37):

|
= ci |fi
with the expansion coefficients ci = fi |
. (2.39)
i

The latter relation follows directly with (2.22). If we measure now the observable
 many times (as one does in a real experiment), the result of each individual mea-
O
 The probability to detect this particular
surement is one of the eigenvalues i of O.
eigenvalue i is determined by the probability amplitude ci :
 

O|

=O ci |fi
= ci i |fi
. (2.40)

The average value measured for this observable, i.e. the result of many individ-
ual measurements applied to the same state |
, is called expectation value of the
observable:


O

|ci |2 i = |O
. (2.41)

The latter identity follows from

     
  

|O|
= ci fi O ck f k = ci f i   k
ck Of
i k
  
= k ci ck fi |fk
= k ci ck ik = i |ci |2 .
i k i k i

 ()
Somewhat more general, if the state of the system is |
= i ci |gi
, i.e. it is
 its expectation
given in an arbitrary basis {|gi
} and |gi
are not eigenstates of O,
value is
 ()
  ()
 = |O|

O
 = ci 
gi |O|
()
ck |gk
= ci  k
c() . (2.42)
gi |O|g k
i k ik

Unit Operator
We note in passing a nice mathematical trick by rewriting (2.39) as

 
 
|
= |fi
ci = |fi
fi |
= |fi
fi | |
.
i i i
2.3 Basics and Denitions of Quantum Mechanics 99

From this we deduce the often very useful fact that the quantum mechanical unit
operator4 (which does not change the operand) may be written as


1= |fi
fi |, (2.43)
i

as long as the states |fi

represent a complete orthogonal basis and the summation
goes over all states of this basis.

Quantization
Experimentally, when an observable O  is determined in an individual measurement
one always finds one of its eigenvalues. With the measurement one prepares also
 One
the corresponding eigenfunction (eigenstate, eigenvector) of the observable O.
may say that by a measurement one projects the eigenvector out of the state |

under investigation.

Example: HAMILTON Operator

The eigenvalues of the H AMILTON operator H  are the eigenenergies Wn of a sys-
tem. Thus, the Hamiltonian is a particularly important example of an observable. Its
eigenvectors |n
and eigenenergies are determined by solving the S CHRDINGER
equation (2.7). We may also write it in algebraic form:

|n
= Wn |n
.
H

Example: Spin Projection onto the z-Axis

As a further example we mention the projection of the spin of a particle onto a given
axis in 3D space. Typically, but not necessarily, one measures the 
Sz component of
the spin. We have already discussed such a measurement in Sect. 1.10, the S TERN -
G ERLACH experiment. The eigenvalues are here ms  and we write the eigenstates
quite formally as |sms
. The eigenvalue equation is then


Sz |sms
= ms |sms
.

2.3.2 Representations

We have already made use of different ways to describe quantum systems and their
changes. The standard terminology speaks about representations of states and oper-
ators.

4 In matrix representation this corresponds to the identity matrix

1 0 0
0 1 0

1=. . . .
.. .. . . ...
0 0 1
100 2 Elements of Quantum Mechanics and the H Atom

SCHRDINGER Representation
In the S CHRDINGER representation (or picture) the operators are differential oper-
ators. The states are represented by wave functions. The scalar product is an integral
according to (2.27) and the orthogonality of basis states is defined by (2.28). The
matrix elements of an operator A  in respect of an arbitrary basis set |fk
, |fi
, . . .
 are
(in general not eigenfunctions of A)

  
 k
= fi (r)Af
Aik fi |Af  k (r)d3 r = fk A
 fi = A , (2.44)
ki

where we have used the definition of adjoint operators (2.32). If the operator is
Hermitian, i.e. represents and observable, this relation reads

 

Oik fi |Ofk
= fi (r) Of  k (r) d3 r (2.45)
 
 
=  k (r) fi (r)d3 r
Of  i
= Oki
= fk |Of
. (2.46)

HEISENBERG Representation
In the H EISENBERG representation (or picture) the operators (we mention in this
context the N OBEL prize for H EISENBERG 1932) A  are matrices, which are de-
termined by their matrix elements Aik . The states, say |
or |
, are vectors in
H ILBERT space5 which we write

|
= = b1 f 1 + b2 f 2 + b3 f 3 +
|
= = c1 f 1 + c2 f 2 + c3 f 3 +

with their components bi f i or ci f i , respectively. The scalar product is here


|
= bi ci . (2.47)

Both representations are physically as well as mathematically fully equivalent.

2.3.3 Simultaneous Measurement of Two Observables

The following is a generalization of the H EISENBERG uncertainty relation which

states that two canonically conjugate coordinates, such as position and momentum,
cannot be measured simultaneously.
Two observables A  and B  can be measured simultaneously if and only if the
eigenstates of A are also eigenstates of B,
 i.e. if the following holds:

 i
= i |i
and B|
A|  i
= i |i
.

5A H ILBERT space is an extension of the 3D vector space to an arbitrary or infinite number of

dimensions in quantum mechanics to an infinite dimensional function space.
2.3 Basics and Denitions of Quantum Mechanics 101

Thus, also the following relations must be valid for simultaneous measurability of
 and B:
the operators A 

B|
A  i
= A
 i |i
= i A| A|
 i
= i i |i
= B  i
.

B
Hence, the operators must commute, A  =! B
A.
 Equivalently:

 and B
Simultaneous measurement of two observables A  is possible if and only
if their commutator vanishes:
B
A  B
A = [A,
 B]
 = 0. (2.48)

2.3.4 Operators for Space, Momentum and Energy

From the above follow some simple recipes of how to translate classical quantities
into quantum mechanical operators. One simply has to substitute:

r r and pi i =p
i
xi

 (2.49)

or p i , i , i = i = 
p.
x y z

All other substitutions are derived from these rules. In particular, the classical
Hamiltonian total energy

p2
Hclass = + V (r) = Wkin + V with p 2 = p p
2m
becomes the H AMILTON operator:

 = 1 (i) (i) + V (r) =   + V (r).

2
H
2m 2m
x are the prime
Position in space x and its canonically conjugate momentum p
example for non-commuting observables. As seen from comparing


 
x x(x) = i
p x(x) = i x (x) + (x)
x x

x (x) = ix
with x p (x)
x
the commuted operators p x x and x p
x generate completely different results and
hence, the observables x and px cannot be measured simultaneously. This is, so to
say, a formal endorsement of the H EISENBERG uncertainty relation.
102 2 Elements of Quantum Mechanics and the H Atom

2.3.5 Eigenfunctions of the Momentum Operator 

p

We shall now find the eigenfunctions and eigenvalues of the momentum in the
S CHRDINGER picture, starting with the one dimensional case:
d(x)
x (x) = px (x)
p i = px (x).
dx
One easily verifies that (x) = exp(ipx x/) = exp(ikx x) are solutions of this eigen-
value problem. Each value of px (with < px < ) is an eigenvalue of the mo-
mentum operator p x in x-direction: the eigenfunction is thus a plane wave with a
continuum of eigenvalues.
This is easily extended into 3D space. The eigenvalue equation


p (r) = i(r) = k(r) is solved by
a plane wave (r) = C exp(ik r).

The unit directional vector for an arbitrary direction in space is e = ax ex +ay ey +

az ez with ax2 + ay2 + az2 = 1. If we are interested in the magnitude of the momentum
p in any given direction e, the operator providing this information is:



e = e 
p p = ax p
x + ay p y + az p
z = i ax + ay + az . (2.50)
x y y
Any plane wave exp(ik r) in arbitrary direction k and with arbitrary magnitude k
e , with eigenvalue p cos , as one easily verifies
is an eigenfunction of p

e exp(ik r) = (ax kx + ay ky + az kz ) exp(ik r) = e k exp(ik r)

p
= k cos exp(ik r) = p cos exp(ik r), (2.51)

with p = k and the angle between e and k just as one would guess.

Section summary
In the S CHRDINGER picture, states (bra |
and ket |) of quantum sys-
tems are represented by wave functions (r) and (r), respectively. The
H EISENBERG picture uses state vectors in H ILBERT space.
Quantum states may be expressed as a linear superposition of states (2.21)
from a complete, orthonormal basis with fi |fk
= ik . The unit operator
may be written i |fi
fi |.
The S CHRDINGER representation uses differential operators. Classical the-
ory is translated by replacing r r and p  p = i. 
Matrix elements of an operator A  k
= f (r)Af
 are Aik fi |Af  k (r)d3 r
i
in the S CHRDINGER picture. In the Heisenberg representation operators are
defined by the corresponding matrices.
The adjoint A of an operator A is defined by A
 |
= |A
.
 Hermitian
   
operators are self-adjoint A = A, and Aik = Aki holds.

2.4 Particles in a Box And the Free Electron Gas 103

Observables are represented by Hermitian operators. With O|f  k

= k |fk

their eigenvalues k are the only values of that observable which can be ob-
served experimentally.
Such an experiment projects the eigenstate |fk
of the observable out of a
 and B,
state |
under investigation. If the operators for two observables, A 
commute (commutator [A B]
 = 0) they can be measured simultaneously.
The average value of an observable in a state |
is called its expectation
 = |O

value: O
 = (O)d  3 r.

Eigenstates of the momentum operator  p are plane waves exp(ik r), with
p = k.

2.4 Particles in a Box And the Free Electron Gas

2.4.1 One Dimensional Potential Box
We first consider the one dimensional problem of a particle in a potential box, i.e.
between two infinitively high walls at a distance L. In between the walls, the 1D
S CHRDINGER equation (2.9) simply reads

2 d2 n (x)
= Wn n (x).
2m dx 2
Solutions can in principle be (x) = sin(kx) or cos(kx). However, since the wave
function cannot penetrate into the wall, it must vanish on the walls which at x = 0 is
only possible for the sin(kx) solution. For continuity on the other wall sin(kL) = 0
and thus k = n/L must hold, with n = 1, 2, 3, . . . . In summary, the solutions
(eigenfunctions) are standing waves with nodes on both walls of the box. The
eigenenergies assume discrete values Wn :

2 nx 2 k 2 h2 n2
n (x) = sin with Wn = = . (2.52)
L L 2m 8mL2
The expectation value of the momentum p x is derived from

 x n
= n (x)
px
= n p px n (x)dx


2 nxL d sin nx
= i
sin L
dx
L0 L dx

i2n L nx nx
= sin cos dx 0.
L2 0 L L
This corresponds to the fact that the particle in the box moves with equal probability
back and forth. In contrast, the square of the momentum,
 

 2   2 L nx 2 d2 sin nx
x = n p
p x2 n = n p x2 n dx = sin  L
dx
L 0 L dx 2
104 2 Elements of Quantum Mechanics and the H Atom

2(n)2 L nx 1 h2 2
= sin2 dx = n ,
L3 0 L 4 L2

= 
is not zero. With this and H px2
/2m we verify Wn in (2.52).

2.4.2 Three Dimensional Potential Box

A next step towards reality is the extension into the 3D space. The movement of a
particle is now restricted to a large but finite 3-dimensional box, with rigid walls
beyond which the probability to find a particle is zero. For simplicity we assume
the box to be a cube with edge length L as illustrated in Fig. 2.2(a). Inside the box
particles move freely. Stationary solutions are plane waves (2.18) which we write in
the box as real functions now as product in three dimensions:

(x, y, z) = sin(kx x) sin(ky y) sin(kz z). (2.53)

To be continuous, the wave function must vanish on the walls of the cube:

sin(kj L) = 0 kj = n j for j = x, y, z. (2.54)
L
With these boundary conditions, and in analogy to the 1D case (2.52),

the energy of the particle in a box becomes

2  2  2 k 2 2 2 2
W= kx + ky2 + kz2 = = n , (2.55)
2m 2m 2mL2
now with three integer quantum numbers nx , ny , nz and n2 = n2x + n2y + n2z .

One may view this in k or n space as indicated in Fig. 2.2(b). Equation (2.54) says
that precisely one solution exists for each lattice point with integer nx , ny and nz .
Thus, one reads from the figure that the total number of states with  quantum num-
bers 1 to nx , 1 to ny and 1 to nz , i.e. the number of states with n n2x + n2y + n2z is
given by NZ (n) = 1/8 4/3 n3 . Expressing n by the energy W , the total number
of states with energies W is

1 (2mW )3/2 3
NZ (W ) = L .
6 2 3

Fig. 2.2 Boundary condition

(a) z (b) n z kz
for a particle in a potential
box (cube of edge length L); L
(a) the nodes of the wave n
L
function are on the walls of y
the box in 3D position space; L ny ky
(b) one counts the number of
states n in the n or k space x nx kx
2.4 Particles in a Box And the Free Electron Gas 105

If the particle has a spin s, we also have to account for the energy degenerate ge =
2s + 1 possible orientations in space. Dividing by the volume of the box L3 , we
obtain the total number of available states per unit volume:

ge (2mW )3/2
NZ (W ) = . (2.56)
6 2 3
From this we derive the number of states in an energy interval from W to W + dW ,
called density of states (DOS), here per unit volume:

dNZ (W ) ge (2m)3/2 4 2m3/2
g(W ) = = W = ge W. (2.57)
dW 4 2 3 h3
We note in passing, that assuming the phase space to be quantized in unit cells of
size h3 leads to exactly the same result.6 For later use we also give the density of
states in respect of a specific element of solid angle d and express the energy by k,
the magnitude of the wave vector:

d2 NZ (W ) d ge mk
dg = = d. (2.58)
dW 4 (2)3 2

2.4.3 The Free Electron Gas

An important application are electrons (mass me , s = 1/2, ge = 2). In the context

of the photoelectric effect (Sect. 1.4.1) we have already introduced the free electron
gas model, where one assumes the electrons in a metal to move freely in an electron
sea. Now, as a 1st order approximation, we describe this situation quantitatively by
electrons in a 3D box. It turns out that such a model serves well in many areas of
physics, as a first step e.g. when introducing electron bands in solid state physics,
but also in atomic physics for statistical models of electrons in a large atom (see
Sect. 10.1.5).
Due to the high particle density Ne (electrons per unit volume), F ERMI -D IRAC
statistics of electrons in the bulk is quite different from that in gases treated in
Sect. 1.3.4. We estimate Ne = NA /Mr g mol1 , with the number of valence
electrons per atom, NA the AVOGADRO number, the (mass) density of the mate-
rial and Mr the relative atomic mass. It is typically on the order of 1028 1029 m3 .
In contrast to the situation treated in gases, the chemical-potential is now pos-
itive and  kB T . At absolute zero temperature, T = 0 (or rather at very low
values of T ), each available state (with any given spatial wave function according to
Eqs. (2.53) and (2.54)) will be filled by two electrons (with spin up and spin down,
ge = 2). The potential box will thus be filled up to an energy F . With (2.56) the

6 Thesize of phase space with momenta up to p is (4/3)p3 L3 . Expressing p in terms of kinetic

energy W , and dividing by h3 and L3 gives the number of phase space cells per unit volume:
NZ = (4/3)(2mW )3/2 / h3 . Differentiation in respect of W yields (2.57).
106 2 Elements of Quantum Mechanics and the H Atom

w(W ) / eV -1 (a) W
w(W ) / eV -1 (b)
W
0.2 0.2
T = 0K
T = 50 K
0.1 0.1 T = 500K
Ne Ne
T = 293 K
0 0
0 2 4 6 8 6.8 6.9 7.0 7.1 7.2

F W / eV F

Fig. 2.3 F ERMI -D IRAC probability distribution according to (2.61) as a function of energy for
electrons in a metal with a F ERMI energy F = 7 eV at different temperatures T : (a) energy range
from 0 eV to 9 eV, (b) expanded scale around F ; at T = 0 the electron density Ne extends up to
F (grey shading up to the dashed vertical red line); the full red line indicates the density of states
W

total number of electrons per volume with kinetic energies between 0 and F is
thus


1 2me F 3/2
Ne = 2NZ (F ) = . (2.59)
3 2 2
We may invert this to obtain the so called F ERMI energy F . At absolute zero tem-
perature F is identical to the chemical-potential introduced in Sect. 1.3.4, and
corresponds to the maximum electron energy. One state after the other is filled, each
by two of electrons, up to the F ERMI energy:

2  2 2/3
F = 3 Ne . (2.60)
2me

Typical F ERMI energies for metals range from 1.6 eV (Cs) to 14.3 eV (Be).
Expressing the prefactor A given by (1.64) with ge = 2 in terms of the F ERMI
energy F one may write the probability distribution for finding a given energy W
in the electron gas in a box:


dNe 3 1 3/2 W
w(W )dw = = dW (2.61)
Ne 2 F exp[(W )/(kB T )] + 1
with F  F as long as kB T  F .

This is illustrated in Fig. 2.3 for a characteristic example with F =7 eV (about

the value for Cu). The full red line indicates the density of states W accord-
ing (2.57). The grey shaded area under this curve indicates for T = 0 K the filling
with electrons up to F (dashed vertical red line). For temperatures T > 0 K the
states will be occupied according to the F ERMI -D IRAC statistics (1.66). As clearly
seen on an enlarged energy scale in Fig. 2.3(b) the boundary between occupied and
2.5 Angular Momentum 107

unoccupied states broadens as temperature increases (width 2kB T ) the reduc-

tion of the probability for W < F is approximately compensated  by the increase
at W > F , and the F ERMI distribution remains normalized, i.e. 0 w(W )dw  1.
For metals at room temperature one typically finds kB T /F < 1/100 and the nor-
malization condition holds very well.
However, at higher temperatures, kB T /F  0.1, or for different densities of
states (e.g. in semiconductors), the chemical-potential must be readjusted in or-
der to maintain the normalization of w(W ). In solid state physics it is often called
F ERMI level WF = , which, strictly speaking, is identical to the F ERMI energy F
only at T = 0.

Section summary
The particle in a box model allows a most simple description of electrons
moving freely in a metal. The wave functions (2.53) in the 3D box (vol-
ume L3 ) have nodes at theboundaries of the box. The energies are W =
2 2 n2 /(2mL2 ) with n = n2x + n2y + n2z and ni representing positive val-
ues in 3D integer number space.
From this the DOS (2.57) is derived, which according to (2.57) is
ge m3/2 W , where m is the particles mass and ge = 2s + 1 the degen-
eracy due to its spin.
In the case of electrons (Fermions) each state can be filled with up to 2 elec-
trons. Then, at T = 0 K the highest energy with occupied states is the F ERMI
energy F = 2 (3 2 Ne )2/3 /(2me ).
At temperatures T > 0 the boundary between occupied and unoccupied states
smears out according to (2.61). The width of the boundary layer is on the
order of kB T .

2.5 Angular Momentum

Angular momenta play a central role in atomic and molecular physics and Ap-
pendix B gives a summary on the essentials: their abstract definitions, properties,
combinations and the relevant algebra. Here we introduce the S CHRDINGER pic-
ture of orbital angular momenta as used in the quantum mechanics of the H atom.
The orbital picture emerging from this concept is directly accessible to physical
imagination and visualization. At the end of this section we shall generalize the
basic concepts, including electron spin.

2.5.1 Polar Coordinates

Quantum mechanical problems may be treated with advantage in polar rather than in
Cartesian coordinates if they have a symmetry centre, e.g. if the potential depends
only on the distance r from origin V (r) = V (r) as in the C OULOMB case. The
108 2 Elements of Quantum Mechanics and the H Atom

Fig. 2.4 Cartesian (x, y, z) z

and polar coordinates (r, , )
r

y

x

transformations between Cartesian (x, y, z) and polar coordinates (r, , ) are read
from Fig. 2.4,

x = r sin cos
y = r sin sin (2.62)
z = r cos ,

and the volume element transforms as

dxdydz r 2 sin d ddr. (2.63)

Conversion of the relevant observables such as the kinetic energy


p2 2 2 2 2 2 2
= = + +
2m 2m 2m x 2 y 2 z2
requires some in principle trivial partial differentiations and mathematical rear-
rangements which we shall not explicate here. The result is

  2

p2 2 2 2 1 2 L
= = r + with (2.64)
2m 2m 2m r 2 r r 2mr 2

 
 2 1 1 2
L =  2
sin + 2 . (2.65)
sin sin 2

In full analogy to classical mechanics, the form of (2.64) suggests two components
of kinetic energy:


 2 1 2
radial energy Hr = r and (2.66)
2m r 2 r r
2
rotational energy rot = L .
H (2.67)
2mr 2

This suggestive way of writing the energy already implies that 

2
L might be the
quantum mechanical equivalent to the classical angular momentum. In the follow-
ing, a more formal approach to derive an expression for the angular momentum will
be sketched.
2.5 Angular Momentum 109

2.5.2 Denition of Orbital Angular Momentum

In classical mechanics angular momentum is defined as L = r p. The quantum

mechanical equivalent is the orbital7 angular momentum operator 
L which accord-
ing to the recipe (2.49) is obtained by substituting p 
p:


L = r 
p. (2.68)

This has to be expressed in polar coordinates. We just show this for one coordinate
by way of example:


z = i x y .
L (2.69)
y x
With (2.62) one transforms the expression in brackets into polar coordinates:

x y z
= + + = r sin sin + r sin cos +0
x y z x y

= y +x =x y .
x y y x

Thus, the operator for the z component of orbital angular momentum is

z = i .
L (2.70)

Obviously this is constructed in complete analogy to the linear momentum p x =

i/x, with the pair of canonically conjugate coordinates ( px , x) replaced by
z , ).
(L
The transformation of Lx and L y is slightly more complicated. In summary one
finds, here without proof, that the operator of the squared orbital angular momen-
tum  2x + L
2y + L
2z is indeed given by (2.65). Some details are explained in
2
L =L
Appendix B.

2.5.3 Eigenvalues and Eigenfunctions

We are now ready to discuss eigenvalues and eigenstates of angular momentum op-
erators. They will be used in more or less all of the following chapters. In the spirit
of this textbook, again we only sketch the basic concepts, present a collection of nec-
essary tools, and refer the reader to the standard textbooks on quantum mechanics
and angular momentum algebra for details.

7 Orbital to distinguish it e.g. from the spin angular momentum.

110 2 Elements of Quantum Mechanics and the H Atom

Component L z of the Orbital Angular Momentum

In polar coordinates the z-axis represents a preferred direction, since the polar angle
is defined in respect of it. With (2.70), the eigenvalue equation of L z is an ODE
of 1st order
z () = z ()
L
(2.71)
i = z ()

and may be integrated directly. The solution is


z
= C exp i

with a normalization constant C. We now have to apply some physics: which values
of z are really meaningful? Obviously () has to be unique:


! ! z
(0) = (2) or equivalently exp(0) = exp i 2 . (2.72)

This is only possible for integer values of z / = m with m = 0, 1, 2, . . . . Then


z
exp i 2 = exp(im2) = 1,

and m () = Cm exp(im) are the eigenfunctions solving (2.71). We call m the
projection quantum number (in the literature often also somewhat misleadingly
called magnetic quantum number). These wave functions are orthonormal:
 2
!
 
mm = m |m
= Cm Cm exp(im) exp im d (2.73)
0

with Cm = 1/ 2.

The standard phase convention uses real normalization constants Cm . In summary,

for the projection of the angular momentum onto the z-axis

the eigenvalue equation is z m = mm ,

L

1
with eigenfunctions m = exp(im), (2.74)
2
and eigenvalues m where m = 0, 1, 2, . . . .

Components in x- and y-Direction

For the Lx and L
y components the calculation is more complicated but in principle
trivial. We communicate without proof: Lx , L
y , and L
z cannot be measured simul-
taneously. Each pair of them does not commute. On the contrary, one may show that
the following commutation rules for angular momenta hold:
2.5 Angular Momentum 111

x , L
[L y ] = L
x L y L
y L z ,
x = iL
(2.75)
[L z ] = iL
y , L x z , L
and [L x ] = iL
y .

i are represented by different functions of

Corresponding to this all components L
and (not shown here).

Square of the Orbital Angular Momentum

With (2.65) we write the eigenvalue equation for 
2
L as

2
L Y (, ) = L2 Y (, ) (2.76)

with the eigenvalue L2 and use a the product ansatz towards its solution:

Y (, ) = ( )(). (2.77)

z and substitute ( )m ()
As azimuthal part we try the eigenfunctions (2.74) of L
into (2.65). This leads to

 
1 ( ) 1 2
 2
sin m () + 2 ( ) 2 m ()
sin sin
= L2 ( )m () = L2 Y (, )

 
1 m2
2 sin 2 = L2 . (2.78)
sin sin
Thus, only one ODE remains to be solved. Several procedures lead to the cor-
rect solutions. One may directly use the associated L EGENDRE polynomials, known
from the mathematics of ODEs, or (perhaps more elegantly) by exploiting the prop-
erties of the angular momentum operators to find appropriate recursion formulas.
In any case, one has to demand physically reasonable boundary conditions. In anal-
ogy to (2.72) for the z-component, the wave functions must be finite and unique for
0 . Without proof we communicate here that such physically meaningful
solutions exist for which the following relations hold (for completeness we include
again the z-component):

eigenvalue equation for  

2 2
L L Ym (, ) = ( + 1)2 Ym (, ) (2.79)
eigenvalues of 
2
L L2 = ( + 1)2 (2.80)
eigenvalue equation for 
Lz z Ym (, ) = m Ym (, )
L (2.81)
quantum numbers  = 0, 1, 2, . . . and m = 0, 1, . . . , 
(2.82)
degeneracy 2 + 1 (2.83)
112 2 Elements of Quantum Mechanics and the H Atom

Fig. 2.5 Vector diagram z

illustrating the 2 + 1 Lz /
possible orientations of the
2
angular momentum in space L
(shown for  = 2 as an
example) 1
L
0
y
-1

x -2

z only acts
The validity of (2.81) follows directly from (2.74) and (2.77), since L
onto the component of Ym (, ). This implies
 2
2
L L z 
z=L L
2
or  z = 0.
L ,L (2.84)

Equivalently:  z can be measured simultaneously. This also holds for 

2 2
L and L L
x as well as for 
and L
2
L and Ly not, however, for the components L
x , L
y and L
z
which according to (2.75) do not commute with each other.

Vector Diagram
With (2.79) one may write the magnitude of the angular momentum as:

|
L| = ( + 1). (2.85)

For a given set of quantum numbers m the exact direction of the total angular
momentum is undefined. Precisely defined is only the magnitude and component
Lz = m in respect of the z-axis. One visualizes these relations with the help of
a vector diagram shown in Fig. 2.5. ofthe electron spin (see Fig. 1.43). Figure 2.5
illustrates the example  = 2, |
L|/ = 6  2.45 with L z / = m = 2, 1, 0, 1, 2.
One may consider the vector arrows statistically
distributed around the z-axis, i.e.
on cones of height m with a side length ( + 1).

Spherical Harmonics
The eigenfunctions of 
2
L and Lz are called spherical harmonics Ym (, ). General
formulas and properties are summarized in Appendix B.1.2, and specific expres-
sions up to  = 3 are tabulated in Table B.1. A graphical illustration of the angular
dependence is shown in Fig. 2.6.
The Ym (, ) are orthonormalized:
 2 

d Ym (, )Y m (, ) sin d =   m m . (2.86)
0 0
2.5 Angular Momentum 113

x y

|Y00|2 |Y10|2 |Y11|2 |Y20|2 |Y21|2 |Y22|2

Fig. 2.6 3D-plot of the s, p and d spherical harmonics; plotted are the squared moduli as a func-
tion of angles, the shading colours indicate the sign of Ym (, 0). For an alternative representation
in the real basis see Appendix D.3 and in particular Fig. D.1

The complex conjugate is given by

Ym (, ) = (1)m Ym (, ), (2.87)

and inversion at the origin (r r) leads to

Ym ( , + ) = (1) Ym (, ), (2.88)

which describes (see detailed discussion in Appendix D) so called positive or nega-

tive parity depending on whether  is even or odd, respectively.
At this point, we introduce an important, commonly used notation:

orbital angular momenta  = 0, 1, 2, 3, 4, . . . are labelled s, p, d, f, g, . . . .

In the following text we shall, for compactness, usually write the spherical harmon-
ics in bra and ket form, substituting

Ym (, ) |m
and Ym (, ) m|. (2.89)

In this notion, the orthogonality relations (2.86) and the matrix elements of an oper-
ator A are written as
    
m m =  mm and  m .
Am, m = m|A (2.90)

Several useful relations are summarized in Appendixes B and C.

It has to be pointed out, that the complex form of the spherical harmonics
Ym (, ) illustrated in Fig. 2.6 is well adapted for many problems in atomic physics
but it is by no means the only possible representation of the angular part of atomic
orbitals. An alternative frequently used in molecular physics (see Chaps. 3 and 4,
Vol. 2) and always in chemistry, are real combinations of spherical harmonics. They
are described in some detail in Appendix D.
114 2 Elements of Quantum Mechanics and the H Atom

2.5.4 Electron Spin

As shown by the S TERN -G ERLACH experiment, the electron has in addition to mass
and charge one further property which we have identified in Sect. 1.10 as an intrinsic
angular momentum, called spin. The spin is characterized by the spin quantum num-
ber s = 1/2. Its magnitude is |S| = s(s + 1), and two orientations with angular
momentum components /2 and /2 are possible. Closely related to the spin, the
electron has also a magnetic moment with a g factor as defined by (1.162) close
to ge  2.
One simply transfers the formal rules which we have introduced in Sects. 2.5.2
2.5.3 onto the properties of the spin. Clearly, the spin may not be imaged in position
space. However, we may define quite formally in analogy to the orbital angular
momentum  L a new vector operator  S with a square magnitude operator S 2 and a
component  Sz in z-direction for which the general commutation rules for angular
momenta (2.75) and (2.84) are valid:
 2
Sx , 
[ Sy ] = i
Sz , [
Sy , 
Sz ] = i
Sx , [
Sz ,  
Sx ] = i
S ,
Sy ,Sz = 0.
(2.91)
They imply, as in the general case, that the components of the spin cannot be mea-
sured simultaneously. However, it is possible to determine its magnitude together
with one of its components is (e.g. the z-component 
Sz ).
We now introduce spin states |sms
. In analogy to (2.79)(2.83) (for the orbital
angular momentum)

2 |sms
= s(s + 1)2 |sms

S and 
Sz |sms
= ms |sms
(2.92)

with ms = s, s + 1, . . . , s holds. Specifically, for the electron spin with s = 1/2

and ms = 1/2 only two basis states exist,
1 1 1 1
  = |
= |
,
2 2 = |
= |+
and 2 2 (2.93)

for which the spin points into +z- and z-direction, respectively. We have intro-
duced here three equivalent notations which are commonly used for compactness.
One also finds in the literature the notation spin function and without bra or ket.
Alternatively, one speaks about spin up () and spin down () states. In any
case, the relations

2 |
= 3 2 |

S 2 |
= 3 2 |

S
4 4
(2.94)
   
Sz |
= |
Sz |
= |

2 2
hold, together with the orthonormality relations

|
= |
= 0 and |
= |
= 1. (2.95)
2.5 Angular Momentum 115

From the commutation rules (2.91) one may derive how the other components of 
S
act onto the basis (here without proof):

     i  i
Sx |
= |
Sx |
= |
Sy |
= |
Sy |
= |
. (2.96)
2 2 2 2
In this basis each arbitrary spin state of an electron may be expressed as

|
= + |
+ |
, (2.97)

with the probability amplitudes + and normalized to unity: |

= |+ |2 +
| |2 = 1. The probabilities for finding in this state the and component (or spin
up and spin down ) is given by |+ |2 and | |2 , respectively. The expectation
values of the spin components  Sk (with k = x, y or z) in the spin state (2.97) are
readily obtained from  Sk
= |Sk |
using (2.94) and (2.96).
Note that although the three components of the spin cannot be measured simulta-
neously, magnitude and phase of the (complex) amplitudes + and determine the
orientation of the spin in three dimensional space uniquely. Assume we start with
a pure basis state say |
prepared with an ideal S TERN -G ERLACH experiment,
pointing into an arbitrary direction of space. In a given coordinate system with x-,
y-, and z-direction (differing from that S TERN -G ERLACH coordinate frame) this
state |
will again be a superposition of the type (2.97). The mathematics to do
such a coordinate rotation in general is summarized in Appendix E. Experimen-
tally one may determine the expectation values  Sk
in respect of the x-, y-, and
z-coordinates by using a second, rotatable S TERN -G ERLACH setup. With this one
may perform experiments in each of the corresponding directions and repeat them
many times to obtain expectation values. From these (one needs at least two of them)
the probability amplitudes + and in the new system may easily be derived.
It is convenient to write these amplitudes with (E.16) and = 0 as




+ = cos exp i and = sin exp i , (2.98)
2 2 2 2

which are normalized by definition. As an exercise, the reader may show with the
aid of (2.94) and (2.96), that the parameters and give the polar and azimuthal
angles, respectively, at which the so defined spin state is oriented in space.
The above provides a toolbox which is fully sufficient to describe the properties
of the spin states. Nevertheless one often writes perhaps for historical reasons or
better visualization operators in the form of matrices and eigenstates as vectors,
the so called spinors


+  
= and = + (2.99)




1 0
with the basis = and = .
0 1
116 2 Elements of Quantum Mechanics and the H Atom

The matrix elements of the operators 

Sx , 
Sy and 
Sz are obtained from (2.96). They
may be summarized as spin operators in matrix form,

 
S= , (2.100)
2

with 
being a vector operator, the so called PAULI vector, which is built from the
PAULI matrices:




0 1 0 i 1 0
x = y = and z = (2.101)
1 0 i 0 0 1


 3 1 0
S = Sx2 + 
Sy2 + 
2
Sz2 = 2 . (2.102)
4 0 1

For later use we note here that the PAULI matrices anti-commutate

i j + j i = 2ij , (2.103)

and thus

x2 = y2 = z2 = 
1 and x y = y x = iz . (2.104)

Another useful relation is obtained by applying (2.103):


 3 2 3 2 2 1 0
= r 2
2
3(S r) =  (x x + y y + z z) =  r
2 2
S . (2.105)
4 4 0 1

Section summary
Orbital angular momentum operators may be derived from  L=r  p , with

p = i, or be constructed from the commutation rules (2.75).
From the spatial representations of the operators  z according to
2
L and L
(2.65) and (2.70), respectively, one obtains eigenvalues and wave functions
as summarized in (2.79)(2.83), and schematically illustrated in the vector
diagram Fig. 2.5.
The shape of the orbitals with lowest angular momentum s, p and d shown
in Fig. 2.6 should be memorized. General formulas and properties are sum-
marized in Appendix B.1.2, specific expressions are tabulated in Table B.1.
The electron spin obeys the same commutation rules as orbital angular mo-
menta. Its intrinsic angular momentum, the spin, is however s = 1/2 and the
projection quantum number ms = 1/2. A frequently used representation of
the spin operators are the PAULI matrices (2.101) and (2.102) which act on the
so called spinors two component representations of the spin eigenfunctions.
2.6 One Electron Systems and the Hydrogen Atom 117

2.6 One Electron Systems and the Hydrogen Atom

We are now fully prepared to treat a particle in a centrosymmetric potential V (r),

specifically the one electron problem. Much of the following will be based on what
we have learned about angular momenta in Sect. 2.5. We keep the discussion gen-
eral as long as possible and specialize to the H atom, i.e. to the pure, attractive
C OULOMB potential V (r) < 0 in Sect. 2.6.5.

2.6.1 Quantum Mechanics of the One Particle System

We start by formulating the S CHRDINGER equation precisely. With (2.64)(2.67)

we may write the Hamiltonian (2.10) as:

 2
= 
H
p2
+ V (r) = Hr + L + V (r) (2.106)
2me 2me r 2


 2 1 2
with Hr = r , (2.107)
2me r 2 r r

and obtain the one particle S CHRDINGER equation in polar coordinates:

  2 
r + L
H + V (r) nm (r, , ) = Wnm nm (r, , ). (2.108)
2me r 2

In Sect. 2.5.3 we have discussed in detail the eigenfunctions Ym (, ) and eigen-
values 2 ( + 1) of 
2
L . To solve (2.108) we make the separation ansatz

nm (r, , ) = Rn (r)Ym (, ), so that (2.109)

 2 
r + L + V (r) Rn (r)Ym (, ) = W Rn (r)Ym (, ).
H
2me r 2

Since Hr and V (r) act only on the radial and 2

L only on the angular part we obtain
with (2.107) and (2.79):

 
2 1 d 2 d 2 ( + 1)
r + + V (r) Rn (r) = W Rn (r). (2.110)
2me r 2 dr dr 2me r 2

The sum of centrifugal potential 2 ( + 1)/(2me r 2 ) and C OULOMB potential

1/r is called effective potential:
118 2 Elements of Quantum Mechanics and the H Atom

2 ( + 1)
Veff (r) = V (r) + . (2.111)
2me r 2
With this and the substitution

Rn (r) = un (r)/r (2.112)

one obtains a relatively simple, one dimensional, ordinary differential equa-

tion (ODE) which may be integrated without problems:

2 d2 un 
2
+ Wn Veff (r) un (r) = 0. (2.113)
2me dr

Note: The total energy does not depend on the projection quantum number m and is
thus be written W = Wn . Zero energy is usually set for the completely unbound
system, i.e. for electron and nucleus at infinite distance with no kinetic energy.
Bound electrons have negative energies Wn < 0, while free electrons have total
energies W > 0. Extending (2.89) to the full electron wave function one often ab-
breviates
Rn (r)Ym (, ) |nm
. (2.114)
More specifically, one even writes these atomic orbitals shorthand as n = 1s, 2s,
2p, 3s, 3p, 3d, etc. in the notation introduced in Sect. 2.5.3.

2.6.2 Atomic Units

We recall here the concept of atomic units (a.u.), introduced in Sect. 1.8.3:

energy Eh = me e4 02 h2 /4

length a0 = 0 h2 e2 m1
e / = / me Eh (2.115)

time t0 = 202 h3 e4 m1
e /.

Numerical values of these quantities are given in Appendix A, and the most recent,
accurate updates can be found at NIST (2010). We use these definitions here to
rewrite the radial S CHRDINGER equation 2
(2.113). We multiply (2.113) by me /
and a0 , and apply the identity a0 = / me Eh to obtain in dimensionless form:
2

 
1 d2 un ( + 1) V (r/a0 )
+ W n /E h + un (r) = 0. (2.116)
2 d(r/a0 )2 2(r/a0 )2 Eh

For simplicity, one may just substitute r/a0 r and Wn / Eh Wn as well as
V (r)/Eh V (r). This just implies that all observables are measured in a.u. and
the radial S CHRDINGER equation (2.113) reads now
2.6 One Electron Systems and the Hydrogen Atom 119

1 d2 un 
2
+ Wn Veff (r) un (r) = 0 (2.117)
2 dr
( + 1)
with Veff (r) = V (r) + and for the H atom V (r) = Z/r.
2r 2
Following this scheme one may rewrite all atomic equations in a dimensionless,
rather clean looking form. Theoreticians, in particular, like this kind of equation very
much and even give the recipe to just set  = e = me = 1 which really oversimpli-
fies what has to be done. The procedure has one serious disadvantage: a dimensional
analysis is no longer possible which is often highly commendable to check com-
plex calculations. Thus, we typically try to use equations in a form indicated by
(2.116), and carry the a.u. a0 , Eh , and t0 explicitly along. Sometimes one may even
be able to combine elementaryconstants to truly dimensionless quantities, such as
the fine structure constant = Eh /me c2 according to (1.10).

2.6.3 Centre of Mass Motion and Reduced Mass

Up to now we have treated the problem as if the electron would orbit around a space
fixed centre. As the nuclear mass is much larger than the electron mass me in the
case of the H atom with a proton as nucleus mp  1840me the centre of mass
is indeed very close to r = 0. For more demanding precision one has, however, to
correct for the difference. As in classical mechanics (see corrections to the B OHR
model described in Sect. 1.8.5), in quantum mechanics too, one transforms the two
body problem into an effective one particle problem by replacing the electron mass
me with the reduced mass me (1.143) of the system. All a.u. have, in principle, to
be replaced correspondingly (kinematic correction):
me me me
a0 a0 = a0 , Eh Eh = Eh , and t0 t0 = t0 . (2.118)
me me me
For simplicity we shall, however, in the following text continue to use me and the
units a0 , Eh and t0 , and refer to the exact calculations if relevant.

2.6.4 Qualitative Considerations

While we know already the angular part of the hydrogenic wave functions, we
are still left with the task to find physically meaningful solutions to the radial
S CHRDINGER equation (2.117). They have to behave reasonably at r = 0 (see
below) and must not diverge for r . From this follows necessarily that only a
particular set of discrete total energies Wn < 0 leads to such solutions. To find these
is the task at hand.
Before applying mathematics we want to obtain a qualitative picture to support
our physical intuition. Figure 2.7 illustrates this for the  = 0 case in a C OULOMB
potential V (r) = Z/r. We derive the kinetic energy of the electron at different
120 2 Elements of Quantum Mechanics and the H Atom

W,V(r )
0
Wn r

Wkin
rcl

V
un (r ) large classically for-
bidden region:
= h /p exponential
small decrease of

wavefunction r

Fig. 2.7 Bound state radial wave functions for s states, schematic. Top: C OULOMB potential
V (r) 1/r (red) and total energy Wn < 0 (black) determine the classical turning point rcl
(onset of the classically forbidden region). Bottom: The characteristic behaviour of radial wave
functions un is explained by changes of the kinetic energy Wkin in different regions of the poten-
tial (see text)

positions in the potential from Wkin = Wn V (r) and take the corresponding DE
B ROGLIE wavelength = h/p = h/(2me Wkin )1/2 as an indication for changes in
the radial wave function un (r). It obviously will change more rapidly for small
r (large Wkin ) than in the neighbourhood of the classical turning point rcl , where
Wkin = 0. In the classically forbidden area with r > rk (negative kinetic energies)
we expect exponential damping of the wave function, as illustrated in Fig. 2.7.
In a next step we explore the limits for very large and very small r. For the
limiting case r we may neglect the potential altogether and (2.117) becomes
a simple oscillator equation:

1 d2 un
+ Wn un (r) = 0.
2 dr 2

The classical solution is un (r) exp(i 2Wn r). Since for bound states Wn < 0,
we note for large r
  
lim un (r) r n exp 2|Wn |r . (2.119)
r

In the opposite limit r 0 the centrifugal term (+1)/2r 2 dominates the potential
in (2.117) and
1 d2 un ( + 1)
un (r) = 0
2 dr 2 2r 2
r0
has the solution un (r) = Ar +1 as one easily verifies. Thus, we note for small r
 
lim Rn (r) = lim un (r)/r r  . (2.120)
r0 r0
2.6 One Electron Systems and the Hydrogen Atom 121

2.6.5 Exact Solution for the H Atom

We now specialize to the H atom. In the present chapter we neglect the size of the
atomic nucleus (positively charged with +Ze) since nuclear radii rnuc are much
smaller than atomic radii, typically ratom 105 rnuc . Thus, we are dealing with a
pure C OULOMB potential

1 Ze2
V (r) = , (2.121)
40 r
apart from small and very small effects which will be treated in Chaps. 6 and 9,
respectively. The general solution of the radial S CHRDINGER equation (2.110) is
found by using a power series of the type

  
...
Rn (r) = exp 2|Wn |r Ak r k ,
k=

which includes the limiting cases just discussed. Well known results from mathemat-
ics are used and we summarize here the results, again without proof. For hydrogen
like systems i.e. for one electron in the C OULOMB potentialof a Z fold charged
nucleus the radial function is

Rn (r) = unl (r)/r = An e/2  L2+1

n+ () (2.122)

3/2 
2Z Z 2 (n  1)!
where = r/a0 and An =
n a0 n2 [(n + )!]3

with the so called associated L AGUERRE polynomials:


n1
[(n + )!]2 k
L2+1
n+ () = (1)k+1 . (2.123)
(n  1 k)!(2 + 1 + k)! k!
k=0

With An these radial functions are orthonormalized:


Rn (r)Rn  (r)r 2 dr = nn  . (2.124)
0

We introduce here finally the often used term good quantum numbers: They char-
acterize the eigenvalues of such observables that may be measured simultaneously
with the H AMILTON operator, i.e. their operators commutate with the Hamiltonian.
We already know  and m as typical examples: they are part of the set of quantum
numbers characterizing the total energy of the system;  z are simultaneously
2
L and L

measurable with H .
122 2 Elements of Quantum Mechanics and the H Atom

Wn / eV n
=0 =1 =2 =3 =4
0
8
6
5s 5p 5d 5f 5g
- 0.85 4
4s 4p 4d 4f
- 1.51 3
3s 3p 3d

- 3.40 2
2s 2p Z2
Wn = E h
2n 2
independent of

-13.6 1
1s

Fig. 2.8 Term energies of the hydrogen atom (Z = 1) for different n and 

Table 2.1 The lowest atomic levels, their energies in the H atom and the degeneracy of the states
(with Eh = 27.2 eV)
Shell Orbital n  m Wn Degeneracy
Without spin With spin
sum in shell sum in shell
K 1s 1 0 0 Eh /2 1 1 2 2
L 2s 2 0 0 Eh /8 1 2
2p 2 1 0, 1 3 4 6 8
M 3s 3 0 0 Eh /18 1 2
3p 3 1 0, 1 3 6
3d 3 2 0, 1, 2 5 9 10 18
N 4s, p, d, f 4 Eh /32 16 32

2.6.6 Energy Levels

These solutions of the S CHRDINGER equation are the quantum mechanical equiv-
alent to B OHRs stationary orbits. Substituting unl (r) according to (2.122) into the
radial equation (2.113) one finds the eigenenergies Wn for the H atom. Remark-
ably, they are identical to the energies (1.137) from the B OHR model.8 These results
are summarized in Fig. 2.8 and Table 2.1.
We recall that the states are characterized by the principle quantum number
n = 1, 2, 3, . . . , the angular momentum quantum number  (0  n 1) and
the projection quantum number m ( m ). Each set nm of quantum num-
bers refers to a different wave function (atomic orbital). In addition, we also have to
consider the spin of the electron, with projections ms = 1/2.

8 The corrections for finite mass of the atomic nucleus (Sect. 1.8.5) also apply.
2.6 One Electron Systems and the Hydrogen Atom 123

Veff (r ) / E h
=1 =2
0.2
5 10 15 20
0
n=2 n=3
r /a 0

COULOMB potential
- 0.5 n =1 = Veff for = 0

Fig. 2.9 Illustration of  degeneracy: Shown are the pure C OULOMB potential (red line) and the
effective potentials (black) for the H atom. The term energies Wn are indicated by horizontal
lines in their respective effective potentials: for  = 0 (dotted red), for  = 1 (dashed grey) and for
 = 2 (heavy, full red). As indicated, the C OULOMB potential leads to a characteristic degeneracy
of states with equal n but different 

However, for the H atom the energies Wn depend only on the principle quantum
number n. Thus, the energy levels are degenerate, the total degeneracy in a shell
n being gn = 2n2 . This is summarized in Table 2.1 for n = 1 to 4, also showing
the assignment of orbitals with equal principle quantum number n (i.e. with equal
energies and similar orbital radii) to specific shells (K, L, M, N . . . corresponding
to n = 1, 2, 3, 4, . . .).
It is important to note that  degeneracy is a special property of the pure
C OULOMB potential, while m degeneracy occurs for all atoms if no external field
is present. Figure 2.9 illustrates  degeneracy in the potential energy diagram, also
showing the effective potentials (2.111) for  = 1 and  = 2 (for  = 0 effective and
C OULOMB potential are identical).

2.6.7 Radial Functions

The radial wave functions have very specific shapes, which may be understood from
the properties of the effective potentials. Figure 2.10 illustrates this schematically by
way of example for the n = 3 level and orbital angular momenta  = 0 and 1. Shown
are C OULOMB potential, centrifugal potential and effective potential for  = 1. The
classically forbidden areas (Wkin < 0) are grey shaded, the classical turning points.
While the radial functions for  = 0 start with a finite value at r = 0, for  = 1
the probability there is = 0 (since ( + 1)/(2r 2 ) ). Oscillations of the radial
functions are expected only in between the classically turning points.
Table 2.2 presents the radial wave functions Rn (r) for the six energetically low-
est states (n 3) of atomic hydrogen (Z = 1) and H-like atoms (Z > 1) in closed
form.
From the radial wave functions one derives the probability distributions
 2
w(r)dr = Rn (r) r 2 dr (2.125)
124 2 Elements of Quantum Mechanics and the H Atom

Fig. 2.10 Schematic V, W =0 V, W =1

Veff
illustration of the relation
between potential (top) and
( +1)/ 2r 2
corresponding wave function 0 0
(bottom) for different , W30 r W r
31
exemplified for the n = 3 1/r
1/r
level with  = 0 and 1. Grey
shaded is the classically Rn (r)
forbidden region, red-black
circles indicate classical
turning points 0 r 0 r

Table 2.2 Radial wave n  Rn (r) with = 2Zr/(na0 ) and a0 = a0 me /me
functions for the energetically
lowest states of H and H-like 1 0 R10 (r) = 2( aZ0 )3/2 e/2
atoms
2 0 R20 (r) = 1
( Z )3/2 (2 )e/2
2 2 a0

1 R21 (r) = 1
( Z )3/2 e/2
2 6 a0

3 0 R30 (r) = 1
( Z )3/2 (6 6 + 2 )e/2
9 3 a0

1 R31 (r) = 1
( Z )3/2 (4 )e/2
9 6 a0

2 R32 (r) = 1 ( Z )3/2 2 e/2

9 30 a0

for the electron to be found between r and r + dr. For comparison with the classical
picture of an orbiting electron one has to consult these probability distributions as
a function of distance from the nucleus. A graphical illustration of the radial wave
functions Rn (r) and the radial probability distributions w(r) is shown in Fig. 2.11.
Closer inspection of the probability distributions shows, that their maxima match ex-
actly the radii of the respective B OHR orbits for the largest  = n 1 at any given n!

2.6.8 Density Plots

The complete solutions (atomic orbitals) nm (r, , ) of the S CHRDINGER equa-
tion (2.108) consist of radial and angular part. With the spherical harmonics
Sect. 2.5.3 and the just discussed radial functions the original ansatz (2.109)
nm (r, , ) = Rn (r)Ym (, ) is validated. With (2.86) and (2.124) these wave
functions are already orthonormalized:

  
nmn  m =
nm n  m r 2 dr sin d d = nn  mm . (2.126)

The square of the wave function |nm (r, , )|2 represents the probability distribu-
tion for finding electrons per volume element, or equivalently the electron density
within the atom as a function of position in space. Since these atomic orbitals form
2.6 One Electron Systems and the Hydrogen Atom 125

R n l (r) /a 0-3/2 r 2 [R n l (r) ] 2 /a 0-1

0.1 0.04 0.1 0.1 0.1

0.4
3s 3p 3d 3s 3p 3d
0
0.2 0.2 0 10 20
0.5 0.1 0.1 0.1
2s 2p 2s 2p
0 0
2.0 0 10 20 0 10 20
0.4
1s 1s
1.0 0.2 blow up
0.4
0.2 1s
0 10 20 r /a0 0 10 20
0 2 4

Fig. 2.11 Radial wave functions of the H atoms Rn (r) and probability distributions r 2 Rn 2 (r) for

the K, L and M shell. The dashed, vertical lines in the probability plots for the highest  at a given
n indicate the corresponding B OHR radii. Note the drawing for the 1s orbital on a blown up r-scale

3
z 1s 0 2p 1 3s0 3p 1
5 10 10

0 0 0 0

-5 -10 -10
-3
-3 0 3 -5 0 5 -10 0 10 -10 0 10
3d 1 3d 2 20 4 s 0 40 5s 0
10 10

0 0 0 0

-10 -10
-20 -40
-10 0 10 -10 0 10 -20 0 20 -40 0 40
x

Fig. 2.12 Density plots for some characteristic H atom wave functions nm . Plotted are equiden-
sity lines (red high, grey low probability density). The distances are given in a0

a base for solving many key problems in atomic and molecular physics, we recom-
mend our readers to visualize and memorize their general shape intensively. One
finds a host of instructive Internet-sites, e.g. with Java applets to generate the H or-
bitals in a variety of displays. Thus, we present in Fig. 2.12 only a small selection of
cuts through the 3D density distributions. Plotted are the contour lines of the den-
sity |nm (x, y = 0, z)|2 = |Rn (r)Ym (, )|2 in the zx plane on a linear scale (in
contrast to many presentations in the WWW, where one finds the density plotted on
a log-scale). For clearness we have indicated the highest densities by red areas.
126 2 Elements of Quantum Mechanics and the H Atom

We finally note again, that only the ns orbitals have a finite density at the origin,
|ns (0)| > 0, while
nm (0, , ) 0 for  > 0. Specifically, from (2.122) and with
Y00 (, ) = 1/ 4 we record for later use:
   
n00 (0)2 = Z 3 / a 3 n3 . (2.127)
0

2.6.9 Spectra of the H Atom

Just as in the B OHR model, the transition energies (wavenumbers, frequencies) in

atomic hydrogen are given by the RYDBERG formula (1.147)(1.149). Traditionally,
one characterizes spectral lines series for transitions n n 


1 1 Eh me
 = h = Wn Wn  = Z 2
(2.128)
n2 n2 2 me

according to n (with n < n). Clearly, due to the m and (for the H atom)  degener-
acy, the angular momentum quantum numbers do not influence the position of the
spectral lines as one also verifies by a glance at Fig. 2.8. This holds at least in 1st
order approximation. Finer effects will be discussed in Chap. 6.
A lot of scientific detective work of the early pioneers went into discovering the
connection between spectra and term energies, and the series are named after those
who originally discovered them. Most prominent are the LYMAN (n = 1 in the
VUV), BALMER (n = 2 in the VIS and near UV) and PASCHEN series (n = 3 in
the near IR). Within the series, the BALMER lines are historically referred to as H-
alpha, H-beta, H-gamma etc., more generally the lines of the different series
are designated as Ly-, and Ly-, Ly- , . . . , Ba-, Ba-, Ba- , . . . and so on, with
= n + 2, = n + 3, etc.

2.6.10 Expectation Values of r k

One often needs to know the expectation values of the electron distance from origin
r to a certain power k. In principle, they could be determined by a large number of
individual measurements of this value in an suitably designed experiment. Quantum
mechanics provides:
 
 k
r = n|r k |n
= Rn (r)r k Rn (r)r 2 dr = 2
Rn (r)r 2+k dr (2.129)
0 0

with 2
Rn (r)r 2 dr = 1.
0

These integrations are trivial but somewhat tedious. Using (2.122) and (2.123) one
obtains (for later reference):9

9 Here too, for high precision measurements one has to replace a0 a0 = a0 me /me .
2.6 One Electron Systems and the Hydrogen Atom 127


n2 1 ( + 1)
r
n = a0 1+ 1
Z 2 n2
 !
 2 n4 3 ( + 1) 1/3
r n = a02 2 1 + 1
Z 2 n2
 
1 1 Z
= (2.130)
r n a0 n2
 
1 1 Z2
=
r 2 n a02 n3 ( + 1/2)
 
1 1 Z3
= .
r 3 n a03 n3 ( + 1/2)( + 1)

2.6.11 Comparison with the BOHR Model

One often hears the verdict that the B OHR model is basically wrong albeit predict-
ing the correct term energies Wn and spectra (1.131) for the H atom in agreement
with quantum mechanics and thus should be abolished when teaching modern
atomic physics. We do not adhere to such dogmatic view.
Of course, B OHRs orbits have to be replaced by atomic orbitals, i.e. by den-
sity distributions of the electrons within the atoms, and B OHRs quantization condi-
tion (1.130), L = n, has to be confronted with its quantum mechanical analogue,
z () = m(). Obviously, m  n 1 is not equal to n as postulated in the
L
B OHR model but it is a good first guess.
On the other hand, the concept of angular momentum quantization, of stationary
states, and of radiation emitted upon transition between them with h = Wn was
a brilliant, daring and instrumental step on the way to understand the quantum nature
of microscopic phenomena even though the fact that states without orbital angular
momentum ( = 0) do exist, does not fit at all into the B OHR model. However, the
higher the angular momenta, the closer the atomic orbitals correspond to B OHRs
orbits. And in general, the correspondence principle holds:

quantum mechanical and classical values of observables approach each other

for very large quantum numbers.

A quantitative comparison of atomic orbitals with B OHRs orbits in hydrogen like

atoms shows that the maxima of the electron radial distribution (see Fig. 2.11) for
max = n 1 are indeed found at r = a0 n2 /Z, i.e. they correspond exactly to the
B OHR radii according to (1.135). And more specifically, electron orbitals with m =
 may to some extend be associated with electrons moving on a circle a notion
which holds again particularly well for large . Such circular states are actually
an interesting subject studied in highly excited RYDBERG atoms.
128 2 Elements of Quantum Mechanics and the H Atom

However, the maxima of the probability distributions are of course not directly
observable; rather one may compare expectation values such as n|r|n
= r
. For
the largest angular momenta  = n 1 one obtains from (2.130)
 
1 2 a0 a0
r
= lim n + n = n2 , (2.131)
n1 2 Z Z

which obviously agrees in the limit with B OHRs prediction (1.135). Conversely,
for the smallest values of  = 0, the average radius r
is distinctively larger than
predicted by the B OHR model, namely (3/2)n2 a0 /Z.
In summary, we do not feel that the B OHR model should be completely forgotten.
Apart from its outstanding historical impact, we shall come across a number of spe-
cific aspects in modern AMO physics for which useful, simple models or concepts
have been stimulated by images of electrons moving on classical trajectories com-
bined with appropriate quantization rules. We may think of B ORN -O PPENHEIMER
approximation for molecular physics and of semiclassical trajectory calculations in
atomic scattering theory, to mention just two important, and very successful exam-
ples or, as we shall see in the following section, the derivation of the magnetic
moment of an electron associated with its orbital angular momentum.

Section summary
The eigenenergies of the H atom, Wn = Z 2 /(2n2 )Eh , depend only on the
principle quantum number n . . . a specific consequence of the pure C OULOMB
potential. For precision measurements this has to be corrected by me /me
where me is the reduced mass of the electron.
Electron wave functions for the H atom can be expressed in analytical form
nm (r, , ) = Rn (r)Ym (, ) with the spherical harmonics Ym (, ) and
the radial function Rn (r) being proportional to the L AGUERRE polynomials.
The asymptotic behaviour of the wave functions should be memorized:
limr Rn (r) exp( 2|Wn |r) and limr0 Rn (r) r  .
good quantum numbers characterize the eigenvalues of such observables that
may be measured simultaneously with the H AMILTON operator.

2.7 Normal ZEEMAN Effect

The so called normal Z EEMAN effect is actually not normal at all. It is observed
only in special cases. It concerns atoms in an external magnetic field. The word
normal simply alludes to the classical interpretation of such a situation ignoring
the electron spin. We shall treat atoms in external fields in great detail in Chap. 8.
Thus, the subject is touched here just briefly, and only since it confronts us for the
first time with the removal of a specific energy degeneracy, the m degeneracy in this
case.
2.7 Normal ZEEMAN Effect 129

Fig. 2.13 Electron circling B z

in a magnetic field B and its
orbital magnetic moment M " Mz
M = - B L z /
e- v

2.7.1 Angular Momentum in an External B-Field

As discussed in Sect. 1.9, an orbital angular momentum has a magnetic moment

(1.150) which we rewrite in operator form

L
" = e 
M L = B , (2.132)
2me 
with the B OHR magneton B . Its potential energy (1.153) in an external magnetic
field B is

B = M
V " B = B L B. (2.133)

We choose z  B so that VB = +B (L z /B), as indicated in the vector diagram
B ,
Fig. 2.13. The Hamiltonian contains now an additional term V

=H
H 0 + V 0 + B Lz B,
B = H (2.134)

assuming the unperturbed S CHRDINGER equation to be
0 nm = W (0) nm .
H
0 may e.g. be the H AMILTON operator (2.106) for the H atom. Thus, in the pres-
H
ence of an external field the S CHRDINGER equation to be solved reads
   
0 + B (L
H z /)B |nm
= W (0) + W |nm
, (2.135)

with W being the change of total energy in respect of the unperturbed state. Here
and in the following we use state vectors instead of wave functions nm |nm

for compact writing.

The present problem is a particular simple case for the so called perturbation the-
ory to which we shall come later in some detail. At this point we just remember that
according to (2.79) and (2.81) the eigenfunctions nm (r, , ) = Rn (r)Yn (, )
of the H atom, or their eigenstates |nm
, respectively, are also eigenfunctions
(eigenstates) of  z with
2
L and L
z |nm
= m|nm
.
L (2.136)
130 2 Elements of Quantum Mechanics and the H Atom

Fig. 2.14 The normal Wm m=1

Z EEMAN effect

m=0
B

m =1

Thus, the eigenstates |nm

of the unperturbed Hamiltonian H 0 are also eigenstates
 so that we may insert (2.136) into (2.135) to obtain:
of the full H
 
(H0 + B mB)|nm
= W (0) + Wm |nm

with Wm = B mB. (2.137)

2.7.2 Removal of m Degeneracy

The latter relation obviously implies that in a magnetic field the energy degeneracy
for different m is removed. The originally identical energies of the 2 + 1 states
|nm
which correspond to a given value of n and , now split into 2 + 1 different
energy sub-levels. According to (2.137) the splitting is proportional to m and B.
The origin of this splitting is that the magnetic field breaks the spherical symmetry
characteristic for the unperturbed H atom.
We illustrate this for the example of an np state |npm
with  = 1 and sublevels
m = 1, 0, and 1. Figure 2.14 shows the energy changes Wm as a function of the
magnetic field B.
One may observe this splitting e.g. in optical emission spectra. Figure 2.15 com-
pares the emerging spectra for (a) a p s and (b) a d p transition. The individ-
ual transitions are indicated by black, downward arrows. The selection rules applied
in this plot are  = 1 and m = 0, 1. They will be derived and discussed in
Sect. 4.4.
As the degeneracy and hence the number of split levels is 2 + 1, a manifold
of transitions may occur if states with  > 1 are involved. This is illustrated in
Fig. 2.15(b) where the upper levels correspond to a d state. Since, however, for
the normal Z EEMAN effect the splitting between neighbouring levels is always
B B according to (2.137), independent of  and m, and since for all transitions
m = 0, 1, one nevertheless sees only a line triplet in all cases.
As mentioned at the beginning of this section: in reality this kind of Z EEMAN
effect is seen only in special situations (see Sect. 8.1.2), since usually the spin of
electrons plays an important role and complicates the observations.
We note here an important message from a situation which one typically en-
counters in quantum systems with two or more degenerate states |1
, |2
, |3
: The
degeneracy is removed as soon as some additional, perturbing interaction V1 has to
be considered for which the matrix elements i|V1 |j
between some of these states
do not vanish.
2.8 Dispersion Relations 131

m=+2
(a) (b) +1
+1
BB 0
p 0
d 1
1 BB
2

+1
BB
p 0
s m = 1 0 +1
1
m = 1 0 +1

Fig. 2.15 Normal Z EEMAN effect for (a) p s and (b) d p transitions. In case of equal
splitting in the excited and ground states one observes in each case a line triplet in spite of the
5-fold splitting in the d state

Section summary
A magnetic field B removes the central symmetry and hence the m degener-
acy. For the so called normal Z EEMAN effect, theory predicts a level splitting
Wm = B mB.
The selection rules for optical transitions are  = 1 and m = 0, 1.

2.8 Dispersion Relations

We make a brief detour here, illuminating the borderline between atomic, molecular,
optical and solid state physics. Traditionally, dispersion relations are used in optics
and characterize an important material property: the dependence of the wavelength
(or wavenumber k = 2/) of electromagnetic radiation on its frequency . From
a quantum mechanical point of view one may generalize this to describe the relation
between the energy of a photon W =  (or in fact the energy of any other particle)
and its wave vector k.
For the massless particle photon in vacuo, with c = = /k, the dispersion
relation
W =  = c|k| (2.138)
is obviously a linear relation between energy and wave vector. In contrast, the en-
ergy of a freely moving, nonrelativistic electron (whose mass is me ) is

me 2 p2 2 k 2
W (k) = WP + v = WP + = WP + , (2.139)
2 2me 2me
where we have used the DE B ROGLIE relation (1.118). WP allows for arbitrary en-
ergy calibration and may e.g. account for a potential energy or the rest mass energy.
Thus, in this case the dispersion relation is quadratic. Both cases are illustrated
graphically in Fig. 2.16.
132 2 Elements of Quantum Mechanics and the H Atom

Fig. 2.16 Dispersion W W

relations (a) linear for (a) (b)
a massless particle (e.g.
a photon) and (b) quadratic
for a particle with mass (e.g.
an electron), moving freely in
3D space

k k

It should be noted that the quadratic relation (2.139) for particles with mass is
also in accord with the quantum mechanical calculation for a free particle in a 1D-
or 3D-box according to (2.52) or (2.55). Providing the box is large enough, the
energies may be considered continuous, i.e. they generally follow (2.139). However,
this is only the most simple model for the electronic band structure in a solid. The
particle in a box model does not account for the fact that the electrons in a solid
do not really move freely: rather, the electrons move in the lattice of atomic ions
and experience a periodic potential with strong attraction close to the ionic cores.
Elsewhere the potential is partially screened by bound and other free electrons in
the solid. We mention here two crucial consequences arising from this situation.
First, the dispersion relation (2.139) will have to be modified, which in principle
requires a serious band structure calculation. Many phenomena may, however, be
explained by the so called parabolic approximation. It parameterizes the band en-
ergy by introducing an effective mass me of the electron which may even depend on
the direction into which the electron moves:

2 
kx ky2 kz2
W (k) = WP  2
+ + . (2.140)
2mx 2my 2mz

The sign allows to extend the concept also to electron holes (positive charges in
the latice) and both these quasi-particles may have different masses. This mass
enters into all further calculations on the dynamics and statistics of electrons and
holes in a solid, e.g. into the F ERMI -D IRAC statistics discussed in Sect. 2.4.3.
Second, one has to account for the periodicity of the motion in the lattice. The
solutions for this problem are so called B LOCH waves

(r) exp(ikr)uk (r) (2.141)

which are the product of a plane wave exp(ikr) and a periodic function uk (r). The
latter has to obey the periodic boundary condition

uk (r + T ) = uk (r), (2.142)

where T is any translation from one elementary cell of the lattice into another. Over-
all we still expect the dispersion relation (2.139) for electron energies to be more or
less valid. As detailed studies show, one may have to replace the electron mass me
by a (different) effective mass meff but the quadratic dependence of the energy W
2.8 Dispersion Relations 133

on the wave vector typically holds. The electron motion in general averages over
the periodic potential. However, the energies and eigenfunctions will be influenced
strongly by the lattice potential if the electrons are particularly close to the ions or
particularly far away from them. This is specifically relevant when the electron wave
vector k = k BZ is at (or close to) the B RILLOUIN zone (BZ), i.e. if the correspond-
ing wave functions are constructively interfering (see Sect. 1.4.9). Such electrons
feel the periodic potential strongly, all others experience only an average.
We cannot go into detail of these concepts which are fundamental for the the-
ory of band structure in solid states. We just emphasize some aspects which are
also of importance in molecular physics. Thus, let us discuss the particularly simple
situation of the 1D case, which e.g. describes a chain of atoms with a distance a
from each other (also, with slight modifications, a ring like molecule). According to
(1.95) and (1.93) the B RAGG condition for the ntn BZ then reads

k = kBZ = n . (2.143)
a
The corresponding wave functions are essentially exp(ikBZ x) and exp(ikBZ x), and
for free travelling electrons the energy in that situation would be 2 k 2BZ /2me in both
cases. We have two energetically degenerate solutions. However, the most general
solutions are linear superpositions of both, i.e. standing waves, with the two physi-
cally reasonable cases:

(x) exp(ikBZ x) exp(ikBZ x). (2.144)

These correspond to cos kBZ x and sin kBZ x. The probability |(x)|2 to find the elec-
tron close to the lattice ions is maximal in the first case, minimal in the latter. The
consequence of the perturbing periodic potential is removal of the degeneracy, sim-
ilar to Z EEMAN splitting discussed in the last section. And since the perturbing
potential is highly attractive, we expect the energy to be lowered in the first case,
and to be risen in the second case. In effect, at the boundary of the BZ we expect
the energies to split into two, and a gap to arise between two bands of the otherwise
continuous 2 k 2 /2me distribution.
This is illustrated in Fig. 2.17(a). Since the periodicity of the system does not
favour any particular origin in the reciprocal lattice, one projects all the possible
energies onto the first BZ as shown in Fig. 2.17(b). Electrons in the system may as-
sume all energies W in the grey shaded energy bands. The energy regions marked
band gap are energetically forbidden.
In summary, in the solid state case continuous energy bands, with gaps in be-
tween them, replace the discrete energy levels which we have discussed for the
atomic case (specifically for the H atom in the present chapter). One must, how-
ever, be aware of the fact that Fig. 2.17 shows only a particularly simple situation
(1D case, one valence electron only). In general, the band structure of solid states
is much more complicated, and depending on how many electrons are available to
fill the bands, it provides the basis for such different materials as metals, isolators or
semiconductors.
134 2 Elements of Quantum Mechanics and the H Atom

(a) W W (b)
3rd 2nd 1st 1st 2nd 3rd band gap

band gap

band gap

k k
- 3 a
2 - 2 3
a -
a a 0
a a a

Fig. 2.17 Emergence of energy bands in a periodic system (lattice constant a) and band gaps.
(a) Allowed energies ( ) with distortions at the boundaries of the 1st, 2nd, and 3rd B RILLOUIN
zone in comparison with the free particle ( ) as a function of k. (b) Projection onto the first
B RILLOUIN zone

Section summary
Dispersion relations describe how the energy W of the system depends on
the wave vector k. The most simple cases are (a) the photon (a massless
particle) W = ck, and (b) an electron (a particle with mass) moving freely
W = 2 k 2 /(2me ).
The influence of an average potential can be accounted for by an effective
mass, replacing me which even may depend on the direction of the electrons
momentum.
B LOCH waves, (r) exp(ikr)uk (r), are constructed to include the period-
icity of the lattice in the function uk (r) = uk (r + T ).

Acronyms and Terminology

AMO: Atomic, molecular and optical, physics.

a.u.: atomic units, see Sect. 2.6.2.
BZ: B RILLOUIN zone, represents all wave vectors of radiation which can be
B RAGG-reflected by a crystal lattice. Important concept in solid state physics.
chemical-potential: In statistical thermodynamics defined as the amount of energy
or work that is necessary to change the number of particles of a system (by 1)
without disturbing the equilibrium of the system, see in Sect. 1.3.4.
DOS: Density of states, number of states for a specified observable per unit of
that observable. Most frequently the observable is the energy of a particle in a
system. Typically it is given per unit volume of the system studied.
good quantum number: Quantum number for eigenvalues of such observables that
may be measured simultaneously with the H AMILTON operator (see Sect. 2.6.5).
IR: Infrared, spectral range of electromagnetic radiation. Wavelengths between
760 nm and 1 mm according to ISO 21348 (2007).
References 135

NIST: National institute of standards and technology, located at Gaithersburg

(MD) and Boulder (CO), USA. http://www.nist.gov/index.html.
ODE: Ordinary differential equation.
PDE: Partial differential equation.
UV: Ultraviolet, spectral range of electromagnetic radiation. Wavelengths be-
tween 100 nm and 400 nm according to ISO 21348 (2007).
VIS: Visible, spectral range of electromagnetic radiation. Wavelengths between
380 nm and 760 nm according to ISO 21348 (2007).
VUV: Vacuum ultraviolet, spectral range of electromagentic radiation. part of the
UV spectral range. Wavelengths between 10 nm and 200 nm according to ISO
21348 (2007).

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irradiances. International Organization for Standardization, Geneva, Switzerland.
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