Lecture #5

QM: Basic Postulates

• Topics
– 6 postulates of QM
– Examples
• Handouts and Reading assignments
– van de Ven, Appendix C.
– Miller, Chapters 2-3 (optional)

1
 First Postulate
At any point in time, t0, the state of a physical system is
defined by a ket ψ (t 0 ) that belongs to the state space F.

• F is a Hilbert Space (linear vector space + metric)

€
• Superposition holds, i.e. a linear combination of state
vectors is also a state vector.

2
 Second Postulate
Every measurable physical quantity A is described by an
operator Aˆ acting in F. This operator is observable.

Classical Quantum
mechanics mechanics

The state of a system is state ket

described by a set of physical physical quantities operator
! !
parameters (e.g. r , p ).

€ What is an observable??
3
 Observables *
• Let Aˆ be a Hermitian operator with eigenvalues an and
corresponding normalized eigenkets un for n = 1, 2,…N.
• Aˆ is an observable if its eigenkets form a basis in state space.
€
• Things to note:
€
€ Aˆ Hermitian an real
ui u j = δij
N

∑u n un = Eˆ (closure)
n=1

• The set {an; n = 1,2,…N} is called the spectrum of ˆ.

A
€

€
*discrete, non-degenerate case. 4
 Third Postulate
The only possible result of the measurement of a physical
quantity A is one of the eigenvalues of the corresponding
observable Aˆ .

• The measurement of A always yields a real number.

€
• If the spectrum of Aˆ is discrete, the results that can be
obtained by measuring A are quantized.

5
 Fourth Postulate*
When the physical quantity A is measured the probability
P(an) of obtaining eigenvalue an of the corresponding
observable Aˆ is: P (a ) = u ψ 2
n n

where un is the eigenket of Aˆ associated with an.

• Hence, probability
€ is fundamental to the world in which we live.
No it’s not! Yes it is!
€
iθ
• Consider two kets such that: ψ " = e ψ. 1
ψ : P(an ) = un ψ 2
ψ " : P(an ) = un e iθ ψ 2
= e iθ 2
un ψ 2

Thus, ψ and ψ " represent the equivalent states.

€
* discrete, non-degenerate case. u and ψ normalized. 6
n

€ €
 Phase Factors
• Consider two kets ψ and ψ " that represent the same state,
iθ
i.e. ψ " = e ψ.
iθ 1 iθ 2
• Let ψ = ψ1 + ψ 2 and ζ = e ψ1 + e ψ2 .
€ does it€follow that ψ and ζ represent the same state?
Question:
€
Answer: NO!
€ ζ : P(an ) = un ζ 2
= e iθ 1 un ψ1 + e iθ 2 un ψ 2 2

= un ψ1 2
+ un ψ 2 2
{
+ 2Re e i(θ 1 −θ 2 ) un ψ1 un ψ 2
∗
}
In general, interference terms can not be ignored.
€ € u ψ
ψ : P (a n ) = { }
2 2 ∗
n 1 + un ψ 2 + 2Re un ψ1 un ψ 2
€
Global phase factors do not affect physical predictions, but the
relative phases of the coefficients of an expression are significant. 7
€
 Fifth Postulate
If the measurement of the physical quantity A on a
system in state ψ gives the result an, the state of the
system immediately after the measurement is ψ = un ,
the eigenket of Aˆ corresponding to eigenvalue an.

• This postulate embodies the non-classical concept of a

fundamental interaction between a system and the
measurement of that system.

8
Expected Value of an Observable
• Postulates 4 and 5 deal with the measurement process
and are expressed in terms of probabilities.

• Most measurements don’t involve a single but rather

large number of particles (i.e. protons, electrons, etc).

• The expected (or mean) value of an observable A,

denoted as  ψ or simply  , is defined as the average
obtained from a large number of measurements
performed on systems all in the same quantum state.

• Â generally provides the connection between classical

and quantum mechanical physics.

9
 Expected Value of an Observable
Claim: Aˆ ψ
= ψ Aˆ ψ

Proof:
Aˆ = ∑ aiP ( ai ) = ∑ ai ui ψ 2
(postulate 4)
€ ψ
i i
∗
= ∑ ai ui ψ ui ψ =∑ ai ψ ui ui ψ
i i
$ ' $ '
€ ψ &∑ ai ui ui ) ψ = ψ &∑ Aˆ ui ui ) ψ
= €
% i ( % i (
€ $ '
= ψ Aˆ &∑ ui ui ) ψ ˆ u =a u
remember A i i i
%i (
€ = ψ Aˆ ψ €
€ 10

€
 Compatibility of Observables
• Two observables which can be simultaneously determined
are called compatible.
ˆ
• If Aˆ Bˆ = 0 , then A and B are compatible.
ˆˆ ˆ
Remember A B is superoperator notation for the commutator [ Aˆ , Bˆ ] = Aˆ Bˆ − Bˆ Aˆ .

€
ˆ
• €If Aˆ Bˆ ≠ 0, then A and B are incompatible
€ and cannot be
measured simultaneously.

Can you derive these statements from the QM postulates?

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 Sixth Postulate
The time evolution of the state vector ψ (t) is governed
by the Schrödinger equation:
∂
ψ (t) = −iHˆ (t) ψ (t)
∂t
where Hˆ (t) is the operator for the observable H(t)
associated with the total energy of the system.

• Hˆ (t) €
is called the Hamiltonian operator of the system.
As defined above Hˆ = Eˆ / ! , ( ! emitted in favor of
more compact notation).
• Given an initial state ψ (t 0 ) , the state at any
subsequent€ time is determined
€ (i.e. not probabilistic).
Probability only enters when a physical quantity is
measured, upon which the state vector undergoes an
probabilistic€ change (5th Postulate).
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 Solving Schrödinger’s Equation
∂
ψ (t) = −iHˆ (t) ψ (t)
∂t
In this class, we’ll be interested in addressing three special cases:

• Hˆ (t) independent of time. Easy to verify solution is:

−itHˆ
€ ψ (t) = e ψ (0) .
• Hˆ (t) is periodic. Solution found by changing to a rotating
frame (i.e. change of basis) so that Schrödinger’s equation
becomes€time independent. Example: RF excitation.
• Ĥ (t) random in time. Solution found by considering
ensemble of spins. Example: relaxation theory.
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Example: Stern-Gerlach Experiment
• In 1922, Stern and Gerlach measured the magnetic dipole
moment of silver atoms -- later shown that this moment was due
to intrinsic spin (angular momentum) of an unpaired electron.

stream of silver
atoms z

• Magnet designed so that there is a Bz gradient resulting in a z-

directed force on the atoms proportional to µz, i.e. device measures
z component of the angular momentum (see Lecture #2). 14
 Stern-Gerlach Experiment (cont.)
! !
• Potential energy given by: E = −µ ⋅ B
• Classically, since the atoms can be oriented randomly in
space, device should detect continuum of µz values.
€ detector
Force proportional to the
gradient of the magnetic field
z !
∂Bz B
Fz = µ
∂z x

€
€ • Forced to conclude that µz is not continuous but quantized to
two values ±γ! /2 (result known as space quantization).
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 Stern-Gerlach: Theory
QM description of a silver atom (an example of a spin 1/2 particle).
• Associated with the physical quantity Lz (z-component of angular
momentum) is the observable Lˆ z with eigenvalues ± ! /2.
ˆL α = + ! α and Lˆ β = − ! β α “spin up”
z z β “spin down”
2 2
notation for associated eigenkets
€
€ as given), hence a general
• State space is 2-D (take € form for ψ is:
iθα iθ β
ψ = cα e α + cβ e β with cα 2+ cβ 2= 1 (For now, let’s ignore
θ and θ )
€ α β

• We’ll be dealing with spin operators ( Iˆ = Lˆ /! ) and the

x,y,z x,y,z
corresponding matrix representations in the { α , β } basis are:
1 " 0 1% 1 # 0 −i& 1 #1 0 & Pauli
I x, = $ ' I y, = % ( I z, = % (
2 # 1 0& 2 $ i €0 ' 2 $ 0 −1' matrices
Note, Iˆx,, Iˆy,, and Iˆz € What are the vector
do not commute! representations for
α and β ? 16

€ € €
€
 Stern-Gerlach Experiment (cont.)
• Consider the following two devices:
Small hole that allows +1/2
atoms to pass through.

z z
x x
Iz Detector Iz Polarizer
ψ =α
r
B
Iz Detector z Iz Polarizer
€ x
ψ = cα α + c β β ψ = cα α + c β β ψ =α
ψ = β

Iˆz = ?
€ € % 1( €
€
ˆI = ψ Iˆ ψ = c 2 1 2 Note: for a given atom we
z z α + cβ '− * 1
2 & 2) only measure ± 2 .
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€
 Stern-Gerlach Experiment (cont.)
• Consider the following cases: ψ = α
!
B
oven Iz Polarizer Iz Detector z ?
€ x
ψ = cα α + c β β ψ = α
(actually an ensemble of atoms €
with different cαs and cβs, but
we’ll deal with ensembles later.)
€ €
Ix Detector !
oven z ? B
x

!
B
oven Iz Polarizer
€ Ix Detector z ?
x

€ !
B
oven Iz Polarizer Ix Polarizer Iz Detector z ?
x

[
€ Iˆx , Iˆz ≠ 0.
Remember ] 18
Next lecture: NMR in Hilbert Space
For the love of God, let’s
finally do some NMR!

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Biography: Erwin Schrodinger
(born Aug. 12, 1887, Vienna, Austria—died Jan. 4, 1961, Vienna) Austrian theoretical physicist who contributed to the wave theory
of matter and to other fundamentals of quantum mechanics. He shared the 1933 Nobel Prize for Physics with the British physicist
Paul Dirac. Schrödinger entered the University of Vienna in 1906 and obtained his doctorate in 1910, upon which he accepted a
research post at the university's Second Physics Institute. He saw military service in World War I and then went to the University of
Zürich in 1921, where he remained for the next six years. There, in a six-month period in 1926, at the age of 39, a remarkably late
age for original work by theoretical physicists, he produced the papers that gave the foundations of quantum wave mechanics. In
those papers he described his partial differential equation that is the basic equation of quantum mechanics and bears the same
relation to the mechanics of the atom as Newton's equations of motion bear to planetary astronomy. Adopting a proposal made by
Louis de Broglie in 1924 that particles of matter have a dual nature and in some situations act like waves, Schrödinger introduced a
theory describing the behaviour of such a system by a wave equation that is now known as the Schrödinger equation. The solutions
to Schrödinger's equation, unlike the solutions to Newton's equations, are wave functions that can only be related to the probable
occurrence of physical events. The definite and readily visualized sequence of events of the planetary orbits of Newton is, in
quantum mechanics, replaced by the more abstract notion of probability. (This aspect of the quantum theory made Schrödinger and
several other physicists profoundly unhappy, and he devoted much of his later life to formulating philosophical objections to the
generally accepted interpretation of the theory that he had done so much to create.)In 1927 Schrödinger accepted an invitation to
succeed Max Planck, the inventor of the quantum hypothesis, at the University of Berlin, and he joined an extremely distinguished
faculty that included Albert Einstein. He remained at the university until 1933, at which time he reached the decision that he could
no longer live in a country in which the persecution of Jews had become a national policy. He then began a seven-year odyssey that
took him to Austria, Great Britain, Belgium, the Pontifical Academy of Science in Rome, and—finally in 1940—the Dublin Institute
for Advanced Studies, founded under the influence of Premier Eamon de Valera, who had been a mathematician before turning to
politics. Schrödinger remained in Ireland for the next 15 years, doing research both in physics and in the philosophy and history of
science. During this period he wrote What Is Life? (1944), an attempt to show how quantum physics can be used to explain the
stability of genetic structure. Although much of what Schrödinger had to say in this book has been modified and amplified by later
developments in molecular biology, his book remains one of the most useful and profound introductions to the subject. In 1956
Schrödinger retired and returned to Vienna as professor emeritus at the university. Of all of the physicists of his generation,
Schrödinger stands out because of his extraordinary intellectual versatility. He was at home in the philosophy and literature of all
of the Western languages, and his popular scientific writing in English, which he had learned as a child, is among the best of its
kind. His study of ancient Greek science and philosophy, summarized in his Nature and the Greeks (1954), gave him both an
admiration for the Greek invention of the scientific view of the world and a skepticism toward the relevance of science as a unique
tool with which to unravel the ultimate mysteries of human existence. Schrödinger's own metaphysical outlook, as expressed in his
last book, Meine Weltansicht (1961; My View of the World), closely paralleled the mysticism of the Vednta. Because of his
exceptional gifts, Schrödinger was able in the course of his life to make significant contributions to nearly all branches of science
and philosophy, an almost unique accomplishment at a time when the trend was toward increasing technical specialization in these
disciplines.
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Historical Notes on Spin
Historical Notes on Spin
(from R. Eisberg and R. Resnick, “Quantum Physics”, John Wiley & Sons, 1974, pp 300-301)

Credit for the introduction of electron spin is generally given to Goudsmit and Uhlenbreck in 1925
(both were graduate students at the time!). Uhlenbreck described the circumstances as follows:

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