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Transféré par TommyKMerinoAlama

quantum mechanics

- Chap 35
- m384
- Contents
- Matter as Strings of Oscillating Nodes in a Spatial Continuum.The Schrodinger Wave Equation.
- Understanding Quantum Mechanics
- lec38
- 4. Quantum Mechanics NET-JRF June 2011 - June 2014
- T2_Skript_Ch_4
- MIT8_04S13_ps6
- _Ch5 Delta Function Potential
- Final MSc Physics Ist Year Syllabus 2010
- Mid Exam Solutions
- wavefuncshape
- Ch 1 Quantum Formalism
- PX262 - Quantum Mechanics
- Lenz - Example of poincare anomaly.pdf
- Quantum Physics Problems
- Proposal for Research
- Timotheus Magazine 21
- Lecture_2

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The fundamental theories of classical physics were developed before the nineteen hundreds. The

usefulness of these theories has not diminished with age. However, classical theories do not

describe the machinery of the universe at the fundamental levels of atoms, molecules, and

elementary particles. This is the province of modern physics or quantum physics.

Quantum theory is the ultimate physical theory that evolved after centuries of scientific

endeavor. Many physicists believe that an appropriate combination of quantum physics with

relativity will produce a “theory of everything" to describe all phenomena.

say that they are “included” in quantum theory.

Light is a Wave

We know that light is a wave of electric and magnetic fields. One demonstration that shows light

is a wave is the double slit experiment. Here light comes through two parallel slits. When the

light reaches the screen, it forms a pattern of bars. Waves come from both slits and interfere at

the screen; when two crests meet, they form a higher crest; a bright line. When a crest and

trough meet, they cancel and produce a dark line. The results clearly demonstrate that light is a

wave.

Light is a particle

In order to explain the photoelectric effect, Einstein had to interpret light as little lumps or

particles of energy -- photons.

The photoelectric effect works this way: blue light hits a particular metal and electrons fly out.

Red light hits metal and no electrons are ejected -even when the red light is intensely bright!

Einstein's explanation was that blue light (high frequency) has very

energetic photons that can tear electrons out of the metal. Red light E photon hf

(low frequency) has less energetic photons that are unable to eject

electrons.

True or False

For a particular metal, it is possible that green light will eject electrons, but ultraviolet waves will

not.

Matter-Wave Duality

De Broglie proposed that light should not be the only thing that exhibits

both wave and particle properties. He said all waves have a particle aspect h

mv

and that all particles have a wave aspect. In short, an object is both a

particle and a wave and it reveals one property or the other depending upon

the circumstances.

This conjecture was verified by shooting a beam of electrons through a crystal that serves as a

kind of “double slit.” A pattern appeared on a screen showing characteristic wave interference.

True or False

a) Light exhibits both wave and particle behaviors.

b) Protons exhibit both wave and particle behaviors

Bohr Atom

Bohr first calculated the energy levels of a hydrogen atom by imposing a non-classical

requirement on the orbital angular momentum of the electron. The angular momentum (rp or

rmv) was restricted to integer multiples of a basic number called Planck’s constant, . [rmv = n]

The theory predicted that the atom could realize only discrete orbits and energy levels.

readily seen as the result of an electron-

wave fitting in standing patterns around

the nucleus at just the appropriate

distances. Waves may be imagined to

look something like a string of sausages

so that more sausages (wavelengths) can

fit around larger orbits as seen in the

diagram.

Schrödinger Equation

The de Broglie equation is correct for free particles, but was found to be inadequate for particles

affected substantially by interactions. Schrödinger constructed an equation to fully describe the

“matter wave” for any system,

2 2

V i .

2m t

The Schrödinger Equation is the basic equation of non-relativistic quantum theory. There are

two kinds of information given by the equation, eigenvalues and eigenfunctions:

a) eigenvalues

When applied to bound atoms and molecules, the Schrödinger equation predicts that the

system has definite, discrete, energies:

El. E2, E:3, ....

No solutions exist for any energies “in-between.” This is in sharp contrast with classical

dynamics where there is a continuum of allowed energy values. The equation also

determines that other quantities such as angular momentum and spin have similar discrete

values. However solutions may also include quantities that are not discrete such as the

momentum of a free particle.

The above quantities that are given by the Schrödinger equation are examples of eigenvalues; the

only values which the system can exhibit. In general, we look to the Schrödinger equation to

provide the appropriate eigenvalues for a specific system.

True or False

(a) Eigenvalues are numbers representing physical properties.

(b) Eigenvalues are always discrete.

(c) Eigenvalues represent all possible characteristics of a system.

(d) Only two energies can be determined from the Schrödinger equation when it is applied to an

ammonia molecule in a magnetic field. This means that these two energies and no others are

possible for this molecule

b) eigenfunctions

A state is characterized by a set of eigenvalues. For each state of the system, the

Schrödinger equation gives a corresponding eigenfunction

1 , 2 , 3 , .

Each eigenfunction is associated with specific set of observables like energy, angular

momentum, and spin. The eigenfunctions belong to a more general category of waves

called wave functions that are just combinations of eigenfunctions. We have now to

interpret the wavefunctions.

Born Interpretation

Physicist Max Born was first to correctly interpret the wavefunction. Schrödinger and others

thought was just a measure of the spread of a wavy particle. This belief had flaws that Born

pointed out. Suppose that a single electron is shot through double slits. If the pattern that results

has bright and dark fringes, then the electron has been divided into pieces.

However, electrons are never seen in parts. It must be that the particle itself is not actually an

extended wavy lump. Rather, it is always a point particle when it is detected and wave patterns

must be the result of a statistical accumulation of many particles. The wave must be interpreted

as the probability that the particle is in a particular position or state. (The larger the wave

function at a point, the more likely is the particle to be at that location.)

True or False

Born interpreted eigenfunctions as extended wavy particles.

More on Wavefunctions

When Schrödinger invented the wavefunction, he expected it to be something physical like the

density of an extended particle. It turned out not to be a material substance. Rather, it is a

ghostly probability wave that dictates the positions and outcomes of physical systems.

is not the probability itself. The probability of a state is found from the square of the wave

2

function (much like the energy of an electromagnetic wave is given by the square of its

fields).

question

The diagram shows the eigenfunction for the location x of

an electron in a particular molecule.

(a) Which labeled position is the most likely neighborhood for the electron?

(b) The electron is never at which of the labled points?

Superposition of Waves

An important property of waves is that they “add” (or “subtract”). This is called

superposition of waves. Superposition has profound implications for quantum physics

If 1 and 2 are eigenfunctions for two possible states, then the system may exist with

a wavefunction that is a combination like 2 1 2 and 53 1 54 2 . However, the only

1

values that we can obtain from a single measurement are eigenvalues associated with 1 or 2

, and the probability that the system will be found in condition 1 or 2 depends on the proportion

of 1 and 2 represented in the combination (superposition).

A cat spends several minutes in a sound proof box with an atomic device that has a 50%

chance to kill the cat. Consequently, the cat is 50% live and 50% dead According to the

conventional quantum interpretation, the cat becomes alive or dead (according to chance)

when the box is opened for observation.

questions

A photon strikes a glass pane. The eigenfunctions for the photon to be transmitted through or

reflected from the pane are t and r, respectively.

The wavefunction of the photon is

0.6t 0.8r

(a) Is this photon more likely to be transmitted or reflected?

(b) In the event that the photon was transmitted, what has its wavefunction become?

Our exposition may obscure the simple fundamentals of quantum physics, so it is desirable

to summarize them here as a kind of “how to” list.

a) Given a physical system like an atom or a crystal, write the Schrödinger equation. This is

done with a simple set of rules that transforms an energy relation for the system into a

differential equation.

b) Solve the Schrödinger equation to find the eigenvalues and eigenfunctions for the system.

The eigenvalues are the only physical quantities that the system can exhibit and

corresponding eigenfunctions determine the likelihood that a specific state (set of

eigenvalues) will be found at a given position.

(i) systems may be described by wavefunctions that are superpositions of

2

eigenfunctions and (ii) probabilities depend on the square of a wavefunction, .

(The first of these allows alternative possibilities to exist and the second allows the

alternatives to interfere.)

Some Philosophical Features of Quantum Physics

Quantum mechanics has a profound influence on the philosophy of nature. Indeed, it has

altered our view of objective reality and classical determinism.

In quantum theory, what you know is what you measure (or what some physical system

“records”). The acts of measurement and observation can create the resulting state. A system

does not have a definite value for a quantity until it is observed. Thus an electron is given a

specific spin by an observation; before this, it had only potential spins. A photon in the double

slit interference experiment does not pass through a single slit unless we try to detect that slit

passage and Schrödinger's cat is not dead or alive until an observation makes it so. Quantum

physics does not accept objective reality independent of observation or interaction.

We see that quantum physics differs from classical physics In another basic philosophical sense.

Classical physics is deterministic in that when enough initial information is specified, the

consequences can be predicted with certainty (the clockwork universe). Quantum theory shows

that for a given initial situation, nature can “choose” among alternatives according to predictable

probabilities. The theory asserts that nature is indeterministic.

x p h

says that a particle’s position and velocity can not both be measured with

complete accuracy at the same time. One must sacrifice accuracy in one

to increase accuracy in the other. A similar uncertainty exists between the

energy and lifetime of a particle.

t E h

Another remarkable feature of quantum physics is that the outcome of a process is influenced by

other possible outcomes that are not themselves realized.

02 QUANTUM BASICS

Before you study quantum mechanics in a more formal and systematic way, it helps to learn a

few basic equations, rules, and examples that are used throughout. Here the topics of the last

unit are repeated, but with associated equations and problems.

Light is a Wave

For the present, the most important expression associated with the wave nature of light is the

relation between wave velocity v, wavelength and frequency f:

(0) v f

problem 1.

Find the frequency of light with 4.5 X 10-7 m wavelength. (c = 3.0 X 108 m/s.)

Background Note

Constructive interference of two coherent waves causes the bright fringes in the double slit

experiment. This occurs when the two light rays differ only by an integer number n of whole

wavelengths:

Destructive interference causes the dark fringes in the double slit experiment. In this case the

two rays differ by odd half-integer numbers of wavelengths:

Light is a particle

radiation. Planck was able to describe how the amount of radiation from a heated object depends

upon the wavelength and temperaturebut only when he assumed that energy was emitted and

absorbed in “lumps” proportional to the frequency of the radiation,

(0) E hf

where the proportionality constant h is a universal constant now called Planck's constant.

(0) h = 6.626196 X 10-34 J-s

Equation (2) was taken by Einstein to be the expression of photon energy, and this is the

accepted view today.

problem 2.

Calculate the frequency of a photon emitted when an electron falls from a hydrogen

energy level of -3.4 eV to -13.6 eV. (1 eV = 1.60 X 10-19 J)

In the photoelectric effect, the photon energy hf went into the work W needed to rip the electron

from the metal, and into the kinetic energy K of the freed electron,

(0) hf W K

W is called the work function and is different for different metals. K in Eq. (4) represents the

maximum possible kinetic energy of the electron; as it may be slowed by collisions in the metal.

problem 3.

The work function of Aluminum is 4.25 eV. Calculate the maximum kinetic energy of

electrons ejected from Aluminum when irradiated by an ultraviolet beam of wavelength

2.10 X 10-7 m. (1 eV = 1.60 X 10-19 J)

Matter-Wave Duality

De Broglie expressed the wavelength of the matter-wave in terms of the momentum of the

particle, p = mv:

h

(0)

p

problem 4.

The momentum of a photon is known to be hf/c. Use this fact and the de Broglie relation

to find an expression for c in terms of f and

problem 5.

A particle of mass m is confined in a box of length L such that its de Broglie wave must

form a standing wave. This can be done only when half-integer wavelengths fit the box.

Use Eq. (5) and the fact that the energy (all kinetic) can be written as

p2

E

2m

n2h2

and derive the allowed energy levels E n .

8mL2

Niels Bohr found the correct energy levels of hydrogen in 1913 by proposing that the electron

can only exist in orbits allowed by his “Bohr quantization rule” for angular momentum :

nh

2

This rule is easily derived from the deBroglie relation.

problem 6.

Derive the Bohr quantization rule for angular momentum by requiring that an integer

number n of de Broglie wavelengths fits around the perimeter of a circular orbit

n 2 r .

Schrödinger Equation

The de Broglie relation is accurate for particles that are not subjected to external forces, but it

was found to be a special solution of the more general equation of quantum mechanics, the

Schrödinger equation.

To construct the Schrödinger equation for 1-dimensional systems, follow these rules:

i) Write the energy relation for the system of interest. The kinetic energy K must be written in

terms of the momentum p rather than velocity v,

p2

K

2m

The total energy E including the potential energy V(x) is then given by K(p) + V(x) = E or

p2

(0) V x E

2m

d

ii) Replace the momentum p in Eq. (6) by a differential operator D :

dx

p i D

where (called “h-bar”) is the Planck constant divided by 2,

h

(0)

2

Equation (6) is then converted into the operator form

(0) 2

D 2 V x E

2m

iii) Produce the 1-dimensional, time-independent Schrödinger equation by applying both sides of

Eq. (8) to the wavefunction The result is

2

(0) D 2 V x E

2m

Schrödinger Wave Equation

The following three problems are exercises in writing the wave equation. It will be important to

solve these and other differential equations in later chapters. Here you are given trial solutions to

verify.

problem 7.

Follow the rules above to write the Schrödinger equation for a free particle, V = 0. Show

by substitution that Asin kx is a solution and determine the relation between E and

k. (A and k are constants.)

problem 8.

Follow the rules above to write the Schrödinger equation for a particle in a constant

potential V = V0, where E > V0. Show by substitution that A exp i k x is a solution

and determine the relation between E, V0, and k. (A and k are constants.)

problem 9.

Write the Schrödinger equation for a simple harmonic oscillator, V 12 m x . Show by

2 2

accompanies this wavefunction. (A and a are constants.)

Particle in a Box

The particle-in-a-box problem illustrates how the solution of the Schrödinger equation produces

a set of energy eigenvalues E1 , E 2 , and corresponding wavefunctions 1 , 2 , This is

done by writing the particle's wave equation and finding solutions for that satisfy conditions

imposed by the probability interpretation.

There is no potential energy inside the box, so the wave equation is the same as in problem b-7.

The trail solution x A sin kx will satisfy the equation, but it must also be made to satisfy

the probability conditions.

The probability that a particle is at position x with energy En is proportional to the square of the

2

wavefunction, n . Consequently, if a particle is confined to a box of length L,

0 x L,

it must have zero probability of being outside and we require that

0 0 and L 0

(0)

These are the boundary conditions that must be met by the trial solution.

problem 10.

Write the wave equation for a particle-in-a-box and calculate the energy eigenvalues and

wavefunctions. Use a trial solution of the form A sin kx .

1. AMPLITUDES & PROBABILITIES

The notation and principles of quantum theory are introduced in the next few units. We illustrate

these with two simple examples; a one-dimensional particle-in-a-box and a bead on a circular

ring.

Dirac notation embraces the quantum philosophy that what you know is what you measure.

Consider the one-dimensional particle-in-a-box with allowed energy levels En. The state of this

system is completely characterized by the energy level and the Dirac notation for the nth state is |

En>.

Writing the symbol |En> infers that we have complete knowledge of the particle's nth energy

level, but given this knowledge, what is known about the position x of the particle? The Dirac

symbol for what we want to measure is <x| and the notation that expresses that we want to know

the value of x when we have prior knowledge that the system has energy En is called an

amplitude and is written

x En

“bra” “ket”

what we want to know what we know

problem 11.

The Dirac notation above represents the amplitude for a particle with energy En to have

position x. (a) Write the Dirac notation representing the amplitude for the particle with

energy En to have momentum p. (b) A bead on a ring can be completely specified by its

momentum p. Write the Dirac notation representing the amplitude for the bead with

momentum p to have position x. (c) For the bead in part b, write the Dirac notation

representing the amplitude for the bead with momentum p to have energy E.

Summary:

When a system is known to be in a state the event of finding it in a condition is

characterized by an amplitude written as .

Probability Principle

The probability for an event to occur is the absolute square of the amplitude for that

event. When a system is characterized by |>, the probability of it being found in the

condition |> is

P |

2

(0) discrete

and P | d is the probability of a measurement yielding a value in a neighborhood

d of .

P | d

2

(0) d continuous

For the particle-in-a-box amplitude <x|En>, the probability of a particle with energy En being

found in a neighborhood dx around the point x is |<x|En>|2dx. Amplitudes of the form <x|> that

are probability densities for position and are called wave functions. Not all amplitudes are wave

functions; <p|E> and <E1|E2> are counterexamples.

problem 12.

Use probabilities or probability densities where appropriate and identify any amplitudes

that are wave functions:

(a) Write the Dirac notation representing the probability for a particle with energy En to

have momentum p.

(b) Write the Dirac notation representing the probability for a particle with energy E2 to

be found with different energy E1.

(c) A bead on a ring can be completely specified by its momentum p. Write the Dirac

notation representing the probability for the bead with momentum p to have position x.

The amplitude for position (a wave function) must be a continuous, and single-valued function of

position x.

problem 13.

Given that the wave function for a bead on a ring of circumference L is

1 2inx

x p exp ,

L L

find (a) the probability of an n=-3 particle being between x=0 and x=L/4 and

(b) the probability of particle with arbitrary n being in the interval between x=0 and x=L.

problem 14.

Given that the wave functions for a particle in a box of length L are

2 nx

x En sin ,

L L

find (a) the probability of an n=2 particle being in the “middle” between x=L/4 and

x=3L/4 and (b) the probability of an n=1 particle being in the same interval. Sketch the

probabilities for both cases and comment on the differences. ans:1/2, 1/2 + 1/

2. VECTORS & SUPERPOSITION

Kets describe that which is known about systems and the mathematics obeyed by kets is that of

vectors. This unit describes the vector properties and their physical consequences. For the

present, we continue to treat amplitudes like <x|p> as “given” information instead of deriving

them.

Review of Vectors

A linear vector space is a set of objects called vectors a, b, c,... for which the following

operations are defined:

1. Addition: the sum of two vectors is a vector and addition is commutative and associative

ab ba

a b c a b c

2. Multiplication by a Scalar: multiplication by any complex number is distributive and

associative.

a b a b

a a a

3. A null vector 0 exists in the space such that

a0a

4. Every vector a has an additive inverse -a such that

a a 0

problem 15.

Show that the following are vector spaces: (a) displacements in 2-D space and

(b) the set of all continuous functions f(x) defined on the interval (0,L).

Base Vectors

Any two-dimensional vector v can be written as a sum of the form v = vxi + vyj. Generally, when

any vector in a vector space can be expanded similarly with a minimum of N vectors e1, e2, ..., eN,

(0) v c i ei ,

the space is said to be N-dimensional. The c's are called components and the e's are called base

vectors. When Eq.(1) is satisfied for all vectors in the space, we say the base vectors are

complete. A set of base vectors is a basis of the space.

problem 16.

A vector in 2-dimensional Euclidean space has a magnitude of 10 units and is inclined at

60o above the x-axis. (a) Expand this vector in unit vectors i and j. (b) Write this vector

in column matrix form and expand it in column vectors representing i and j.

The Fourier theorem shows that a function f(x) defined on the interval (0,L) can be expanded in

an infinite series of sine and cosine functions. In general,

nx nx

(0) f x a n cos bn sin

L L

problem 17.

Identify the base vectors in Eq.(2). What is the dimension of the function space?

Scalar Products

A scalar product of two vectors |a>, |b> is written <a|b> and has the following properties:

1. <a|b> = <b|a>*

2- <a|b+c> = <a|b>+<a|c>

3. <a|a> > 0 and <a|a> = 0 implies |a>=0

Two vectors whose scalar product is zero are said to be orthogonal. The length of vector |a> is

defined as <a|a>½

problem 18.

Write definitions of the specific scalar products for the following: (a) Euclidean vectors,

(b) column vectors, (c) functions f(x). In each case, demonstrate that the scalar product

properties are satisfied.

problem 19.

Calculate <u|v> for the following: (a) u=5i cos60-5j sin60 and v=10i (b) u= (4, -1, -5)

and v= (2, -3, 2) (c) u= (1+i, 1-2i) and v= (2, -i) (d) u sin x / L and v sin 2x / L

on the interval (0,L) (e) u exp 2ix / L and v exp 4ix / L on the interval (0,L)

problem 20.

Calculate the lengths of the u vectors in the previous problem.

problem 21.

Show that u=5i cos60-5j sin60 is orthogonal to v=i cos30+j sin30. Which of the vector

pairs in Prob.2 are orthogonal?

Unit Vectors

Ordinary Euclidean vectors are easily treated when they are expanded in terms of unit vectors i,

j, k. Similar useful expansions are also available for more general vectors—including functions.

Notice that i, j, k are orthogonal and have unit lengths. In the scalar product notation; <i|j>=0

and <i|i>=1, etc. In order to have base vectors that are as convenient as these, it is usual to use a

basis that is both orthogonal,

en em 0

(0)

and normalized to a unit length,

en en 1.

(0)

When the base vectors satisfy both Eqs.(3) and (4), we say the basis is orthonormal.

problem 22.

Show that i, j, k are orthonormal.

problem 23.

1 2n ix

Show that the set of functions x p exp with n=0, 1, 2,... are

L L

orthonormal.

problem 24.

2 nx

Show that the set of functions x E n sin with n = 1, 2,... are orthonormal.

L L

Physical states |> are vectors in a linear vector space and amplitudes are

associated scalar products.

This principle has profound consequences. First, we note from the definition of the scalar

product that

(0) <a|b> = <<b|a>*,

indicating that forward and reverse events are closely related.

problem 25.

1 2n ix

Given that x p n exp for a particle on a ring, write the amplitude for the

L L

particle to be found with momentum pn when its position is known to be x.

A second, more remarkable consequence is the fact that a state |> of a system can be expanded

in terms of any base states |u1>, |u2>,... Thus the state of polarization of a photon is a sum of left-

and right-polarized photons and the vitality of Schrödinger’s cat is a sum over the live and dead

cat states. This feature is called the superposition principle. It can be written symbolically as

(0) cn u n

n

problem 26.

A special case of Eq.(6) is |> = 0.8|u1> + 0.6|u2>.Show that the u1 component equals

<u1|> and the u2 component equals <u2|>. 2-14 Show that Eq.(6) can be written as

un un

(0) n

un un

n

problem 27.

Write the state |> of Schrödinger’s cat given that the amplitude for it to be alive is 2

3 .

Use the symbols |L> and |D> for the live and dead states.

The most succinct expression of the superposition principle follows from Eq.(7),

(0) 1 u

n

n un

problem 28.

1 2n ix

Use the orthonormal functions x n exp and Eq.(8) to expand an

L L

arbitrary function f(x)=<x|f> in terms of these functions and coefficients <n|f>. The result

is a Fourier series.

summary:

Quantum states are vectors. As a consequence, an arbitrary state |> can be expanded in

base vectors |un> that represent a complete set of known states. It is then said that |> is

a superposition of |un> states. See Eqs.(6) and (7) for expressions of superposition.

Averages

As an example of averaging with probabilities, consider averaging quiz grades for an imaginary class of

10 students. The possible grades are 0, 50, and 100. One student got 0, four got 50, and five got 100. Here

is the class average:

1 0 4 50 5 100

g 70

10

Another way to look at the same average is:

1 4 5

g 0 50 100 .

10 10 10

Notice that the probability of a student getting 0 is 1/10 and the probability of getting 50 is 4/10, etc. We

write

g p 0 0 p 50 50 p100 100 .

This is a special case of a general way to take an average over g1, g2, when the corresponding

probabilities p1, p2, are known:

g g j pj

j

In quantum mechanics we often have a continuous range of possible outcomes (think 0 to 100 with any

fraction between). Then we modify the average above using a probability density :

x dx probability of system being between x and x dx

In this case, average g is ,

b

g g x x dx

a

We expect in quantum mechanics to be *. A slight wrinkle occurs in quantum theory where we

make a “sandwich” of the thing being averaged so that it looks like this:

b

g * g x dx

a

d

This form works even when g represents an operator like momentum ( i ).

dx

3. OPERATORS & OBSERVABLES

Objects that transform vectors according to some rule are called operators. In quantum physics,

operators represent the instruments or objects that measure or otherwise record physical

quantities. An operator (measuring device) is applied to a state (system in a specific

condition) in order to render a value of the observable .

(0)

For example, the momentum operator P is applied to the bead-on-a-wire wavefunction in order

to measure the momentum of the corresponding system.

In quantum physics, the acts of measurement and observation create the resulting state. A

system does not have a definite value of a quantity until it is observed. Thus a bead-on-a-wire is

given a specific momentum by an observation; before this, it had only potential momenta.

Schrödinger’s cat is not dead or alive until an observation makes it so.

Linear Operators

A linear operator transforms a vector |a> into another vector |a> according to a rule that

obeys the following linear relation:

problem 29.

A translation operator T is defined by T|x> = |x-b> or <x|T = <x-b|. Using the notation

x x , show that x T x b .

problem 30.

Given x p exp ixp / / L , show that the effect of T can be expressed in momentum

language as

1

pT

L

exp ixp / x b dx

Eigenvalues and Eigenvectors

In the special case that an operator acts on a vector and the result is a constant times the

original vector as in Eq.(0), the vector is called an eigenvector and the constant is called an

eigenvalue. The eigenvector is said to belong to the eigenvalue.

Most often, the operator is known and the “eigenvalue problem” is to find the possible

eigenvalues and eigenvectors. Note that the eigenvector in Eq.(0) could be multiplied by any

scalar, so eigenvectors are arbitrary by a constant factor (unless they are normalized to unit

length).

problem 31.

Find the eigenvalues and eigenvectors of the matrix operator

0 1

1 0

problem 32.

Find the eigenvalues p and eigenvectors (x) (eigenfunctions) for

d

i x p x

dx

where we require that 0) = (L).

problem 33.

Find the eigenvalues E and eigenvectors (x) (eigenfunctions) for

2 d 2

x E x

2m dx 2

where we require that (0) = (L) = 0.

Since the eigenvalues and eigenvectors are linked, it is conventional to label the ket with the

eigenvalue. In this notation, the fundamental eigenvalue problem (0) is written as

(0)

Hermitian Operators

A class of linear operators called Hermitian operators has special properties that are important in

quantum mechanics.

a b b a

(0)

The right hand side of Eq.(0) is called the Hermitian adjoint and is denoted with a dagger,

a b b a

The following results obtain for Hermitian operators:

i) The eigenvalues of are real numbers.

ii) The eigenvectors are orthogonal.

iii) The eigenvectors are a complete basis for the vector space.

problem 34.

Confirm that the matrix of problem 3 is Hermitian. Show directly that the eigenvectors

are orthogonal and are a complete basis of the vector space.

problem 35.

Confirm that the operator of problem 4 is Hermitian. Note that the eigenvectors form the

basis for expanding functions in Fourier series.

problem 36.

Prove that the eigenvalues of an Hermitian operator are real and that the eigenvectors are

orthogonal.

Operator Principle

Hermitian operators represent the act of measuring physical observables and the

corresponding eigenvalues are the only possible results of measuring these observables.

problem 37.

The y-component of spin angular momentum is represented by

0 i

sy

2 i 0

Find all possible values for the y-component of spin.

The operator principle does not say how to construct the operators for physical quantities, and it

is convenient to simply assert that the momentum operator p is given in x-space by

(0)

p i

x

or, in bra-ket notation,

(0’) x p i x

x

This enables us to construct many operators by analogy with the classical counterparts. For

example, the energy operator corresponds to the Hamiltonian H of the system,

1 2

(0) H p V

2m

Equations (0) and (0) are restricted to one dimension and to non-relativistic systems. A three-

dimensional form will be given later. We find it simple and direct to accept Eq.(0) as a

subordinate principle.

problem 38.

Demonstrate that x p p x i .

This completes the presentation of the basic quantum principles for several chapters. A principle

of time development will be added later, but we now have the apparatus to analyze many

standard systems and processes.

Wave Mechanics

Wave mechanics is the form of quantum mechanics that is obtained when the amplitudes being

used are wave functions <x|> and the operators are differential operators. Here we outline a

sequence of conceptual steps in treating systems with wave mechanics:

i) problem statement

The fundamental problem is, for a specified system, to find the allowed values of an

observable and the corresponding states |>. The abstract form of the associated eigenvalue

problem is

(0)

The classical form of the observable is usually a function of the position x and momentum p,

classical x, p

then the appropriate quantum mechanical operator is obtained by replacing p by the operator

p i D . (It is not necessary to replace x by an operator x in position space because

x x x x and the value x may be substituted for x .)

(0) x , i D

where is a differential operator

iii) write the wave mechanical eigenvalue problem

The wave mechanical counterpart of Eq. (0) is a differential equation,

x , i D

(0)

where x

When the operator is the Hamiltonian, = H, then the eigenvalue is energy, = E, and Eq. (0) is

Schrödinger’s equation, H E .

A variety of methods must be used to solve the different differential equations that arise.

Boundary conditions play an important role in these equations. A particle on a loop of length L

must satisfy a single-valued condition x x L whereas a particle bound to a potential

source must have 0 (no probability of escape to infinity). A particle in a box of length

L with impenetrable walls satisfies the condition 0 L 0 . Reflection and transmission

from a boundary requires a smooth connection at the boundary; left right and

D left D right .

problem 39.

Calculate the allowed values of momentum p for a bead constrained to a loop of

perimeter L.

problem 40.

Calculate the energy eigenvalues and eigenfunctions of a bead of mass m constrained to a

loop of perimeter L. Compare your result with that of the last problem.

problem 41.

Calculate the energy eigenvalues and eigenfunctions for a particle-in-a-box.

Quantum mechanics describes how light is reflected or transmitted upon striking a transparent

material. The simplest model of this process has a free particle (V=0) hit a “barrier” material

with a constant potential V=Vo. The particle (wave) can then be reflected back from the barrier

or transmitted through the barrier (when E > Vo). The probability of reflection will depend on

the initial energy E and the barrier “height” Vo

transmitted C exp(iKx)

incident A exp(ikx)

reflected B exp(-ikx) Vo

The relative probability that the particle will be reflected is the ratio R called the

reflection coefficient,

R = |B exp(-ikx)|2 / |A exp(ikx)|2

or

2

B

(0) R 2

A

Since the particle must be either reflected or transmitted, the sum of R and the relative

probability for transmission T, the transmission coefficient, must add to unity:

R+T=1.

Equation (0) requires a relation between A and B in order to evaluate the ratio R. This is

established from the boundary conditions for a smooth connection at the boundary; left right

and D left D right .

problem 42.

Calculate reflection and transmission coefficients for a particle incident on a potential

step Vo < E.

4. HARMONIC OSCILLATOR

Here we analyze a system of great importance in physics, the quantum mechanical harmonic

oscillator. The physics and mathematics of the oscillator are relevant to the emission and

absorption of light by matter (blackbody radiation), the analyses of radiation and fields, the

treatment of systems of identical particles, and other basic problems.

The methods used in solving the harmonic oscillator problem are illustrative of the standard

techniques for treating other bound systems. These include i) wave mechanics, where an

eigenvalue problem is represented as a differential equation (usually the Schrödinger equation),

ii) matrix mechanics, where an eigenvalue problem is represented with matrices applied to

column vectors, and iii) abstract operator mechanics, where an eigenvalue problem is solved

using abstract symbols for operators and states. The last approach is the most sophisticated, but

we will emphasize it because, with some modifications, it can be used to solve basic angular

momentum problems and the hydrogen atom relatively easily.

The kinetic energy of a particle of mass and momentum p is p2/2 and the potential energy of

an oscillator can be written as 2x2/2, where is related to the spring constant k by the relation

k

(0) 2

The classical Hamiltonian is the sum of kinetic and potential energies,

(0) p2 1

H 2 x 2

2 2

H E

The quantum analogue of this expression is an eigenvalue problem for energy:

(0) H E E E ,

where H is an operator having the same form as Eq.(2), but with scalars p and x replaced by

operators p and x .

When the state in Eq.(3) is taken to be in the x-representation, <x|E>, the expression becomes a

differential equation called the (time-independent) Schrödinger equation:

(0) 2 2 1

D x E 2 x 2 x E E x E

2 2

problem 43.

Construct Eq.(4) from Eqs.(2) using the momentum operator given in Unit 3.

Equation (4) is the time-independent Schrödinger equation for the harmonic oscillator. Its

solution is shown in all quantum mechanics texts. Bound state solutions exist only when

(0) E n n 12

where n is an integer. Each value of En has an associated wavefunction n = <x|En> (this is

written more simply as <x|n>), and some solutions are graphed below.

n=1

n=3

n = 10

classical case corresponds to n

Abstract Operator Approach (Dirac)--Eigenvalues

The eigenvalues of the Harmonic oscillator can be found from the following information alone,

without the use of the Schrödinger equation:

(0) x , p i

(0) H n E n

where H is given by Eq.(2). The core idea is to construct “raising and lowering” operators a+ and

a with the ability to produce one state from another:

a+|n> = constant |n+1>

a|n> = constant |n-1>

These are then applied repeatedly to Eq.(7) with the result that all the possible energy levels are

produced.

In the following problem sequence, let 1 . These quantities can be restored in the

results by dimensional analysis. (Since we are dealing with three fundamental quantities—mass,

time, and distance—three units may be arbitrarily chosen to specify the values of three

quantities.)

problem 44

Define the operator a

1

2

x ip and derive the relation

(0) [a, a+] = 1

problem 45

Show that H = = a+a + ½.:

(0) H = = a+a + ½.

problem 46

Demonstrate that a+a is the “number operator,” that is,

(0) a+a |n> = n |n>.

problem 47

Use the result of the last problem to show the eigenvalue spectrum of the Harmonic

oscillator is given by Eq.(5). (Use dimensional arguments to restore and .)

Eigenfunctions can be generated by first finding the lowest eigenfunction <x|0> and then

“raising” it repeatedly to <x|1>, <x|2>, etc.

problem 48

Use the fact that <<x|0> corresponds to the lowest n value to calculate the ground state

wavefunction.

problem 49

Use the result of the previous problem to generate the wavefunction of the first excited

state.

Solution 4.2

x , p i

xp px i

(0)

. Substitute operators a

1

2

x ip and a

† 1

2

x ip into the expression

aa † a †a

and preserve the order of the x and p factors because they do not commute like ordinary

numbers. Using Eq. (0), we obtain

a, a †

1 (0)

Solution 4.3

The purpose of this problem is to write the Hamiltonian in terms of the creation and annihilation

operators a and a † . This will later help us with algebraic manipulations that will give the energy

levels.

It is easiest to introduce a

1

2

x ip and a

† 1

2

x ip into the expression

H a † a 21 (0)

H 1

2 p2 x 2 .

Solution 4.4

First we note that any operator with the form a†a is Hermitian* so the eigenvalues of a†a are real.

We write

a †a n = n n (0)

where n is real, but not yet known to be an integer. Apply the operator a to both sides of Eq. (0). Label

the quantity a n as , so that

†

aa | n| (0)

We would like the operator to be converted to a†a so, with the help of the commutation relation (0),

Eq. (0) becomes

Two important observations are made from Eq. (0). Clearly, if n is an eigenvalue of a†a, then so

is n-1. The process can be repeated to produce (n-any integer) and since the oscillator energy cannot

become negative, the process must produce zero for some integer. Consequently, n must be an integer.

a n n 1

(0)

The reason we use a proportionality sign is because we cannot guarantee that is normalized even

when n is. Expression (0) shows why a is called a lowering operator (and often, in the context of

particle physics, an annihilation operator).

Subordinate Problem

Alter this solution to demonstrate the effect of the raising or creation operator a†:

a† n n 1 (0)

* †

Solution 4.5

From Equations (0) and (0) we have

a † a 21 n n 21 n

or

H n n 21 n (0)

Now we have to restore the constants m, , . The dimensions of these are respectively [M], [M]

[L] [T] , and [T]-1. The dimensions of H (energy) are [M] [L]2[T]-2. The latter dimension must be

2 -1

M x M L 2 T 1 T 1 M L 2 T 2

y z

H n n 21 n (0)

Solution 4.6

The lowest energy corresponds to n = 0. This state cannot be lowered so

a0 0

(0)

The wave function equivalent of this is

1

2

ip x 0 0 (0)

where p is the usual differential operator with = 1. The resulting differential equation is

d 0

x 0 (0)

dx

0 const exp 21 x 2 (0)

The exponent must be dimensionless, so the constants m, , must be restored.

03 ATOMS AND CHEMISTRY

Hydrogen Eigenvalues

The simple Bohr picture of hydrogen gives the right energy levels, but modern quantum mechanics gives

much more information. In fact, all of chemistry is explained in principle by quantum theory. Here we

will see that the Schrödinger solution for hydrogen gives us quantum numbers that reveal the basic plan

behind the periodic table.

When we apply quantum theory to hydrogen, four eigenvalues (or associated quantum numbers) are

needed to fully describe each state. These are

(1) the electron's energy level En characterized by the principal quantum number n, an integer

corresponding to the levels in Bohr theory;

(2) the orbital angular momentum L of the electron characterized by an integer such that

L 1 .

positive or negative integer quantum number m, Lz m .

(4) the intrinsic angular momentum of the electron spinning on its axis called the spin, sz.

The eigenvalues (or the corresponding quantum numbers) are related to each other. For a given energy,

only a limited amount of angular momentum is possible and this restricts the values for and m. The

rules restricting the quantum numbers are given below:

n = 1, 2, 3, ...

· orbital angular momentum quantum number is limited to a value below the value of n,

Lz=m

= 0, 1, 2, ..,n-1

· m the azumuthal quantum number can be negative or positive, but may not exceed the magnitude of

the total orbital angular momentum,

m 0, 1, 2,..,

The situation can be pictured as in the diagram where the L vector precesses around the z-axis. The

projection of L on the axis is Lz.

sz 21

1 Use the rules to find how many Hydrogen electron states are possible when

(a) n = 1, and (b) n = 2.

2 Calculate and sketch the possible angles between L and the z-axis for

(a) = 1, (b) = 2

Many-Electron Atoms

Pauli's exclusion principle asserts that no two electrons can occupy the same quantum state. For atoms

with many electrons, this implies that only 2 electrons can be in the n=1 ground state. Similarly, there are

8 different states with the next higher energy level (n=2). We say that a maximum of 8 electrons can exist

in this energy level. At the n=3 level, the simple counting rules for hydrogen's electron must be modified

to account for the complicating effects of additional electrons in many-electron atoms. The result for n=3

is that 8 states are allowed.

We have treated each n level or shell as if all the electrons therein have exactly the same energy. This is

not strictly true for many-electron atoms. Very small differences in energy occur for the different values

due to various interactions between electrons. For example, when these complications are included for n =

2, the =0 state is found to be slightly lower in energy than the = 1 state. Electrons with different

values of within the same shell are therefore called subshells.

The number of electrons in each subshell is the product of the number of m values (2 +1) and the

number of spin states, 2:

maximum number of electrons in a subshell = 2 (2 +1)

Some historic names for the values are

= 0 s wave

= 1 p wave

= 2 d wave

= 3 f wave

and the subshells are denoted by the combination “n ” so that the n=1, =0 subshell is written 1s and

the n=2, =1 subshell is written 2p. (This is often called “spectral notation.”)

(b) Write the spectral notation for the n =4, =3 subshell.

Periodic Table

The rules we've established for three energy levels can be used to construct a simplified periodic table.

The elements in each row or period have their outer electrons occupying the same shell or n-quantum

number.

Each column or group has similar chemical properties because the elements in the group have the same

number of outer electrons (called valence electrons). These are the electrons that encounter the world

outside and account for most chemical interactions.

1 2

1 2 3 4 5 6 7 8

2 2 2 2 2 2 2 2

8

1 8

2 8

3 8

4 8

5 8

6 8

7 8

8

2 2 2 2 2 2 2 2

1

4 The diagram depicts the orbital

electrons of Lithium. Without reference to 2

the above table, make similar sketches for the

elements just to the right and just below

Lithium on the periodic table.

Calculations that include the complexities of many-electron atoms give the following sequential order for

the filling of subshells from lowest energy to highest:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d,...

Based on this notation, the orbital structure of Boron (atomic number Z=5) is: 1s 1s 2s 2s 2p or

1s2 2s2 2p.

Simplified View of Bonding for Organic Molecules

A full description of a chemical bond is given in terms of electron wavefunctions merging together. We do

not need this kind of detail here. A covalent bond is due to the sharing a pair of electrons (more

accurately, overlap of electron wavefunctions) between elements. The bond is depicted with a simple stick

so that two hydrogen atoms bound together as H2 is depicted as

H—H.

The number of such bonds formed by an element is usually equal to the number of outer electrons it must

share to obtain a closed shell. Here are the most ubiquitous elements depicted with unconnected bonds:

H O N C

Carbon forms the most bonds with its neighbors and it is the most characteristic chemical of life. In fact,

the term organic chemistry is synonymous with carbon chemistry. The sticks representing bonds can be

shared by elements. For example, water can be drawn as

H—O—H and methane (CH4) is H

H C H

H

problem

An amino acid is drawn here without hydrogen atoms. Complete O the

picture using H’s and sticks. N C C O

problem

A sugar is drawn here without hydrogen atoms. The corners or C O vertices

are assumed to be carbons. Complete the picture using C’s, H’s and

sticks. O

O O

5. HIGHER DIMENSIONS & ANGULAR MOMENTUM

A few new complexities arise when we consider systems with more than one dimension. In

one dimension, we used a single observable like p or H to describe the system (although it is

possible to use more than one in some cases). In higher dimensions, we must begin with a

sufficient set of such observables a “complete commuting set of observables.”

The motion of a particle in two or three dimensions is usually much more complex than

motion on a line, but the complexity can be reduced by dealing with conserved quantities like

angular momenta. An analysis of the quantum mechanical properties of angular momentum is

therefore addressed here.

Commuting Observables

[A,B] = AB BA = 0, then both quantities can be measured simultaneously. For example, it is

easy to see that p and p2/2 commute, so momentum and kinetic energy can be observed at the

same time.

[A,B] 0,

these quantities cannot be measured simultaneously; it is said that the measurement of one

destroys any knowledge of the other. The important commutation relation [x,p]=i shows that x

and p do not commute and indicates that position and momentum cannot have simultaneous

values.

To prove the theorem, consider the simultaneous measurement of A and B. This means that

applying A or B to the same state |> results in an eigenvalue for each:

A|> = a|>

B|> = b|>.

Premultiply the first by B and the second by A. Subtracting gives (AB-BA)|> = 0, and the

result [A,B]=0 follows. If the eigenstates were different at the outset, we could not get this

result.

5-1 Show that if any two observables can be measured simultaneously, their operators must

commute.

5-2 For the following, indicate whether the operators in brackets can or cannot have

simultaneous values: (a) [p, p2/2m], (b) [x, y]=0, (c) [x, p]=i, (d) [Jx, Jy]= iJz (this

defines angular momentum), (e) [Jz, J2]=0

States and Probabilities in 2-D

A particle's position in two dimensions can be specified by two values, x and y. The position

state can therefore be symbolized by |x, y>. Similarly, momentum has two components in two

dimensions and a momentum state can be indicated as |px ,py>. The wavefunction for the latter

state is written as <x, y|px,py>.

These examples illustrate two general requirements. First, the quantities in a bra or ket must

be able to be specified simultaneously. This means that their operators must commute. The

examples above originate with the relations [x,y]=0 and [px,py]=0. Secondly, the number of

observables specifying a state must be equal to or greater than the number of dimensions. (In

most practical cases these entries are equal in number to the number of dimensions.) In two

dimensions we need two eigenvalue entries like |x,y> or |px,py>.

The requirements can be summarized by saying we must have a complete set of commuting

observables for a given system. This means that for an n-dimensional system we must specify at

least n operators that are linearly independent and mutually commuting. Consider, for example,

a two-dimensional harmonic oscillator with the following commutation relations: [x,H]0,

[px,H]0, [J,H]=0. The first two expressions show that there cannot be states like |x,E> or |px,E>.

The last expression shows that angular momentum and total energy commute so J and H are a

complete commuting set and |j,E> is a legitimate state.

5-3 Consider a free particle in space. Using the information in the following commutation

relations, select a convenient set of complete commuting observables and write a corresponding

ket label:

[x,px]=[y,py]=[z,pz]=i,

[px, py]=[py, pz]=[px, pz]=0.

5-4 A particle is confined to the surface of a sphere. Using the information in the following

commutation relations, select a convenient set of complete commuting observables and write a

corresponding ket label:

[Jx, Jy]=i Jz

[Jy, Jz]=i Jx

[Jz, Jx]=i Jy

[Jx, J2]=[Jy, J2]=[Jz, J2]=0

(Note that in the last problem the linear momenta are related because the particle is constrained

to move on a sphere. This causes the relations given in problem 5-4, [px,py]=[py,pz]=[px,pz]=0, not

to hold in this case.)

5-5 An electron is bound to a stationary proton (Hydrogen atom). Using the information in the

following commutation relations, select a convenient set of complete commuting observables

and write a corresponding ket label:

[Jx, Jy]=i Jz

[Jy, Jz]=i Jx

[Jz, Jx]=i Jy

[Jx, J2]=[Jy, J2]=[Jz, J2]=0

[Jx, H]=[Jy, H]=[Jz, H]=0

[J2, H]=0

Calculating probabilities from amplitudes in higher dimensions is practically the same as for

one dimension. The quantity P(m,En|) = |<<m,En|>|2 is the probability of

measuring the system represented by |> to be in a discrete state with angular momentum m and

energy En.

Probability densities are only slightly more involved. The quantity P(x,y|) = |

<<x,y|>|2 is the probability of measuring the system represented by |> to be in a

neighborhood dx dy of point (x,y). In three dimensions, the neighborhood is dx dy dz. If two

particles are involved with labels like (x1,y1,z1,x2,y2,z2), then the "volume element" to be

integrated over is dx1dy1dz1dx2dy2dz2. If the bra is labeled by, say, two continuous momenta,

<<px,py|, then the volume element is dpxdpy.

dimensional factors, the problem is made tractable. An example of a separable wavefunction is

<<x,y|px,py> = <<x|px> <y|py>. This separation is not always possible. It takes a judicious

choice of representation to accomplish it. As a counterexample, the wavefunction <<r,<2>q<1>|

px,py> cannot be separated.

5-5 A particle is constrained to move on a flat tabletop but is otherwise free. Calculate an

appropriate (unnormalized) wavefunction.

Angular Momentum

Energy and angular momentum are the most familiar conserved quantities in standard

problems. Angular momentum is essentially a two-dimensional quantity because it describes

angular motion for two angles, the polar angle <2>q<1> and the azimuthal angle <2>f<1>.

Earlier in this unit we saw that a 2-dimensional system must be specified by 2 mutually

commuting operators and 2 associated compatible eigenvalues. The two most convenient

commuting observables were seen in problem 5-4 to be the z-component Jz and the total angular

momentum,

Before we evaluate the eigenvalues of angular momentum, we want to review the classical

definition and state the formal quantum definition of angular momentum. In classical

mechanics, angular momentum J is written as

j(zpx-pzx) +

k(xpy-pxy)

When the operator equivalent of Eq.(2) is used, the following commutation relations can be

proved:

These commutation relations are taken to be the definition of quantum mechanical angular

momentum.

5-7 Write the defining commutation relations for the components of angular momentum.

Finally, from Eqs.(1) and (3), we can show that each component of angular momentum

commutes with total angular momentum J2:

(4) [Jx,J2]=[Jy,J2]=[Jz,J2]=0

Eigenvalues for Jz

We can generate the eigenvalues for Jz using only the defining relations, Eq.(3). Construct

"raising and lowering" operators J+ and J-,

5-10 Given the raising and lowering operators of Eq.(5), demonstrate the following commutation

relations:

Now we write an eigenvalue equation for Jz in a convenient form, Jz|j,m>=hm|j,m> and apply

the J+ and J- operators to generate a spectrum of eigenvalues (in much the same way that it was

done for the harmonic oscillator).

5-11 Given the relations (6), show that the eigenvalues of Jz are separated by integer multiples of

h. That is, show that if Jz|j,m>=hm|j,m>, then h(m+1) and h(m-1) are also eigenvalues of Jz

(assuming higher and lower values of m exist).

In the next section we will establish that the eigenvalues of Jz range from +<3>l<1> to

-<3>l<1> , where <3>l<1> is a positive integer or half-integer.

Eigenvalues of J2

The following sequence of problems will establish the familiar eigenvalues of total angular

momentum h2<3>l<1> (<3>l<1> +1).

5-13 Given Eqs.(7), demonstrate that the eigenvalues of J2 are h2<3>l<1> (<3>l<1> +1), where

<3>l<1> is the maximum possible value for m associated with this total angular momentum.

5-14 Given Eqs.(7), demonstrate that the eigenvalues of J2 are h2K(K-1), where K is the

minimum possible value for m associated with this total angular momentum.

5-15 Given the results of problems 5-13 and 5-14, show that K=-<3>l<1> . Use the fact that

values of m differ by integer amounts to show that <3>l<1> must be an integer or half integer.

The results are in; eigenvalues of total angular momentum J2 are (8) J2 = h2<3>l<1>

(<3>l<1> + 1), where <3>l<1> is integer or half-integer

When states |<3>l<1> ,m> are expressed in wavefunction form <<<2>q,f<1>|<3>l<1> ,m>,

they are called <ib>spherical harmonics<ie> and often written in the notation Y<3>l <1>,m.

The hydrogen atom is the model upon which we base our concepts of atomic physics and the

periodic table. We will find that an isolated hydrogen atom is characterized by discrete energy

levels En and each of these levels has subordinate orbitals having associated angular momenta

and m.

coordinates r, , . Let pr and J be the operators for radial and angular momenta, respectively.

Then the Hamiltonian is

1 2 J 2 ke 2

H pr 2

2 r r (0)

where ke 2 r is the potential associated with the Coulomb force.

It can easily be shown that H commutes with J2 and Jz so these three operators are a

complete commuting set of observables. The hydrogen states can therefore be written as |E,

,m> and the energy eigenvalue problem is

H E , , m E E , , m (0a)

Schrödinger’s equation for hydrogen results when this is converted to wave-mechanical form

with differential operators and with kets replaced by wave functions. Usually, textbooks find the

allowed eigenvalues and eigenfunctions by solving the Schrödinger differential equation. It is a

tedious process and here we will find solutions by an easier operator approach closely akin to our

harmonic oscillator solution.

J 2 E , , m 2 1 E , , m , we can write

H E , , m E E , , m (2b)

where

1 2 2 1 ke 2

H pr (0)

2 r2 r

“factored” form 1 2 A A b . The A operator will raise the eigenvalue and A will

lower it.

H in Factored Form

Define an operator A with the form

A pr i 1 r 1 b (0)

where

ke 2 (0)

b

2 1

The problem sequence that follows will determine H in terms of the A+ and A operators.

2

6-2 Given the required commutation relation between r and its conjugate momentum,

r, pr i , show that r 1 , pr ir 2 .

6.3 Use the results of problems 6-1 and 6-2 to derive the form

H

1

2

A A b (0)

The next two problems determine the raising and lowering properties of the A operators.

6-4 Show that A , A 2 1 / r . (Use the results of problems 6-1 and 6-2.)

2 2

6-5 Demonstrate that A E , , m is proportional to E , 1, m ; that is, A is a raising

operator for . Similarly, show that A E , , m is proportional to E , 1, m such that

A is a lowering operator for . Note that these operations do not change the value of E.

The energy of the hydrogen atom must dictate upper and lower bounds for angular

momentum, so the A operators cannot raise or lower without limit. Let * be the maximum

angular momentum at a particular energy E so that E , , m cannot be “promoted” to higher

*

:

A E , * , m 0 (0)

This condition enables us to determine eigenvalues & eigenfunctions of hydrogen.

6-6 Show that the energy eigenvalues for operator H in Eq. (6) are given by

e 4 1

En (0)

2 2 n 2

where n = 1, 2, 3,...

nm Rn r Ym , (0)

where Rn(r) is the radial wavefunction. It is easily determined when operator pr is expressed in

differential operator form:

d 1 (0)

pr i

dr r

(This expression can be verified from the commutation relation r , pr i .)

6-7 Find the hydrogen radial eigenfunctions (un-normalized) for a maximum allowed value of

angular momentum. (Use Eqs. (7) and (10).)

6-8 Calculate the radial ground state R10 of the hydrogen atom. Demonstrate that the probability

density 4r 2 R10 is a maximum at the Bohr orbit. (Use A0 R 0 )

2

Selection Rules for Hydrogen

Transitions between Hydrogen energy levels can only occur when the change in total angular momentum changes by

1:

1

Background

Classical electrodynamics says an accelerating charge e radiates power P according to

2 ke 2 2

P a

3 c3

1

.

problem

ke 2 2

Use dimensional analysis to find P a .

c3

The acceleration of an oscillating electron is given in three dimensions by a = –2 r , so average power can be

written as

k 2 2

P 3 er .

c

2

The quantity er is the (average) dipole moment of the atom. Only non-vanishing averages nm r n' ' m'

allow transitions between the primed and unprimed levels. It can be shown that the integrations over vanish unless

1

problem

Show that 100 r 201 0 and 100 r 210 0 using only integrations over .

2 2

7. MATRIX MECHANICS

We saw that matrices are one kind of operator and column vectors are the associated kind of

state. Here we will show that all linear operators have a corresponding matrix and all ket vectors

have a corresponding column vector. As a consequence, all quantum mechanical problems can,

in principle, be cast into matrix and column vector form. This formulation is called matrix

mechanics to distinguish it from wave mechanics where differential operators and wavefunctions

are used. In practice, both forms of quantum mechanics are used side by side along with the

abstract Dirac approach. Usually the form of quantum mechanics chosen is the one that makes

the current problem easiest.

A matrix associated with an operator is an ordered array of numbers i,j given by the

expression

i, j i j , (0)

where i and j represent sets of quantum numbers specifying the states. Note that the specific form

of the matrix depends on the base states used to describe it. We say the description in a particular

basis is a representation of the operator.

7-1. Spin ½ corresponds to angular momentum (J2=S2, Jz=Sz) with j = ½ and m = –½ ,+½ . (a)

Use the definition (1) to derive a matrix for Sz . (b) Find the eigenvectors and show that

0 1 0 0

S and S

0 0 1 0

are the respective raising and lowering operators and use these to construct Sx and Sy.

7-2. Evaluate the matrix elements x0,0 and x0,1 for the simple harmonic oscillator. Indicate an infinite

matrix for the Hamiltonian of the harmonic oscillator (Hi,j).

Column Vectors

A general vector | has a column vector form given by the array

1

2

(0)

n

7-3. Calculate normalized column eigenvectors for spin Sz directly from the eigenvalue

equations. Show that the matrix for Sz gives the appropriate eigenvalues when it is applied

to these vectors.

3 L 1

3 D , calculate the corresponding

eigenvector in the “live” and “dead “basis.”

8. TIME DEVELOPMENT

Most often, it is convenient and desirable to use eigenstates | that correspond to conserved

quantities of operator . Since conserved quantities do not change with time, we have not yet

had occasion to see any explicit time development. Here we give the time development principle.

The Hamiltonian operator H determines the time development of a quantum mechanical

system:

H i (0)

t

or

H i . (1’)

t

|(t) = |(0) exp(-itH/)

8-6. Show that when observable commutes with H, [,H] = 0, then is conserved.

8-7. Write the time-dependent Schrödinger equation for a simple harmonic oscillator.

APPENDICES

A6 HYDROGEN EIGENFUNCTIONS

The following is a list of some normalized wavefunctions for hydrogen n m for various

values of n, , and m. a0 denotes the Bohr radius.

4 0 2

a0 2

0.529 1010 m .

e

The separated form for the wavefunctions is

where

m e im

m sin polynomial in cos

m

(0)

Rn r e constant r / n r polynomial in r

A7 Identical Particles

Fermi and Bose Particles.................................................................................................2

Fermi Particles.....................................................................................................2

Bose Particles.......................................................................................................2

Quantum Statistics...........................................................................................................3

Applications.....................................................................................................................4

Free Electron Model for Metals...........................................................................4

Density of States for Electrons................................................................5

Black-Body Radiation..........................................................................................6

However similar they are, the members of a set of twins or a pair of billiard balls are

clearly different objects. Fundamental particles, however, are identical in all respects so that

when two electrons in the same state are interchanged, there is no possible way to distinguish the

exchanged system from the original.

The simple fact that the interchange of identical particles cannot change a system has

profound consequences. We will find that only two kinds of particles can exist. For one kind,

bosons, an unlimited number can coexist in the same state (including the same place). The other

kind, fermions, can have only one particle per state.

Consider a system with two identical particles at positions x1 and x2 . The system is

governed by a wavefunction x1 , x 2 . We can exchange the particles so that the positions are

reversed producing a wavefunction x 2 , x1 . This is expressed mathematically by having an

exchange operator applied to the original wavefunction,

x1 , x 2 x 2 , x1 . (0)

2 x1 , x 2 x1 , x 2 . (0)

eigenvalue problem of the form = where is some observable. Clearly, Eq. (0) must

correspond to 2 = 2 and we find that

1

(0)

Particles that exhibit the + sign upon exchange so that = are called bosons where those

that exhibit the - sign with = are called fermions.

problem 1

When two particles are not interacting, their composite wavefunction is a product of

the independent wavefunctions u a x1 and u b x 2 , where a and b refer to different quantum

numbers. To see this, write

H 1 H 2 E . (0)

Setting

u a x1 u b x 2 , (0)

we can separate Eq. (0) into two parts,

H1ua Ea ua

(0)

H2 ub Eb ub

where

E E a Eb

problem 2

Fermi Particles

Notice that the product function u a x1 u b x 2 does not obey for either

eigenvalue 1. However, it is easy to check that the exchanged product u a x 2 u b x1

is also a solution to Eq. (0). The difference of both products is a solution that satisfies the Fermi

condition,

(0)

with

1

2

u a x1 ub x 2 u a x2 ub x1 (0)

problem 3

Now note that when a=b. That is, there is no chance that two identical fermions can

coexist in the same quantum state! This stuff is familiar matter. It includes electrons, protons,

and neutrons—in fact, all particles with half-integer spins, 21 , 23 , 25 ,... ,are Fermi particles.

Bose Particles

, (0)

applies to bosons and is easily constructed from the sum of the two products:

12 u a x1 u b x 2 u a x 2 u b x1 . (0)

problem 4

You can see immediately that does not vanish when a=b. An unlimited number of

these particles can occupy the same state. These particles are usually associated with fields and

the most familiar examples are photons and mesons. Bosons all have integer spins, 0, 1, 2,..

problem 5

, n, e - , 0 , p, quark , gluon

Quantum Statistics

particle aggregates. For instance, we can describe conductivity with a free electron model and

blackbody radiation with a photon gas model. The passage from quantum mechanical

information to macroscopic physics is effected by the methods of statistical mechanics. Here we

introduce some results of statistical mechanics without proof:

Individual particles with energy j have an average occupation number nj given by the

following expressions:

j

n j exp Maxwell - Boltzmann

kT

1

nj Fermi - Dirac

j

exp 1

kT (0)

1

nj Bose - Einstein

j

exp 1

kT

(The Maxwell-Boltzmann distribution applies to distinguishable particles)

Applications

There are many applications of the distributions above. Here we focus on the free

electron model and the Planck formula for blackbody radiation.

When we plot the Fermi-Dirac distribution

for very low temperatures, we get the curves

shown in the diagram. The curve drops to

half the maximum value at 0 where 0

is the value of at T=0. This energy is

termed the Fermi energy and is roughly the

typical energy per particle near zero

temperature. In metals, room temperature is

a good approximation to .T=0.

spectrum for . That is,

N n

j

j n d (0)

where d is the number of states in energy interval d. is called the density of states

factor. To proceed with the calculation of N, we need to determine .

Density of States for Electrons

nh

px x (0)

2L

with similar expressions for the y and z dimensions. The n’s can be approximated as

continuous variables in a macroscopic volume so an increment of the total number of

states is

dnx dn y dnz

We find

8 L3

dnx dn y dnz 3 dpx dp y dpz .

h

The product dpx dp y dpz is a volume element in momentum space in direct analogy with

the standard spatial volume. This can be converted to spherical coordinates using

dpx dp y dpz = 4 p 2 dp where the total momentum magnitude p is the analog of radius r.

Finally, we must (i) divide by 8 because only positive values of n’s (and p’s) are used and

this applies to only 18 of a sphere of radius p; (ii) multiply by 2 to account for the two

possible spin states of an electron. The result is

8V 2

d (number of states) p dp (0)

h3

problem 6

We want to identify the left hand side of (0) with d so we need to convert

from momentum to energy. Since

p2

,

2m

Eq. (0) becomes

8Vm 2m 2 12

1

(0)

d d

h3

Now we can complete the calculation of Eq. (0). Note from the diagram that at T=0, n=1

below 0 and n=0 above 0 . The integral can be solved for :

2

2 N

3

0 (0)

3 V

h2

2m

problem 7

N

3. 7 1022 conduction electrons per cm 3 .

V

so that

0 4.1 eV .

This Fermi energy is huge compared with typical thermal energy kT 0. 025 eV. That is, room

temperature is a lot like absolute zero to conduction electrons.

We see that the cathode of a vacuum tube must be heated to increase electron emission.

Likewise, a photomultiplier must be cooled to decrease spontaneous emission of electrons.

Calculations similar to those done here can establish the heat capacity of the metal and detail the

features of thermionic emission.

Black-Body Radiation

Light and radiation in equilibrium with heated material can be treated as a photon gas.

The model material is termed a “black body” because it absorbs all the radiation incident upon it.

The energy of radiation in volume V is given by the expression

E j nj

j

n d

0

(0)

where n is the Bose-Einstein distribution (with =0 because photons have no ‘rest’ energy) and

is the energy density of states for photons.

Fortunately, we have done most of the work already. Photons have two polarization

states (corresponding to two spin states for electrons) and Eq. (0) applies to the number of

photon states. Photon momentum and energy are given in terms of frequency n ,

hn

p and hn (0)

c

so that Eq. (0) becomes

8V

d 3 n 2 dn (0)

c

8hV n3 (0)

0 c 3

e hn / kT

1

dn .

The integrand of this expression enables us to write the energy density per unit frequency

interval (n),

8h n3

n (0)

c 3 e hn / kT 1

problem 8

x3 4

ex 1dx

15

giving the detailed T4 law,

8 5 k 4 4 (0)

E 3 3

VT

15c h

A8 Dirac Delta Function

Kronecker Delta...................................................................................................1

Dirac Delta...........................................................................................................1

Properties and Representations........................................................................................2

Properties.............................................................................................................2

Representations of the Delta Function.................................................................3

Fourier Integral Theorem.........................................................................3

Other Representations..............................................................................3

Applications.....................................................................................................................4

Boundary Conditions...........................................................................................4

Bound State..........................................................................................................5

Reflection and Transmission................................................................................5

The Kronecker delta ij is familiar from relations like i j ij . In this case the states

are discrete like the eigenfunctions of a one-dimensional well or harmonic oscillator. However,

quantum states may also be continuous like the eigenstate of free-particle momentum, k . The

Dirac delta function x is the analog of ij for inner products of continuous states,

k k k k .

We introduce x by first writing properties of ij for discrete sums. We then insist that

the change ij x preserves these properties when we convert the sums to continuous

integrals, .

Kronecker Delta

1 i j

ij (0)

0 i j

and two central properties are

ij 1

j

(0)

f j ij f i

j

problem 9

4

Evaluate the sum f j j 3 by expanding it and using the definition (0).

j 1

Dirac Delta

Changing from sums in Eqs. (0) to integrals and changing the notation by the

replacement ij x , we write

x dx 1 (0)

f x x dx f 0

where the integration intervals include the neighborhood

around x=0. These properties can be realized by a curve

like the one shown in the diagram. It is zero everywhere

except for a narrow spike of unit area around x=0.

Imagine now that the rectangle is made narrower and taller so that the area remains the

same but the width approaches zero and the height approaches infinity. The resulting Dirac

delta function satisfies the desired conditions and is defined by the relations (0) and

x0

x (0)

0 x0

problem 10

2

cos d .

Properties and Representations

Properties

Several delta function properties are collected here: Among the most important is

f y y a dy f a (0)

problem 11

Prove Eq. (0). Hint: change the variable from y to x = y-a then use one of the basic

relations (0)

problem 12

2

Evaluate cos d

0

problem 13

x x

(0)

1

a x x

a

The delta function is written in many ways. The most important of these is based on the

Fourier integral theorem.

f x g k e

ikx

dk

1

(0)

g k f x e

ikx

dx

2

A way to look at this theorem is to suppose you are given a function f(x) that you

want to expand in the base states exp(ikx). The second expression shows how to find the

coefficients of the expansion and the first is the expansion. You can use this view to

prove the most important delta function representation:

1

x e

ikx

dk (0)

2

problem 14

Other Representations

Applications

Delta functions are easy to manipulate and are used here to analyze simplified versions of

standard problems. We treat a bound state of a delta function well and reflection-transmission

from a delta function barrier.

Boundary Conditions

The boundary conditions imposed on the usual square well or square barrier are that at

the interface of regions I and II obey

I II and I II

with similar conditions at the interface of regions II and III.

When the barrier or well is infinitesimally narrow, the wavefunction must still match on

both sides, , but the slope changes abruptly. This can be seen by writing the

Schrödinger equation with potential V x and integrating over an infinitesimal interval

, surrounding x=0. Taking the limit 0 gives the result

2mV

0 0 2 0 (0)

problem 15

Show that in the neighborhood x=0 of a potential V x , the boundary condition for

2mV

slopes is given by 0 0 2 0 .

Bound State

(a) Find solutions to the Schrödinger equation for regions outside of x=0 that assure

0 as x . The form for the wavefunction to the left and right of the potential are then

e x and e x where is a positive real constant, (b) Apply the boundary conditions at

x=0:

0 0

2mV

0 0 2 0

This imposes a condition on the constant that determines the allowed energy.

problem 16

Find the bound state energy and wavefunction for V x S x . Sketch the

mS 2

wavefunction and well. ans E 2

2

follows: (a) Find a solution to the Schrödinger equation for the region to the left of x=0 that

describes waves traveling both left and right (reflected and incident waves). The form for the

wavefunction here is x Ae ikx Be ikx where k is a positive real constant. (b) For the region

to the right of the delta function, find a solution to the Schrödinger equation that represents a

transmitted wave moving to the right, x Ce ikx . (c) Apply the boundary conditions at x=0:

0 0

2mV

0 0 2 0

These give relations between the coefficients. (d) Determine the reflection and transmission

2 2

B C

coefficients using any two of R ,T , and R + T=1.

A A

problem 17

what incident energy are reflection and transmission equally likely?

A9 Perturbation Theory

Basic Problem..................................................................................................................1

First Order Results...............................................................................................1

Derivation............................................................................................................2

Applications.....................................................................................................................4

Alkali Atoms........................................................................................................4

Normal Zeeman Effect.........................................................................................5

We can find exact solutions to only a few basic systems like the simple harmonic

oscillator and the Hydrogen atom. More complex systems must be treated with approximation

techniques. Foremost among these is the perturbation approach where we neglect relatively

small terms to arrive at a simple system (however artificial) that can be solved. Then we add

back corrections (perturbations) due to the formerly neglected quantities.

As an example, consider finding the ground state energy of He. If we neglect the

interactions between the electrons and consider only the forces between the nucleus and each

electron, the wavefunction is made of Hydrogen wavefunctions. The electron—electron

interaction is then treated as a perturbation and its approximate contribution to energy is added to

the energy of the simplified system.

Basic Problem

H,

H H0 V ,

where H0 is the unperturbed Hamiltonian for a fully solved system and V is a relatively small

perturbation term. Find corrections to the unperturbed eigenvalues and eigenfunctions to various

degrees of accuracy.

At present, we limit ourselves to the simplest case of first order corrections. Denote the

energy and eigenstate of the unperturbed system as E0 and 0 (here the zero does not necessarily

refer to the ground state). Then we have

H0 0 E 0 0

(0)

and the correction to the energy (to first order) is

E E0 0 V 0 .

(0)

nV 0

0 0 n (0)

n 0 E0 En

where the sum is over the possibly infinite number of unperturbed eigenstates. In practice, only

a few states near the original 0 are included.

problem 18

Find first order corrections to both energies and wavefunctions for a particle in a rigid

one-dimensional box of length L containing potential V x x, 0 x L where is a

small parameter.

Derivation

A clever but simple derivation produces Eqs. (0) and (0). Introduce an artificial

parameter as a coefficient for the presumed small interaction V so that

H H0 V .

(0)

Now we can think of the solutions as power series in and write

E E 0 E 1 2 E 2 ...

,

1 2 (0)

0

2

...

where the superscripts indicate the order of the correction. Substitute these into the exact

expression,

H E

(0)

and since Eq. (0) must hold for an arbitrary value of , the coefficients of each power ofmust be

independent and equal on each side of (0). We obtain

0 : H 0 0 E 0 0

1 1

1 : H 0 V 0 E0 E 1 0

(0)

2 1 2 1

2 : H 0 V E0 E 1 E 2 0

problem 19

The first order approximations can be obtained from the second of Eqs. (0), but first the

1

unknown kets must be re expressed in terms of known quantities; in particular, they are

expanded in terms of the complete base states of the unperturbed problem n :

1

a

n0

n n . (0)

Substitute and apply the bra 0 to both sides of the expression so that the normalization

condition 0 0 1 gives Eq. (0). The coefficients an are similarly determined by applying the

bra n and using the orthonormality condition n k nk . Equation (0) then gives the first

order state of Eq. (0).

problem 20

Applications

Perturbation theory is applied so widely that almost every branch of modern physics will

provide examples. Here we give two relatively simple physical applications of first order

perturbation theory.

Alkali Atoms

The alkali elements have one outer electron orbiting an inner core of electrons. On

average, this inner core can be treated as spherically symmetric. When the outer electron is far

from the core, it sees only a single charge and has a Hydrogenic energy level. When it penetrates

the inner core, it sees a larger positive charge and is perturbed from the Hydrogen level.

We can consider the outer electron energy to be a perturbed Hydrogen level. The

situation is shown in the diagram where the total interaction experienced by the valence electron

is the sum of a single proton and a combined point charge +(Z-1)e surrounded by a uniform

cloud of negative charge -(Z-1)e

problem 21

Z 1) 2 e 2 Z 1) 2 e 2 r 2 r R

k k

V r R3

0 rR

The degree to which the outer electron penetrates the inner core depends on its angular

momentum . This agrees with classical ideas where the lower the angular momentum, the

2

closer the orbit approaches the nucleus. It follows that is larger for smaller .

Note that the perturbation V becomes increasingly negative for decreasing r. It follows that the

perturbation in energy,

E 1 V

2

dr

(0)

is more negative for lower angular momenta. This explains why the nS level is lower than the

nP level in Alkali metals (n=2 for Lithium and n=3 for Sodium, etc.)..

problem 22

Briefly explain why the outer electron S wave is lower than the outer electron P wave in

Alkali atoms.

When a hydrogen atom is placed in a strong uniform magnetic field B, certain energy

levels “split” into multiple levels. The interaction of the magnetic field with the orbiting electron

causes perturbations of the original energy levels that depend on the angular momentum. We

note that this “normal” Zeeman effect neglects the contribution of electron spin.

You will recall that a current I experiences a force when it is placed in a magnetic field.

The magnetic moment for a current loop of area A is defined by IA . The classical value

for the electron current is

e

L (0)

2m

where L is the angular momentum and the energy of the interaction with the field is given by

V · B . If the direction of B is chosen to be the z-direction, then

e

V BLz (0)

2m

problem 23

meB

Calculate the energy perturbations for the normal Zeeman effect. ans :

2m

Notice that each level is now split into 2+1 levels by the magnetic field. This is a

special case of a general phenomenon. Levels that are degenerate in energy are often perturbed

differently and they acquire different energies. We say that the degenerate level is split by the

interaction.

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