Class 1.

Quantum
mechanics: IA
Dr. Marc Madou Chancellors Professor
UC Irvine 2012

Schrdinger's Cat could not cope

with a lifetime of uncertainty.

In the IC and NEMS world, we are moving fast into the realm
of quantum mechanics. Moores law might remain valid
until about 2020 but by then the scale of electronic
components will be at the molecular/atomic level, and
hence can no longer be described by classical mechanics.
Quantum computing, nanotechnology, including
nanotubes, nanowires, biological nano-structures and
quantum dots, all require some grounding in quantum
mechanics to be understood at all. Quantum mechanics
must now become a familiar tool not only to physicists but
also to materials scientists, biologists and electrical,
mechanical and bioengineers.

Contents
Classical Theory Starts
Faltering
Quantum Mechanics to
the Rescue
Schrdingers Equation

Classical Theory Starts

Faltering
Electrical conductivity
Heat capacity in
metals and insulators
Temperature
dependence of
electrical conductivity
and heat capacity
Hall effect
Blackbody radiation
Photoelectric effect

Paul Drude
(1863-1906).

Classical Theory Starts

Faltering

Moderncondensed
matterphysicsreally
startedwiththediscovery
oftheelectronbyJ.J.
Thompsonin1897.
Drudedescribeselectrons
inametalasafree
electrongas(FEG)to
explainelectrical
conductivityandOhms
lawwith: m2e
ne

Classical Theory Starts

Faltering
Usingthelatticeconstant,a,
forthemeanfreepath,andthe
MaxwellBoltzmannEquation
atT=300Ktocalculatevth,
valuesfortheresistivityofa
metalareobtainedthataresix
timestoolarge.
Temperaturedependenceis
wrongtoo.ExpectedwasaT
butwhatweget
experimentallyis:

0 + T

1
me v th
me 8k BT
= 2 = 2

ne ne a me

Classical Theory Starts

Faltering
Sincesolidscontainanumber
ofatomsandelectronswith
similardensity,whythelarge
conductivitydifferences?
Moreintriguingyet,basedon
theabovewhywouldcarbon
allotropescomewithsuch
highlyvaryingelectrical
conductivities?

Classical Theory Starts

BasedontheDrudeassumptionthat
Faltering

electronsinametalbehaveasamono
atomicgasofNclassicalparticles,they Atomsinalatticeusuallyhaveno
translationalenergyandas
shouldbeabletotakeupatranslational
temperatureincreasesonlyvibrational
kineticenergywhenthemetalisheated
energyincreases.
Accordingtotheequipartitionprinciple
Inthecaseofamonovalentmetal,the
ofenergyinagasthereisaninternal
latticespecificheatcontribution,Cv,lat,
energyU=1/2kBTperdegreeoffreedom
equals3R.Thevibrationofaclassical
Sotheelectroncontributiontothe
1DharmonicoscillatorisU=kT
with1/2kTforkineticand1/2kTfor
specificheatcapacity(expressedper
potentialenergy.
mole)is:
FromthelatterweexpectCv,lattobe
U 3N
3
3
=
k BT = N Ak B T = RT
constantat3Ror25J/molKtheso
n 2n
2
2
calledDuLongPetitlaw.

U
3
C v,el =
( )v = R
T n
2

Classical Theory Starts

Faltering
tobeconstantat3Ror25J/molK(

WeexpectCv,lat
DuLongPetitlaw).Experimentally,Cv,thesumof
vibrationalandelectroniccontributions(Cv=
Cv,el+Cv,lat=4.5R),isproportionaltoT3atlowTand
approachesaconstant3R,athighT.
ThetotalCvformetalsisfoundtobeonlyslightly
higher than that for insulators, which only feature
lattice contributions. Where is the electronic
contribution? The absence of a measurable
contributionbyelectronstotheCVwashistorically
one of the major objections to the classical free
electron model. Conduction electrons only
contributeasmallpartoftheheatcapacityofmetals
but they are almost entirely responsible for the
electricalconductivity.

Classical Theory Starts

Faltering
In 1853, long before Drudes time, Gustav
Wiedermann and Rudolf Franz found the
ratio of thermal and electrical conductivities
of all metals has almost the same value at a
given temperature or one obtains Lorenz
numberLas: 2

c mv

3 k
= v,el 2 dx = ( B ) 2 = L
T
3ne
2 e

Thiswasobtainedby:
3
1
3
c v,el = nk Band mv 2dx = k BT
2
2
2

LorenznumberLin108Wattohm/K2
Metal
273K
373K
Ag
2.31
2.37
Au
2.35
2.40
Cd
2.42
2.43
Cu
2.23
2.33
Ir
2.49
2.49
Mo
2.61
2.79
Pb
2.47
2.56
Pt
2.51
2.60
Sn
2.52
2.49
W
3.04
3.20
Zn
2.31
2.33

Classical Theory Starts

Faltering
Drudeusingclassicalvaluesfor
theelectronvelocityvdxand
heatcapacityCv,el,somehowgot
anumberveryclosetothe
experimentalvalue.Buthow
luckythatDrudedudewas:bya
tremendouscoincidence,the
errorineachtermhemadewas
abouttwoordersof
magnitude.intheopposite
direction

Miscalculation

Classical Theory Starts

Faltering
FormostmetalstheHallconstantisnegative.ButforBeand
Zn,forexample,RHispositive.Ofcourseenergybands
werenotheardofyetandtheresultsofapositiveRHwere
bafflingatthetime:howcanwehaveq>0(evenfor
metals!?).

Classical Theory Starts

AblackbodyoftemperatureTemitsacontinuous
Faltering
spectrumpeakingat .Atveryshortandvery
max

longwavelengthsthereislittlelightintensity,with
mostenergyradiatedinsomemiddlerange
frequencies.Asthebodygetshotterthepeakofthe
spectrumshiftstowardsshorterwavelengths.
Classicalinterpretationpredictedsomething
altogetherdifferent;intheclassicalRayleighJeans
model,insteadofapeakintheblackbodyradiation
andafallingawaytozeroatzerowavelengththe
measurementsshouldgooffscaleattheshort
wavelengthendtowardsultravioletcatastrophe
MaxPlancktooktherevolutionarystepthatledto
quantummechanics:E=h

6.626 x 10-34 J.s

Classical Theory Starts

never appreciated how far
Faltering

Planck, interestingly,
removed from classical physics his work was. The
Planckconstanth,wasabitlikeanuninvitedguestat
a dinner table; no one was comfortable with this new
guest.Discontinuitiesinthenanoworldaremetedoutin
units based upon this constant. It is the underlying
reason for the perceived weirdness of the nanoworld;
theexistenceofaleastthingthatcanhappenquantitya
quantum. The ubiquitous occurrence of discontinuities
in the nanoworld, constantly upsets our commonsense
understanding of the apparent continuity of the
macroscopicworld.

Max Planck April 23, 1858 October 4, 1947

Classical Theory Starts

Photoelectriceffect;noelectronsareejected,regardlessofthe
Faltering
intensityofthelight,unlessthefrequencyexceededacertain
thresholdcharacteristicofthebombardedmetal(redlightdidnot
causetheejectionofelectrons,nomatterwhattheintensity).
Thephotoelectricphenomenoncouldnotbeunderstoodwithoutthe
conceptofalightparticle,i.e.,aquantumamountoflightenergy.
Einstein's1905paperexplainingthephotoelectriceffectwasoneof
theearliestapplicationsofquantumtheoryandamajorstepinits
establishment.
Theremarkablefactthattheejectionenergywasindependentofthe
totalenergyofilluminationshowedthattheinteractionmustbelike
thatofaparticlewhichgaveallofitsenergytotheelectron!

Einstein reintroduced a modified form of the old corpuscular theory

of light, which had been supported by Newton but which was long
abandoned.

Classical Theory Starts

Faltering
Theelectronchargewas
determinedbyRobertMillikan
in1909andwiththatvalue
andtheslopeofthelinesa
valueforhof6.626x1034J.s
canbecalculated,identicalto
theonederivedfromthe
hydrogenatomspectrumand
blackbodyradiation(see
above)

Classical Theory Starts

Faltering
TheyoungEinstein,in1905,wasthe
firstscientisttointerpretPlancks
workasmorethanamathematical
trickandtookthequantizationof
light(E=h)forphysicalreality.He
gavetheuninviteddinnerguestthe
Planckconstanthaplaceatthe
quantummechanicsdinnertable.
WhatEinsteinproposedherewas
muchmoreaudaciousthanthe
mathematicalderivationsbyPlanck
toexplaintheUVcatastropheaway.

Classical Theory Starts

Faltering
The three experiments that
made
the
quantum
revolution,
Blackbody
radiation, the photoelectric
effect and the Compton
effect all indicate that light
consistsofparticles.

Arthur Harry Compton (1892-1962).

Quantum Mechanics to
the Rescue
Einsteinsspecial
relativityallowsoneto
calculatethemomentum,
p,ofaphotonstarting
from:

DeBroglie,whilestudyingfor
hisPhDinParisin1924,
postulatedthatthislast
equationalsoappliedtoa
movingparticlesuchasan
2
2
2 2
electron,inwhichcaseisthe
E = (pc) + (m0c )
wavelengthofthewave
associatedwiththemoving
E 2 = (pc) 2 + 0orE = pc
particle,i.e.,amatterwave.
h
E h h

p = =
=
mv
c
c

Quantum Mechanics to
the Rescue
Inhis1928testsThompsonjuniorandReid
observedinterferencepatternsfromelectrons
reflectingfromathinpolycrystallinemetalfoil
surface.
ClintonDavissonandLesterGermer,atBell
Laboratories,in1927foundthesame
experimentalevidence:abeamofelectrons
scatteredfromasinglecrystalofnickelresulted
inadiffractionpatternfittingtheBragg
diffractionlaw
Thisestablishedthewavecharacterofelectrons,
formingthebasisofanalyticaltechniquesfor
determiningthestructuresofmolecules,solids
andsurfaces,suchasinLEED(lowenergy
electrondiffraction)andSEM.

Davisson-Germer experiment (1927).

Quantum Mechanics to
the Rescue
LouisVictor,7thducde
Broglie(18921987)
discoveredthusthatthesecret
ofPlancksandEinsteins
quantalayinagenerallawof
naturei.e.,thedualcharacter
ofwavesandparticles.
Einsteincommentedaboutthis
fantasticinsight:deBroglie
hasliftedthegreatveil.
Evenbuckyballsarewavy

Quantum Mechanics to
the Rescue
Einsteingave,whatwehadcometo
thinkofasawave(light)aparticle
characteranddeBrogliegavewhat
wethoughtofasaparticle(electrons)
awavecharacter.Radiationhaswave
characterandparticlecharacterand
matterhasparticleandwave
characteroratthenanoscale,nature
presentsitselfwithawaveparticle
duality.

mv

Quantum Mechanics to
the Rescue
Thewaveparticleduality
introducedintheprevious
sectionforcedphysiciststo
reconsidertheirdescriptionof
thepositionandmomentumof
verysmallparticlesandisatthe
coreoftheHeisenbergs
uncertaintyprinciple(HUP).
Inthenanoworld,the
Heisenbergprinciplestatesthat
therearephysicalparametersin
quantumphysicswhosevalues
cannotbeknownaccurately
simultaneously.

Quantum Mechanics to
the Rescue

h
pxx2=h
h
Et
=h
2

Quantum Mechanics to
the Rescue
Theuncertaintyabouttheenergyofaparticledependsonthetimeinterval t
that the system remains in a given energy state. Importantly this also means
thatconservationofenergycanbeviolatedifthetimeisshortenough.
Fromtheuncertaintyprinciplesitispossiblethatemptyspacelocallydoesnot
havezeroenergybutmayactuallyhavesufficientEforaveryshorttimet
tocreateparticlesandtheirantiparticles.Thiscanbedemonstratedthroughthe
Casimireffect.
This effect is also responsible for lifetime broadening of spectral lines.
Shortlivedexcitedstates(smallt)possesslargeuncertaintyintheenergyof
the state (large E). As a consequence, shorter laser pulses (e.g., femto and
attosecondlasers)havebroaderenergy(thereforewavelength)bandwidths.

Quantum Mechanics to
the Rescue
Basedontheideathatthe'vacuum'of
spaceisactuallyaseethingfoamof
quantumfluctuationsofdifferent
frequencies,Casimirproposedthatif
twoelectricallyconducting,but
unchargedparallelplatesweremounted
asmalldistanceapartinavacuum,they
wouldtendtobedrawntogether.An
importantpointisthattheplatescarry
noelectricalchargesothatany
interactionbetweentheplatesmust
comefromsomeothersource.
UsingMEMSdevicestheCasimirforce
hasbeenmeasured

Quantum Mechanics to
the Rescue
TheexistenceofaZeroPoint
Energy:vibrationalenergy
cannotbezeroevenatT=0K
isalsoaconsequenceofthe
Heisenbergprinciple.Ifthe
vibrationwouldceaseat
T=0K,thenthepositionand
momentumwouldbothbe0,
violatingtheHUP.

Schrdingers Equation
Schrdinger, after attending a seminar
on Einsteins and de Broglies ideas
that wavelike entities can behave like
particles and vice versa, thought that
there must be a wave equation, (x,t),
todescribeparticles.
Schrdingers picture of the atom has
theelectronstandingwavesvibratingin
their orbitals much like the vibrations
on a string but in three dimensions
instead of one. In this figure a two
dimensional
representation
of
Schrdingerwaves,likevibrationsona
drumskin,isshown.

Schrdingers Equation
Aconceptthatplaysanimportantroleinbothclassicalandquantum
theoryisthatoftheHamiltonianofasystem.
H=En(TotalEnergy)=KE(KineticEnergydependsonv)+PE
(PotentialEnergyVdependsonposition)
Example 1: free moving object: V=0, knowing x0 and p, we can
predict xt at t in other
words we can predict the trajectory at all
2
p
H
=
E
=
+ V(x)andsinceV(x) = 0,E = E k
timeslater.
2m
v = dx/dt =

dp
d2x
F =
= ma = m 2
dt
dt

2E k
m

2E k
2p 2
p
xt x0 =
t=
t
=
t = vt
2
m
2m
m

Schrdingers Equation
Example2:harmonicoscillators,2
dx
k
=

x
Hookeslaw(F=kx)
dt 2
m
As the amplitude (A) can take
any value, this means that the

energy (E) can alsotake

any
valuei.e.,energyiscontinuous.
Any energy value is allowed by
simply changing the force
constantk.

2
2
22
p
k
x
m
v
k
x
E
=2

o
r
a
l
s
o
E
=

m
2
22
2
2

kk
k
m
A
c
o
s
tk
A
s
i
n
t

m
m
m

=2m

Schrdingers Equation
In the late 18th century the mathematician Pierre Simon de Laplace (17491827)
encapsulatedclassicaldeterminismasfollows:ifatonetimeweknewthepositions
andmotionofalltheparticlesintheUniverse,thenwecouldcalculatetheirbehaviorat
anyothertime,inthepastorthefuture.Inclassicalphysics,particlesandtrajectories
are real entities and it is assumed that the universe exists independently from the
observer,thatitispredictableandthatforeveryeffectthereisacausesoexperiments
arereproducible.
Heisenbergsuncertaintyprincipledestroyedallthis.Inquantumphysicsthemeasured
and unmeasured particle are described differently. The measured particle has definite
attributessuchaspositionandmomentum,buttheunmeasuredparticledoesnothave
one but all possible attribute values, as Nick Herbert in his book Quantum Reality
writessomewhatlikeabrokenTVthatdisplaysallitschannelsatthesametime.

Schrdingers Equation
Erwin Schrdinger (18871961), in
1926, encouraged by Debye who
remarked that there should be a wave
equation to describe the de Broglie
waves, proposed a wave equation that
can be applied to any physical system
in which it is possible to describe the
energy mathematically. In one
dimensionhepostulated:

(x,t)
8 m
+
[E V(x,t)] (x,t) = 0
2
2
x
h
2

Schrdingers Equation
Thefirsttermistherateofchangeoftherateofchangeofthewavefunctionwith
distancex.TheenergyoftheparticleisEandthepotentialenergyfunctionto
describetheforcesactingupontheparticleisrepresentedbyV(x,t).
TheSchrdingerequationhasthesamecentralroleinquantummechanicsthat
NewtonslawshaveinmechanicsandMaxwellsequationsinelectromagnetism.
SolutionstoNewtonsequationsareoftheformv=f(x,t),whilesolutionstothe
wavearecalledwavefunctions(x,t).
LikeNewtonsequation,itdescribestherelationbetweenkineticenergy,potential
energy,andtotalenergy.Ifoneknowstheforcesinvolved,onecancalculatethe
potentialenergyVandsolvetheequationtofind.
SolvingtheSchrdingerequationspecifies(x,t)completely,exceptforaconstant;
if(x,t)isasolutionthenA(x,t)isasolutionaswell.

(x,t)
8 m
+
[E V(x,t)] (x,t) = 0
2
2
x
h
2

Schrdingers Equation
ThesocalledCopenhagenInterpretationofSchrdingersequationisthat
the(x,t)functionisnotsomephysicalrepresentationofaphysicalsubstance
asinclassicalphysics(e.g.,theamplitudeofawaterwave)butaprobability
amplitudeoftheparticlewhich,whensquared,givestheprobabilityof
findingtheparticleatagivenplaceatagiventime:|(x,t)|2dx=probability
theparticlewillbefoundbetweenxandx+dxattimetandthewavefunction
itselfhasnophysicalmeaning.
Sincetheprobabilitythattheparticleissomewheremustequalone,itholds
thatonecannormalizethisprobabilityfunctionas:
+

| (x,t) | dx = 1
2

TheCopenhageninterpretationalsoholdsthatanunmeasuredparticleina
certainsenseisnotreal:itsattributesarecreatedorrealizedbythemeasuring
act.Anotherwayofsayingthisisthatawavefunctioncollapsesupon
measurement;beforemeasurementaparticleisdescribedbyawavefunction

describedbytheSchrdingerequationbutuponmeasuringthatparticles
wavesuddenlyanddiscontinuouslycollapses.

(x,t)
8 m
+
[E V(x,t)] (x,t) = 0
2
2
x
h
2

Schrdingers Equation
Because (x,y,z,t)iscomplexandcanbepositiveornegative,itcannotbe
theprobabilitydirectly.TheBorninterpretationofplacesrestrictionson
theformofthewavefunction:
(a)mustbecontinuous(nobreaks);
(b)Thegradientof(d/dx)mustbecontinuous(nokinks);
(c)musthaveasinglevalueatanypointinspace;
(d)mustbefiniteeverywhere;
(e)cannotbezeroeverywhere.

(x,t)
8 m
+
[E V(x,t)] (x,t) = 0
2
2
x
h
2

Schrdingers Equation
In operator form the SE is Hoperatoracting on function an eigen
function=EfunctionmultipliedbyanumberEaneigenvalue)
WhereHistheonedimensionalHamiltonianoperatorandinwhichtheenergyEofthe
particlesiscalledtheeigenvalue,andtheeigenfunction.
Expressed yet another way, kinetic and potential energies are transformed into the
Hamiltonian which acts upon the wavefunction to generate the evolution of the
wavefunctionintimeandspace.TheSchrdingerequationgivesthequantizedenergies
ofthesystemandgivestheformofthewavefunctionsothatotherpropertiesmaybe
calculated.

22
h

H
=

V
(
x
,
t
)
[822

V
(
x
,
t
)
]
(
x
,
t
)

(
x
,
t
)
8

m
x
m
x

22
22

(x,t)
8 m
+
[E V(x,t)] (x,t) = 0
2
2
x
h
2

Quantum Jokes