PlanforFri,31Oct08

Lecture
Emissionspectrumofatomichydrogen(7.3)
TheBohrmodelofhydrogen(7.4)
Quantummechanicalmodel(7.5)

Quiz5

Emission

PhotonEmission
Relaxationfromone
energyleveltoanother
byemittingaphoton.
WithE=hc/
If=440nm,
=4.5x1019J

AtomicEmission
Whenweheatasampleofanelement,theatomsbecomeexcited.Whentheatom
relaxesitemitsvisiblelight.Thecolorofthelightdependsontheelement.

Li

Na

Ca

When the light emitted

from excited atoms is
passed through a
prism, we see discrete
bands of color at
specific wavelengths.

Sr
H
Li
Ba

EmissionspectrumofH(cont.)
LightBulb

HydrogenLamp

Quantized,notcontinuous

EmissionspectrumofH(cont.)

Wecanusetheemissionspectrumtodeterminethe
energylevelsforthehydrogenatom.

TheBohrModel
NielsBohrusestheemissionspectrumof
hydrogentodevelopaquantummodelforH.
Centralidea:electroncirclesthenucleusin
onlycertainallowedcircularorbitals.
BohrpostulatesthatthereisCoulombicattractionbetweeneandnucleus.
However,classicalphysicsisunabletoexplainwhyanHatomdoesnt
simplycollapse.

TheBohrModelof
theatom

Principle Quantum number: n

An index of the energy levels
available to the electron.

TheBohrModel(cont.)
2

Z
18
E 2.178x10 J 2
n

Energylevelsgetclosertogether
asnincreases
atn=infinity,E=0

Identifytheenergyleveldiagramthatbest
representshydrogen:

TheBohrModel(cont.)
WecanusetheBohrmodeltopredictwhatEis
foranytwoenergylevels

E E final E initial
1
1
18
18
E 2.178x10 J 2 (2.178x10 J) 2
n initial
n final

18

E 2.178x10

1
1
J 2 2
n final n initial

TheBohrModel(cont.)
Example:Atwhatwavelengthwillemissionfrom
n=4ton=1fortheHatombeobserved?
18

E 2.178x10

1
1
J 2 2
n final n initial
1

E 2.178x10

18

E 2.04 x10

hc
J

18

1
J 1 2.04 x1018 J
16

9.74 x108 m 97.4nm

TheBohrModel(cont.)
Example:Whatisthelongestwavelengthoflight
thatwillresultinremovaloftheefromH?
1

1
E 2.178x1018 J 2 2
n final n initial
1

E 2.178x1018 J 0 1 2.178x1018 J
18

E 2.178x10

hc
J

9.13x108 m 91.3nm

Then=4ton=1transitioninhydrogencorresponds
toawavelengthof97.4nm.Atwhatwavelengthis
then=4ton=2transitionexpected?
A.
B.
C.
D.

ExtensiontoHigherZ
TheBohrmodelcanbeextendedtoanysingle
electronsystem.mustkeeptrackofZ
(atomicnumber).
2

Z
18
E 2.178x10 J 2
n

Z=atomicnumber
n=integer(1,2,.)

Examples:He+(Z=2),Li+2(Z=3),etc.

ExtensiontoHigherZ(cont.)
Example:Atwhatwavelengthwillemissionfrom
n=4ton=1fortheHe+atombeobserved?
1

1
E 2.178x1018 J Z 2 2 2
n final n initial
2

E 2.178x10

18

E 8.16x10

18

hc
J

1
J 4 1 8.16x1018 J
16

2.43x108 m 24.3nm

H He

SowhathappenedtotheBohrModel?
Althoughitsuccessfullydescribedthelinespectrumofhydrogen
andotheroneelectronsystems,itfailedtoaccuratelydescribe
thespectraofmultielectronatoms.
TheBohrmodelwassoonscrappedinfavoroftheQuantum
Mechanicalmodel,althoughthevocabularyoftheBohrmodel
persists.
However,Bohrpioneeredtheideaofquantizedelectronicenergy
levelsinatoms,soweowehimbig.

Thanks Niels Bohr!

QuantumConcepts
TheBohrmodelwascapableofdescribingthe
discreteorquantizedemissionspectrumofH.
Butthefailureofthemodelformultielectronsystemscombinedwith
otherissues(theultravioletcatastrophe,workfunctionsofmetals,etc.)
suggestedthatanewdescriptionofatomicmatterwasneeded.

QuantumConcepts(cont.)
Thisnewdescriptionwasknownaswave
mechanicsorquantummechanics.
Recall,photonsandelectronsreadilydemonstrate
waveparticleduality.
Theideabehindwavemechanicswasthattheexistenceoftheelectron
infixedenergylevelscouldbethoughofasastandingwave.

QuantumConcepts(cont.)
Whatisastandingwave?
Astandingwaveisamotionin
whichtranslationofthewavedoes
notoccur.
Intheguitarstringanalogy
(illustrated),notethatstanding
wavesinvolvenodesinwhichno
motionofthestringoccurs.
Notealsothatintegerandhalf
integervaluesofthewavelength
correspondtostandingwaves.

QuantumConcepts(cont.)
LouisdeBrogliesuggeststhatforthee orbitsenvisionedbyBohr,
onlycertainorbitsareallowedsincetheysatisfythestandingwave
condition.

h
h

p mv
wavelength
m mass
v velocity
h Planck'sconstant

notallowed

QuantumConcepts(cont.)
ErwinSchrodingerdevelopedamathematical
formalismthatincorporatesthewavenatureof
matter:

E
H
H,theHamiltonian,isaspecialkindoffunction
thatgivestheenergyofaquantumstate,whichis

describedbythewavefunction,.

QuantumConcepts(cont.)
Whatisawavefunction?

=aprobabilityamplitude

Probabilityoffindingaparticleinspace:

Probability=

Withthewavefunction,wecandescribespatialdistributions.

TheProbabilityDistributionfortheHydrogen1sOrbitalin
ThreeDimensionalSpace(b)TheProbabilityofFindthe
ElectronatPointsAlongaLineDrawnFromtheNucleus
OutwardinAnyDirectionfortheHydrogen1sOrbital

Hydrogens Electron

CrossSectionoftheHydrogen1s
OrbitalProbabilityDistribution
DividedintoSuccessiveThin
SphericalShells(b)TheRadial
TwoRepresentationsoftheHydrogen1s,2s,
ProbabilityDistribution
and3sOrbitals(a)TheElectronProbability
Distribution(b)TheSurfaceContains90%of
theTotalElectronProbability(theSizeofthe
Oribital,byDefinition)

QuantumConcepts(cont.)
AnotherlimitationoftheBohrmodelwasthatit
assumedwecouldknowboththepositionand
momentumofanelectronexactly.
WernerHeisenbergdevelopmentofquantummechanicsleads
himtotheobservationthatthereisafundamentallimittohow
wellonecanknowboththepositionandmomentumofaparticle.

h
x p
4
Uncertainty
inposition

where

p (mv) mv

Uncertaintyin
momentum

QuantumConcepts(cont.)
Example:
Whatistheuncertaintyinvelocityforanelectronina1
radiusorbitalinwhichthepositionaluncertaintyis1%
oftheradius.(1=1010m)

x=(1)(0.01)=1x1012m
34
6.626x10
J.s

h
23
p

5.27x10
kg.m /s
12
4 x
4 1x10 m
p 5.27x1023 kg.m /s
7m
v

5.7x10
s
m
9.11x1031 kg

huge

QuantumConcepts(cont.)
Example(yourequantumaswell):

Whatistheuncertaintyinpositionfora80kgstudentwalking
acrosscampusat1.3m/swithanuncertaintyinvelocityof1%.

p=mv=(80kg)(0.013m/s)=1.04kg.m/s
34
6.626x10
J.s

h
x

5.07x1035 m
4 p 4 1.04kg.m /s
Verysmallweknowwhereyouare.