physics 2203, fall 2012 modern physics monday, oct. 15th ......physics 2203, fall 2012 modern...
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Physics2203,Fall2012ModernPhysics
.
Monday,Oct.15th,2012.‐‐Ch.10,Wearegoingtocreatetheperiodictable.Supplementalreading:“ModernPhysics”Serway/Moses/Moyer
Announcements‐‐‐NextMidtermonOct.31st—Chapters8‐12.‐‐‐Midtermgradespostedtoday.‐‐SubmitadetailedoutlineofyourpaperbyMonday,Oct.29th
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3d
4p
Red Δml = −1Blue Δml = 0Green Δml = +1
Threelines
Quiz#3:average7.5/10
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We now have four quantum numbersn =1,2,3,....l = 0,1,2,3,....,(n −1)ml = l,l −1,.,0,...,−l
ms = ±12
En = −1n2
mec2 ke2( )2
c( )2
Next Energy n=2l = 0,1l =1 :ml = 1,0,-1l = 0: ml = 0
ms = ±12
Lowest energy n=1l = 0ml = 0
ms = ±12
Next Energy n=3l = 0 and, 1 and 2 l = 2 :ml = 2,1,0,-1,-2l =1 :ml = 1,0,-1l = 0 :ml = 0
ms = ±12
Howdowefillthesequantumstates?Howmanyelectronsineachquantumstate?Withinagivenshell(n)whichstatesfillfirst?
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We need to learn how to fill different levels ⇒ Zeff : s, p, d, fPauli Exclusion Principle ⇒ How to occupy quantum states
Hund's Rule ⇒ Lowest Energy maximizes Spin Sz , consistent with Pauli ExclusionHund's Rule (2)⇒ Maximizes L z whenever possible
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ThePauliPrincipleisaconsequenceofQuantumMechanics:IdenXcalparXclesareindis;nguishableinQM.
(a)and(b)showtwodifferentclassicalpicturesofatwo‐electronsca\eringprocess.Itiseasytokeeptrackofelectron1andelectron2becauseweknowthepaths.
(c)Depictsaquantumprocesswherethepathsareblurredbythewavenatureoftheelectrons.Oncetheyinteractyoucan’tknowwhoiswho—indis;nguishable!
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Let ψ x1, x2( ) describe the wave function of two identical particles in 1D
ψ x1, x2( )2dx1dx2 ⇒ probability of finding
#1 between x1 ⇒ x1 + dx1
#2 between x2 ⇒ x2 + dx2
What is required is that
ψ x1, x2( )2= ψ x2 , x1( )
2 or
ψ r
1,r
2( )2= ψ r
2 ,r
1( )2
There are two obvious options
ψ r
1,r
2( ) = ±ψ r
2 ,r
1( )
+ sign are Bosons (photons): spin 0− sign are Fermions (electrons, protons, ): spin 1/2
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ψ r
1,r
2( ) = ±ψ r
2 ,r
1( ) + sign are Bosons (photons)− sign are Fermions (electrons, protons, )
Look at product wave Functions
ψab r
1,r
2( ) =ψa (r1)ψb (r2 )
These product wave functions are solution, butψa (r1)ψb (r2 ) is not proper for indistinguishabity.
ψab r
1,r
2( ) =ψa (r1)ψb (r2 ) ±ψa (r2 )ψb (r1)
+ sign are Bosons (photons)− sign are Fermions (electrons, protons, )
ψab r
2 ,r
1( ) =ψa (r2 )ψb (r1) ±ψa (r1)ψb (r2 )
ψab r
2 ,r
1( ) = −ψ r
1,r
2( )
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Fermions: ψab r
1,r
2( ) =ψa (r1)ψb (r2 ) -ψa (r2 )ψb (r1)
Lets try to put two electrons into the same state, a=b
ψab r
2 ,r
1( ) =ψa (r2 )ψa (r1) -ψa (r1)ψa (r2 )
ψab r
2 ,r
1( ) =ψa (r2 )ψa (r1) -ψa (r2 )ψa (r1) ≡ 0
Bosons: ψab r
1,r
2( ) =ψa (r1)ψb (r2 ) +ψa (r2 )ψb (r1)
Lets try to put two bosons into the same state, a=b
ψab r
2 ,r
1( ) =ψa (r2 )ψa (r1) +ψa (r1)ψa (r2 )
ψab r
2 ,r
1( ) =ψa (r2 )ψa (r1) +ψa (r2 )ψa (r1) ≡ 2ψa (r2 )ψa (r1)
Bose Condensation
1945NobelPrizefordiscoveryoftheExclusionPrinciple.”
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n=1n=2
n=3
n=4
n=5
En,l = −Zeff
2 (n,l)n2
mec2 ke2( )2
c( )2 Foragivenn,howwillZeffdependuponl?
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Letusconstructthe2electrongroundstate(Xmeindependent)oftheHeatom
Assump;on:independent‐parXcleapproximaXon.Eachelectronseestheprotonbutnoteachother.
According to the Pauli exclusion principle the two electons go inton=1, l=0, ml = 0,ms =1 / 2n=1, l=0, ml = 0,ms = −1 / 2Spectroscopic notation: 1s2
ψ100 r( ) = 1π1/2
2a0
3/2
e−2r /a0 : Z=2
ψa = (1,0,0,+) and ψb = (1,0,0,−)
Ea = Eb = −21
2
(13.6eV ) = −54.4eV
ψ(r1,r2 ) =ψ100+(r1)ψ100−(r2 )−ψ100−(r1)ψ100+(r2 )
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Ea = Eb = −21
2
(13.6eV ) = −54.4eV
ψ(r1,r2 ) =ψ100+(r1)ψ100−(r2 )−ψ100−(r1)ψ100+(r2 )
The spatial dependence is the same only spin part different
ψ(r1,r2 ) = 1π
2a0
3
e−2(r1+r2 )/a0 +− − −+
Veryimportant:secondspinisalwaysoppositefirst–Pauli!
Total Energy is E=Ea + Eb = −108.8eVExperimental number is -79.0 eVNeed to include screening of one electron by the other.
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En = −mZ
eff
2 ke2( )2
2n2( )2
ΔEn→n ' = −mZ
eff
2 ke2( )2
2 ( )21n2 −
1n '2
Eionization =mZ 2 ke2( )2
2n2( )2 =13.6eV Z
eff
2( )
rn =n2
2
ke2Zm
ForHethe1sstatesarelowerthanforHbecauseZ=2,butoneelectronwillscreentheothersoweshouldhave1>Zeff<2.
The measured ionization is 24.6eV
24.6eV =mZ 2 ke2( )2
2n2( )2 = 13.6eV Z
eff
2( )Zeff = 1.35e
The first excited state is 19.8eV
19.8eV = −mZ
eff
2 ke2( )2
2 ( )2112 −
122
Zeff = 1.39e
The measured radius is 0.05 nm
0.05 = n2
2
ke2ZmZeff = 1.6e
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Pauli Exclusion Principle ⇒ How to occupy quantum states
Li has the configuration 1s2 2s1 :⇒ Because of Pauli Exclusion Principle.
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LetsStartoffbymakingsureweknowhowtousethePauliExclusionPrinciple
HerewewilljustassignstatesUsingthePauliExclusionPrinciple H
1s 2s
He
Li
Be
Sz
1/2
0
1/2
0
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En = −mZ
eff
2 ke2( )2
2n2( )2
ΔEn→n ' = −mZ
eff
2 ke2( )2
2 ( )21n2 −
1n '2
Eionization =mZ 2 ke2( )2
2n2( )2 =13.6eV Z
eff
2( )
rn =n2
2
ke2Zm
ForLithe1sshellisfilled.ThefirstguessisthatZ=1.Sincethethirdelectronisinthen=2statetheionizaXonenergywouldbe3.4eV.
The measured ionization is 5.4eV
5.4eV =mZ 2 ke2( )2
2n2( )2 =
13.6eV4
Zeff
2( )Zeff = 1.26e⇒Why??
The measured radius is 0.20 nm
0.20 = 42
ke2ZmZeff ≈ 1.5e
This simple picture breaks down for too large Z and n.
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En = −mZ
eff
2 ke2( )2
2n2( )2
ΔEn→n ' = −mZ
eff
2 ke2( )2
2 ( )21n2 −
1n '2
Eionization =mZ 2 ke2( )2
2n2( )2 =13.6eV Z
eff
2( )
rn =n2
2
ke2Zm
ForBeboththe1sand2sshellsarefilled.Can’tdomuchhereusingthesimplehydrogenmodel.YouwouldthinkthatBewouldbelikeHewithahighexcitaXonenergybutitisnot.ThelowestexcitaXonenergyisonly2.7eV.YoufindtheeffecXveZ!
Next comes B, C, N, O, F,---Need to learn about Pauli and Hund!
2p
Be
1s 2s
Firstexcitedstate
Be
1s 2s
Groundstate
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We need to learn how to fill different levels ⇒ Zeff : s, p, d, f
6Atoms:2pelectrons
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Quantum Numbers still the same.Principal n= 1, 2, 3, ...Orbital l = 0,1,2,...(n-1) Magnetic ml ≤ l
But with Zeff (n,l) the l statesfor a fixed n will have different En,l En.0 < En,1 < En,2
Lookatthen=2states.Themaximum(mostprobableposiXon)is4‐5Xmeslargerthat1s.Butthe2shasasecondmaximummuchclosertor=0than2p.Bo\omlineisthatZeffforthe2slargerthanfor2p.Forn=3theZeff(3s)>Zeff(3p)>Zeff(3d).
4s<3d
2s<2p
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Hund's Rule ⇒ Lowest Energy maximizes Spin Sz , consistent with Pauli ExclusionHund's Rule (2)⇒ Maximizes L z whenever possibleNowwearereadytokeepgoingwiththeperiodicchart
1s 2s
2p
ml=1 ml=0 ml=‐1
B
C
N
0
F
Ne
SZ LZ
1/2 1
1 1
3/2 0
1 1
1/2 1
0 0
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Na‐‐‐3s(Ne)—1s22s22p63s1
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Na‐‐‐3s(Ne)—1s22s22p63s1:IonizaXonenergyis5.14eV
E = −Zeff2
32(13.6eV ) = 5.14eV
Zeff = 35.1413.6
=1.84e
YoulookupradiusandcalculateaZefffromtheradius?
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2:(25points)ThisisaproblemaboutusingHund’sRuleandthePauliPrincipleinamanyelectronatom,Oxygen(Z=8).WritedownthegroundstateconfiguraXonofOusingthePauliPrinciple.
ElectronicconfiguraXon1s2
AnswerElectronicconfiguraXon1s22s22p4
b) UsetheHund’sruleandthePauliprincipletodescribethegroundstate,usingtheboxesbelowandarrowsforthespinstates.
0
1s 2s
2p
ml=1 ml=0 ml=‐1 SZ LZ
1 1
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2:(25points)ThisisaproblemaboutusingHund’sRuleandthePauliPrincipleinamanyelectronatom,Oxygen(Z=8).WritedownthegroundstateconfiguraXonofOusingthePauliPrinciple.
c)Theenergyneededtoremoveoneofthe1selectronsin540eV.FindZeff.
Zeff= Whyisn’tZeff=8?
The measured ionization is 540eV
540eV =mZ 2 ke2( )2
2n2( )2 = 13.6eV Z
eff
2( )Zeff = 6.3e
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We need to learn how to fill different levels ⇒ Zeff : s, p, d, f
Example of complexity ⇒ Filling 3 d shell⇒10 electrons
11Atoms
Ni configuration is Ar closed shell plus 3d 8 4s2 : Cu is 3d10 4s1
n=3
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Hund's Rule ⇒ Lowest Energy maximizes Spin Sz , consistent with Pauli Exclusion
Nitrogen is 1s2 2s2 2p3 with Sz = 3 / 2 :Why???
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InPrinciplewejustusetheSchödingerequaXontosolvefortheenergyofamulX‐electronatom.InpracXcewecan’tsolvetheproblemfor2electrons,i.e.He!
−2
2m∇2Ψ r1,r2,.....rn( ) +U r1,r2,.....rn( )Ψ r1,r2,.....rn( ) = EΨ r1,r2,.....rn( )
First and essential approximation is assume we can represent the potential as some effective potential only dependent upon the electron density n(r).
Second assumption is that the many particle wave function can be written as a product function.
Ψ r1,r2,.....rn( ) =ψ 1 r1( )ψ 2 r2( ).......ψ n rn( )
This gives us n differential equations to solve.
−
2
2m∇2 +Un,effψ n = Enψ n
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This gives us n differential equations to solve.
−
2
2m∇2 +Un,effψ n = Enψ n
Example HeUse two 1s functions with some Zeff
Use Poissions Equation to find Ueff
Use Ueff to calculate wavefuctionsover and over again until you converge.
What will this effective potential look likeIf the electron is very close to the nucleus Zeff = ZIf the electron is far from the nucleauZeff = 1
Guess the wave functions.Use Poissions Equation to find Ueff
Use Ueff to calculate a new set of wavefuctionsover and over again until you converge.Self Consistent CalculationHartree theoryHartree Fock TheoryDensity Functional Theory.
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Guess the wave functions.Use Poissions Equation to find Ueff
Use Ueff to calculate a new set of wavefuctionsover and over again until you converge.Self Consistent CalculationHartree theoryHartree Fock TheoryDensity Functional Theory.
Kohn and Sham proved that there is Functional of the density F(ρ) that isan exact solution to the many electronSchördinger EquationsBut only God knows what this Function is!!
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ViolatesHund’s1stRule
ViolatesPauliPrinciple
ViolatesPauliPrinciple
ViolatesHund’s2ndRule