Na ρ

π /2
COORDINATE SYSTEMS SCHRÖDINGER EQUATIONS 4a 2 ⎡ y 3 ⎛ y 2 1 ⎞ y cos ( 2 y ) ⎤
n= [/ m3 ] ,A = atomic mass, [kg/mol] = ⎢ + ⎜ − ⎟ sin ( 2 y ) + ⎥
π3 ⎣ 6 ⎝ 4 8⎠
Spherical ( r ,θ ,φ ) ⎦0
4
A p2 ∂2 ∂
+V = E , (p ) 2
→− 2
, ( E )op → i a2
[ dA]det ( Rdθ )( R sin θ dφ ) ∂x 2 ∂t = ⎡π 2 − 6 ⎤⎦ = ( ∆x )
2
2m op
z x = r sin θ cos φ 12π 2 ⎣
θ p ( r ,θ ,φ ) dΩ = = 2 2 − ∂ 2 2
∂ ⎛ π x ⎞ ⎛ −π ⎞ ⎛ π x ⎞
y = r sin θ sin φ R R Ψ ( x, t ) + V Ψ ( x, t ) = i Ψ ( x, t )
2 a/2
p = ∫ cos ⎜ ⎟ dx = 0 [int. of odd fnc ]
r
⎟ ⎜ ⎟ sin ⎜
y
Energy of radiating wavelength 2m ∂x 2 ∂t a −a / 2 ⎝ a ⎠i⎝ a ⎠ ⎝ a ⎠
φ
z = r cosθ
x − ∂2 2 ∞ ⎛ d2 ⎞ ∞ π2 2
ψ ( x ) + Vψ ( x ) = Eψ ( x ) p = ∫ ψ * ( x) ⎜ − ψ ( x ) dx = ∫ ψ * ( x )( 2mE1 )ψ ( x ) dx = 2
o
1.24 × 104 [eV ⋅ A ] time ind. S.E.: 2 ⎟
MATH STUFF E= , V=
E
, ν=
c
2m ∂x 2 −∞
⎝ dx ⎠ −∞ a
λ q λ
∞ r probability: Ψ = Ψ *Ψ , normalize: 1 = ∫
2 ∞
Ψ ( x, t ) dx
2
Radiative transitions
4 −
Bohr Model
Vsphere = π r 3 Asphere = 4π r 2 ∫r e dr = n!r0 n+1
n −∞ ∞
Pelec − e x = −e ∫ x Ψ ( x, t ) dx
r0 2
consider elec. dipole
3 0 mvr = n Particle in a box V = ∞ at x = ± a / 2 En − En '
−∞

em rad: ω =
Trig Functions n 2 4πε 0 2
n 2 a0 ⎛ me ⎞ − 2 ∂2
sin 2α = 2sin α cosα
rn = = ⎜ ⎟ , a0 = 0.0529 nm inside: ψ ( x ) + Vψ ( x ) = Eψ ( x ) ∞
dipole transition amplitude: χ nn ' = ∫ xψ n* ( x )ψ n ' ( x ) dx
z e2 µ z ⎝ µ ⎠ 2m ∂x 2 −∞

sin ( x ± y ) = sin x cos y ± cos x sin y 2

∂2 intensity ∝ χ nn ' ⇒ calculate χ nn ' , if χ nn ' = 0, no dipole rad. emitted
2

z ⎛ e ⎞ µ
2 2
E ⎛ µ ⎞ mm 2mE
set: k = 2 ⇒ 2 ψ ( x ) + k 2ψ ( x ) = 0
cos ( x ± y ) = cos x cos y ∓ sin x sin y En = − ⎜ ⎟ = − z 2 2o ⎜ ⎟ , µ = 1 2 Harmonic oscillator em radiation
n 2 ⎝ 4πε 0 ⎠ 2 2 n ⎝ me ⎠ m1 + m2 ∂x
sin 2 x = (1 − cos 2 x ) / 2 cos2 x = (1 + cos 2 x ) / 2 2 ψ ( x ) = A cos kx + B sin kx ⎛ 1⎞
∆E = ω , En = ⎜ n + ⎟ ω , ψ n = H n (ξ ) exp ( −ξ 2 / 2 ) , ξ 2 =
mk 2
x
cos ( 90 ± θ ) = ∓ sin θ sin ( 90 ± θ ) = cosθ Z 2 ⎛ e2 ⎞ µ ⎝ 2⎠
Eo = − ⎜ ⎟ = 13.6 eV ka ka
= 0 = B sin χ nn ' = ∫ H n ' (ξ ) ξ H n (ξ ) exp ( −ξ 2 ) d ξ
∞
n 2 ⎝ 4πε 0 ⎠ 2 2 BC's: A cos
Complex Numbers 2 2 −∞

1
z = x + iy = reiθ = r ( cosθ + i sin θ ) from Herm. polynom. recurs. rel.: ξ H n = [ H n+1 + 2nH n−1 ]
transition from nÆk: hν = ∆E = z 2 E0 ⎛⎜
1 1⎞ ka
B = 0 : ψ = A cos = 0
− 2⎟ 2
⎝k n ⎠ 2 = ∫ H n ' ( ξ ) [ H n +1 + 2nH n−1 ] exp ( −ξ 2 ) dξ
2 1 ∞
z* = x − iy z = zz* = x2 + y 2 = r 2
2
⇒ χ nn '
ka 2 −∞
phase θ where tan θ = y / x X-ray production A = 0 : ψ = B sin =0 Potential step V ( x < 0 ) = 0, V ( x ≥ 0 ) = V0
Braking radiation results from deceleration of charged 2
Re eiθ = cosθ =
(e iθ
+ e −iθ )
; Im eiθ = sin θ =
(e iθ
− e −iθ )
part. k = π n / a ⇒ n odd with cos, even with sin − 2 ∂2 2mE
at x < 0 ψ = Eψ , k12 = 2
2 2 normalize to find that A = B = 2 / a 2m ∂x 2
BB, PE, RUTH., BOHR, CS, X-RAYS, UNC. PR. General solution ∂2
ψ + k12ψ = 0 ⇒ ψ = A cos k1 x + B sin k1 x
Ideal Gas Law hc hc consider V ≠ V ( t ) : ∂x 2
λmin = = , Eγ = hν = Te − Te ' 2m (V0 − E ) ∂2
⎛ m ⎞
3/ 2
⎛ −mv 2 ⎞ 2 Te eV − 2 ∂2 at x > 0 k2 2 = ψ − k2 2ψ = 0 ψ = Ce − k2 x
n ( v ) dv = 4π N ⎜ ⎟ exp ⎜ ⎟ v dv ψ ( x ) + V ( x )ψ ( x ) = Eψ ( x ) 2
∂x 2
⎝ 2π kT ⎠ ⎝ 2kT ⎠ at Te ' = 0, hν max = Te =
hc 2m ∂x 2 dψ
λmin ∂ 2
2m make ψ , continuous at x = 0
2kT 8 kT 3 ⇒ 2 ψ ( x ) = 2 ⎡⎣ E − V ( x ) ⎤⎦ψ ( x ) dx
vm = ,v = , v 2 = kT ∂x dψ
X-rays from ionization: En = ( zeff 2 )
m 3 m 2 E0 ψ : A=C , : Bk1 = − k2C
2m
Black Body Radiation n n2 inside: ( x1 , x2 ) E > V ( x ) set k 2 = 2 ⎡⎣ E − V ( x ) ⎤⎦ dx
⎛ k ⎞
Emittance W or Intensity I: Compton Scattering ∂2 ⇒ x < 0 :ψ = C ⎜ cos k1 x − 2 sin k1 x ⎟ ⇒ x > 0 :ψ = Ce− k2 x
⇒ ψ ( x ) + k 2ψ ( x ) = 0 ⇒ ψ ( x ) = A cos kx + B sin kx ⎝ k1 ⎠
M λ = P / A , where P = power, A = Area at thermal ∂x 2
Potential barrier V = V0 in ( 0, a )
equilibrium: Eabs = Eemit outside: ( x > x1 , x2 )
k1 as defined above for region before and after barrier
∂2
∞
PBB = ∫ M λ d λ = M = σ T 4 ⇒ 2 ψ ( x ) − k 2ψ ( x ) = 0 ⇒ ψ ( x ) = e − k x k2 for barrier region (also as above)
∂x
( −∞,0 ) :ψ = Aeik x + Be−ik x
0 1 1
set boundaries equal
σ = 5.67 × 10−8 [W / m 2 K 4 ] ( 0, a ) :ψ = Ce− k x + Dek x2 2

I = M λ / aBB = M BB , because aBB = 1 Potential Well V = V0 at x > a / 2

( a, ∞ ) :ψ = Ae ˆ −ik x ⇒ set Bˆ = 0 for no reflection from ∞
ˆ ik x + Be 1 1

2m 2m dψ
λmaxT = const = 2.90 × 10−3 [m° K ] inside: k12 = 2
E , outside k2 2 = 2 (V0 − E ) continuity of ψ , at x = 0, a
dx
Jean’s #: # of allowed standing waves, nλ h h h x = 0: ψ : A + B = C + D
x : = cos α + mv cos β , y : 0 = sin α − mv sin β ⎪⎧ A cos k1 x ⎪⎫ ⎪⎧Ce 2 ⎪⎫
k x

λ λ' λ' ψ inside = ⎨ ⎬ , ψ outside = ⎨ − k2 x ⎬ dψ

⎩⎪ B sin k1 x ⎭⎪ : ik1 ( A − B ) = −k2 ( C − D )
8π ⎪⎩ De ⎭⎪
Ψ λ = nλ Ewave = Emod e h
dx
λ 4
If e: ∆λ = λ '− λ = (1 − cos α ) , m = γ Lorentz mo continuity at boundaries observe: x = a : ψ : Ce − k2a + De k2a = Ae
ˆ ik1a
mo c dψ
Ψ = energy density of EM field [ J/m3] 1 dψ ⎛V − E ⎞ : − k2 ( Ce− k2a − Dek2a ) = ik1 Ae
1/ 2
a k ˆ ik1a
⇒ tan k1 = 2 = ⎜ 0 ⎟ dx
m ψ dx 2 k1 ⎝ E ⎠
Where E is average energy If scattered part atom: ∆λ = e λc (1 − cos α ) A
2
1 ⎛ k2 k1 ⎞
2
B 1 ⎛ k2 k1 ⎞
2 2

M =1+ ⎜ + ⎟ sinh k2 a , ˆ = ⎜ + ⎟ sinh k2 a

2 2

Energy for each level: En = nhν ma 2 π π

2 2
π E V −E Aˆ 4 ⎝ k1 k2 ⎠ A 4 ⎝ k1 k2 ⎠
h
E = ⇒ E1 = ⇒ tan = 0
λc = = 0.00243nm 2 2 2 2ma 2 2 E1 E Prob. Current density and T and R coefficients
Diff in E level (Energy quanta): ∆E = hν me c
k 2 ⎛ * dψ dψ * ⎞
c c
M λ (T ) = Ψ λ = nλ E = ⋅ 4 ⋅
c 8π hν Franck-Hertz Experiment Harmonic Oscillator with V ( x ) = x j ( x, t ) = ⎜ψ
2im ⎝ dx
− ψ ⎟ , for above this results in:
dx ⎠
4 4 4 λ exp ( hc / λ kT ) − 1 T fin = Tinit − ∆E
2
k1 2 k
d 2ψ mk ⎛ 2 2 E ⎞ x < 0 : j ( x, t ) = A − 1 B = jinc + jrefl
2 2
hc 1
= 2π 5 ⋅ = 2 ⎜x − ⎟ψ
( where Tinit > ∆E , VGA fixed)
arrange S.E.: m m
λ exp ( hc / λ kT ) − 1 dx 2 ⎝ k ⎠
k
x > 0 : j ( x, t ) = 1 Aˆ = jtrans
2

2π h ν3 d 2ψ ⎛ mk 2 2 E m ⎞
Mν ( T ) = 2 Diffraction ⇒ = ⎜⎜ x − ⎟ψ m
c exp ( hν / kT ) − 1 mk dx
2
⎝ k ⎠⎟
1 λ
2 2

Two slit: a sin θ max = nλ , sin θ min = ⎛⎜ n + ⎞⎟

2 2
j Aˆ j B B Aˆ
mk 2E T = trans = R = refl = =
Planck’s derivation: En = nhν ⎝ 2⎠d set: ξ 2 = x2 , λ = jinc A jinc A Aˆ A
ω0
N N
One slit: sin θ min ≈ λ / a d 2ψ
2 Particles in 1D
∑ E n ∑ E Ne
i i i
Ei / kT

hν Bragg Scattering
⇒
dξ 2
= (ξ 2 − λ )ψ ⇒ ξ max 2 =
mk 2 E
k
=λ
Ψ ( x1 , x2 ) = ψ ( x1 )ψ ( x2 )
E = i =1
= i =1
= dψ
N N
e hν / kT − 1 Condition: 2d sin θ = nλ ,d = spacing between ψ (ξ ) exp ( −ξ 2 / 2 ) = exp ( −ξ 2 / 2 ) ⇒ = −ξ exp ( −ξ 2 / 2 ) 2 identical particles:
∑n i ∑ Ne Ei / kT

atoms, n = integer multiple

dξ 1 ⎡
i =1 i =1 sym. ψ S ( x1 , x2 ) = ψ ( x1 )ψ ( x2 ) + ψ ( x2 )ψ ( x1 ) ⎤⎦
d 2ψ
= (ξ 2 − 1) exp ( −ξ 2 / 2 ) ⇒ satisfies if λ = λ0 = 1 2⎣
Photoelectric Effect Matter Waves ⇒
dξ 2 1 ⎡
asym. ψ A ( x1 , x2 ) = ψ ( x1 )ψ ( x2 ) −ψ ( x2 )ψ ( x1 ) ⎤⎦ = −ψ ( x2 , x1 )
work function=binding energy=E to release e− λ=
h
=
h
→ e- diffraction max at λ = 2d sin θ ⇒ E0 = λ0 = 0
ω0 ω 2⎣
mv p 2 2 2 disting. part. in a box
W c
ν th = ν min = o = , when stopping V =0 Uncertainty Principle eigenfunction gives normalized stationary-state wave fnc.
h λmax
( ) exp ( −iE t /
1/ 8
⎛ mk ⎞ π ⎡ n12 n2 2 ⎤
2 2

∆x∆p ≥ , ∆E ∆t , ∆ω∆t , ∆x∆k ≥ Ψ 0 ( x, t ) = ⎜ 2 2 ⎟ exp − mk x 2 / 2 ) Ψ n1n2 ( x1 , x2 ) = Ψ n1 ( x1 )Ψ n2 ( x2 ) En1n2 = ⎢ + ⎥

Tmax = Vs e = hν − Wo 2 2 ⎝π
0
⎠ 2a 2 ⎣ m1 m2 ⎦

WAVE PACKETS other solutions have: ψ (ξ ) = H (ξ ) exp ( −ξ 2 / 2 ) 2 ⎛πx ⎞ ⎛πx ⎞ 2 ⎛ π x1 ⎞ ⎛ 2π x2 ⎞

γ / s = P / Eγ , E = hν = hc / λ eg : // Ψ11 =
a
cos ⎜ 1 ⎟ cos ⎜ 2 ⎟
⎝ a ⎠ ⎝ a ⎠
Ψ12 = cos ⎜
a
⎟ sin ⎜
⎝ a ⎠ ⎝ a ⎠
⎟
k2 ⎛ dω ⎞ p ⎛ 1⎞
can find that λn = 2n + 1 so En = ω0 ⎜ n + ⎟
Rutherford Scattering ω= , vgroup = ⎜ ⎟ = = v particle Ψ12 = Ψ 21 =
1 2 ⎡ ⎛ π x1 ⎞ ⎛ 2π x2 ⎞ ⎛ π x1 ⎞ ⎛ π x2 ⎞ ⎤
⎝ 2⎠ ⎟ + cos ⎜
S S
2m ⎝ dk ⎠k =k m ⎢cos ⎜ ⎟ sin ⎜ ⎟ cos ⎜ ⎟ ⎥
2 a⎣ ⎝ a ⎠ ⎝ a ⎠ ⎝ a ⎠ ⎝ a ⎠ ⎦
1 2 ze2 ∆P ∆P Expectation Values
∆P = θ≈ = ⎧⎪ A , k − κ , k + κ ( )⎫⎪⎬ similarly: − Ψ 21 = Ψ12
A A

4πε o Rv Pα M α vα given A ( k ) = ⎨ 0
∞ ∞
A = ∫ A ( x ) P ( x, t ) dx = ∫ Ψ* ( x, t ) A ( x ) Ψ ( x, t ) dx 1 particle in 3D box
⎩⎪0 , otherwise ⎭⎪
−∞ −∞
∞
x = ∫ Ψ* ( x, t ) xΨ ( x, t ) dx ,
∞
x 2 = ∫ Ψ * ( x, t ) x 2 Ψ ( x, t ) dx ⎡ ∂2 ∂2 ∂2 ⎤
⎢ 2 + 2 + 2⎥= ∇2
k +κ 2 2

(change of vars ⇒ k = k − κ )
−∞ −∞
Ψ ( x) = ∫ A(k ) e
( i kx −ωt )
dk ∞ ∂ ∞ ∂2 ⎣ ∂x ∂y ∂z ⎦
p = ∫ Ψ ( x, t ) *
Ψ ( x, t ) dx , p 2 = ∫ −Ψ * ( x, t ) Ψ ( x, t ) dx
2
k −κ −∞ i ∂x −∞ ∂x 2 ⎡ 2
d ⎤
κ ⇒ ⎢− ∇ 2 Ψ + V ( x, y , z )Ψ = i Ψ ⎥ if V ≠ V (t )
() ∂
∞ ∞
Ψ ( x ) = A k ei kx ∫ ei(κ x−ωt ) dk V = ∫ Ψ* ( x, t )V ( x ) Ψ ( x, t ) dx , E = ∫ Ψ * ( x, t ) i Ψ ( x, t ) dx ⎣ 2m dt ⎦
−∞ −∞ ∂t 2
−κ
( ∆x )
2
= x2 − x
2
, ( ∆p )
2
= p2 − p
2
− ∇ 2 Ψ ( x, y , z ) = E Ψ ( x, y , z ) time ind.
Gaussian amplitude dist. where 2σ k 2 = κ and: 2m
dN = # part. that intersect(are detected) for particle in a box with: π 2 ⎡ n12
n2 n2⎤
( )
2

⎛ − k −κ ⎞ En1 n2 n3 = + 22 + 32 ⎥
( ) = exp ⎜⎜
⎢
dN (θ ) D2 θ A ( k ) = exp − k 2 / κ
2
⎟ 2 ⎡π x ⎤ ⎛ −i ⎞ π2 2 2m ⎣ a 2 b c ⎦
= n ⋅ dx ⋅ ⋅ csc4 ⋅ d Ω ,NB=Intensity(#part./s) 2σ k 2 ⎟ ψ1 ( x) = cos ⎢ ⎥ exp ⎜ E1t ⎟ E1 =
NB 16 2 ⎝ ⎠ a ⎣ a ⎦ ⎝ ⎠ 2ma 2 2 ⎧ sin ⎫ ⎛ n1π x ⎞ 2 ⎧ sin ⎫ ⎛ n2π x ⎞ 2 ⎧ sin ⎫ ⎛ n3π x ⎞
Ψ n1 n2 n3 = ⎨ ⎬⎜ ⎟ ⎨ ⎬⎜ ⎟ ⎨ ⎬⎜ ⎟
( ))
a ⎩cos ⎭ ⎝ a ⎠ b ⎩cos ⎭ ⎝ b ⎠ c ⎩cos ⎭ ⎝ c ⎠
(
∞ 2 a/2
x cos 2 (π x / a ) dx = 0
a ∫− a / 2
Ψ ( x ) = ∫ A ( k ) eikx dk = π ⋅ κ exp − κ x / 2
2
1 zZe 2 z → beam atomic # x = let y = π x / a
D= −∞
4πε o Tαo Z → target atomic # 2⎛ a ⎞
3
π /2
=2 ⎜ ⎟ ∫
2
y cos 2
( y ) dy
a ⎝π ⎠ 0
 CENTRAL FORCES Degeneracy d n = n 2 Spin-orbit splitting of the s = 0 or s = 1; since ms = −s,..., s
pr 2 L2 L2 Probability distributions state nL j in the 1 ms = 0 for s = 0 and ms = −1, 0,1 for s = 1
+ +V (r) = E Veff ( r ) = V ( r ) +
2µ 2µ r 2 2µ r 2 Ψ nlm dτ = ⎡( Rnl ) r 2 dr ⎤ ⎡ Ylm d Ω ⎤ where dτ = r 2 drd Ω
2 2 2
electron atom s = 0 denotes the antisymmetric singlet χ A
⎣ ⎦⎣ ⎦
pr 2 s = 1 denotes the symmetric triplet χ mSs
+ Veff ( r ) = E 0 < θ < 180°; 0 < φ < 360° ⎪⎧ 1 ⎡ l ( l + 1) ⎤ ⎪⎫
Lyman α transition with
∞
2µ r = ∫ rPnl dr = an 2 ⎨1 + ⎢1 − ⎥⎬
0
⎪⎩ 2 ⎣ n 2 ⎦ ⎪⎭ EXAMPLES
In spherical coordinates fine structure energy Ass4 Q3: Given ψ and V(x)=(1/2)kx2 show soln of S.E.
1 1 1 2
L = Lx + Ly + Lz Lz →
∂ = 2 = 2 3 levels: ⎛ x ⎞
a n ( 2l + 1)
2 2 2 2 2

i ∂φ r an r2 Ψ in = Ax exp ⎜ − mk ⎟ ⇐ recognize time ind.

(Notice: 2p->1s is ⎝ 2 ⎠
⎛ ⎞ ⎛ ⎞ ⎛ 1 ∂
2
∂ 1 ∂ ⎞
2 2 1
= 3 3
2
V =−
Ze2 1
=−
Ze2 actually 2 transitions)
Lop 2 → ⎜ ⎟ Λ 2 = ⎜ ⎟ ⎜ sin θ + ⎟ a n l ( l + 1)( 2l + 1) 4πε 0 r 4πε 0 an 2 ⎛ 1⎞ k
⎝i⎠ ⎝ i ⎠ ⎝ sin θ ∂θ ∂θ sin2 θ ∂φ 2 ⎠ r3 this case: E = ⎜ n + ⎟ ω0 ; ω0 =
⎝ 2⎠ m
Ψ ( r,θ , φ, t ) then satisfies the SE: Electric dipole selection rules Hyperfine Structure i) sub in V(x) into Time independent S.E.
∆ml = ∆m j = 0 or ± 1 ii) rearrange to form: (d2/dx2)ψ=Xψ
⎛∂ 2 ∂ ⎞ ∂ nuclear spin quantum number
2
iii) sub in ψ, E, evalulate LHS, RHS, solve for n
− Ψ + Λ2Ψ ⎟ + V ( r ) Ψ = i Ψ = EΨ ∆l = ±1 ( parity of state must change in el. dip. transition )
2µ r 2 ⎜⎝ ∂r ∂r
r
⎠ ∂t Ass4 Q4: b) use SE to find E and V(x):
1 3
∆j = 0 or ± 1 (but 0 →
/ 0) I2 = 2
i ( i + 1)
i = 0, ,1, ,... i) Divide S.E. by ψ to isolate for E
Time independent Radial Wave Equation: 2 2 ii) Evalulate ψ’’(x) iii) Sub ii) into i)
transition amplitude (components x,y,z) iv) use V(inf)=0 assumption and eval for E
ψ ( r,θ , φ ) = Rnl ( r ) Ylm (θ , φ ) ⎧ Yl*'m ' sin θ cos φYlm d Ω ⎫
grand total quantum number v) sub in iv) into i) and eval for V(x)

⎪∫
Ass5 Q3: Reflectance/Transmittance of Step Potential:
Ylm (θ , φ ) = sph. harm.; 1= ∫ Ylm (θ , φ ) d Ω; dΩ = sin θ dθ dφ F = S + I for l = 0 case
2
∞ ⎪ i) define the eigenvunction
all Ω ⎪ * ⎪
1 ∂ ∫0 Rn 'l 'rRnl r dr ⋅ ⎨ ∫ Yl 'm ' sin θ sin φYlm d Ω ⎬ f ( f + 1)
2
eigenvalue formulas: − Λ 2Ylm = l ( l + 1) Ylm and Ylm = mYlm F 2 = S 2 + I 2 + 2S ⋅ I = 2
Ψ ( x) = Aeik1x + Be − ik1x x < 0 and Ψ ( x) = Aeik1 x + Be − ik1 x x > 0
i ∂φ ⎪ ⎪ ii) determine continuity @ ψ(0) and ψ’(0)
⎪⎩ ∫ Yl ' m ' cos θ Ylm d Ω ⎪⎭
*
Rotational motion φ dependence (azimuthal) 1 A + B = A (1) and k1 A − k1 B = k2 A (2)
f =i±
r = R,θ → constant ∴ Ψ (φ, t ) and kin. E sole contrib.
Orthogonalilty: 2 iii) rearrange (1) and solve 2 in terms of one variable, particularly A^hat
iv) Evalulate T & R from prob. current den. formulae
∫R Rn ' l ' r dr = 0 for n ≠ n '
2
nl nuclear g-factor g I , for proton is: Particle on a Ring (mass mu radius R):
Lz 2
=E let Lz , E operate on Ψ SPIN AND MAGNETIC INTERACTIONS gp θ=π/2 azimuthal angle φ=free V=0 on the ring, inf else;
2µ R 2 = 2.792847386 kinetic energy is the sole contributor:
∂2
2
∂ Orbital magnetic moments 2 p⊥ 2 L2
− Ψ=i Ψ ⇒ Ψ = ψ (φ ) e −iEt / spin-spin interaction ( l = 0 ) : = Z = E L Z = only non zero component of L
2µ R 2 ∂φ 2 ∂t L S 2µ 2 µ R 2
µL = − g L µB w/ g L = 1; µS = − g S µ B w/ g S = 2 sub operators: E → i ( ∂ / ∂t ) and L Z = ( / i )( ∂ / ∂φ )
d 2ψ 2µ R 2 2µ R 2 VSS =
= − 2 Eψ ⇒ ψ = Ae± iλφ with λ 2 = E 2
∂2 ∂ 2

dφ 2 2
e − Ψ =i Ψ... Em = m2 ( m=az. qu. # )
µB = = 9.274 × 10−24 A ⋅ m2 = 5.788 × 10−9 eV/G ⎧ 1⎫ 2µ R 2 ∂φ 2 ∂t 2µ R 2
⎪i for f = i + ⎪
restriction ψ (φ + 2π ) = ψ (φ )
2
2me ⎛
e2 g S g I ⎞ me 2 ⎪ 2⎪ exp ( imφ )
⎜ ⎟ Rn 0 ( 0 ) ⎨ ⎬ Ψm = exp ( −iEmt / ) where m=0, ± 1, ± 2...
Ae
± iλ (φ + 2π )
= Ae ± iλφ ⇒ e±2π iλ = 1 ⇒ λ = m Zeeman Effect 4πε 0 3 ⎝ 2me c ⎠ M p ⎪ −i − 1 for f = i − 1 ⎪ 2π
2 External magnetic field is applied, sharp spectral lines ⎪⎩ 2 ⎭⎪ Rigid Rotator example: given hydrogen with R=0.075nm
Em = m normalize to get A = 1 / 2π
2
split into multiple closely spaced lines. Due to where n = 1 : - r = constant therefore r-comp of p = 0
2µ R 2 - setting V=0 (only kinetic energy)
eimφ interaction between magnetic field and magnetic g S g I me ⎡ 3 ⎤ E=L2/2I; I = moment of inertia = L/ω = R2m
Ψm = e− iEmt / with m = 0, ±1, ±2,... dipole moment. VSS = Z 3α 4 me c 2 ⎢ f ( f + 1) − − i ( i + 1) ⎥ 2
2π 3 MP ⎣ 4 ⎦ El = l (l + 1) 2l + 1 diff. wave func. per l value (degeneracy)
µ z = − g µ B m VM = − µ z B VM = + g µ B Bm j 2I
Separation of variables g g m
in "normal" case: δ EM = g µ B B ⇒ Enlm = En + mδ EM δ Ehf = Z α S I e me c 2 ( 2i + 1)
3 4 Particle of mass m inside sphere of radius a, V=0 inside, V=inf outside.a)
ψ ( r,θ ,φ ) = R ( r ) Y (θ ,φ ) 3 MP Find Radial Wave Equation.
− 21 d ⎛ 2 d ⎞ ⎡ l ( l + 1) 2
⎤
eB R ⎟ + ⎢V (r) +
0
µr2 en. diff. from Bohr =δ EM = h ⋅ δν = h COMPLEX ATOMS ⎜r ⎥ R = ER
+ 2 2 ( E − V ( r )) R = λ R
d 2 dR
radial r 4π me 2µ r dr ⎝ dr ⎠ ⎣ 2mr 2 ⎦
dr dr Helium:
λBohr + δλ =
hc
Lowest E: smax , lmax , jmin − 2 d2 ⎡ l ( l + 1) 2
⎤
2
d2 ⎡ 2
⎤ − 2 ( rR ) + ⎢ ⎥ rR = E ( rR )
−
2m dr 2
( rR ) + ⎢V ( r ) +
2mr 2
l ( l + 1) ⎥ ( rR ) = E ( rR ) ∆EBohr − δ EM
δ EM
( ∇12 + ∇22 )ψ + Vψ = Eψ 2µ dr 2 ⎣ 2mr
2
⎦
⎣ ⎦ ⇒ (assume ∆E >> δ EM ) δλ = λBohr
2me
b) show that R(r)=Asin(kr)/kr is a solution
R ( r ) = Ar l as r → 0 ∆EBohr
V=
Ze2
−
Ze2
+
e2 - take two derivatives of given R function
4πε 0 r1 4πε 0 r2 4πε 0 | r1 − r2 | - sub into D.E. and solve for E
angular Ylm (θ , φ ) = Θlm (θ ) Φ (φ ) Normal Zeeman Splitting Energy Level E3 → E2 - Equate E with previous expression for E
Two approaches to modeling: - recall boundary condition, must vanish @ edges->R(r=a)=0
Φ (φ ) = eimφ Obeys l and m selection rules 1. ignore coulomb rep. in potential term, solve for e- Q1: Given n=2, l=1 find most prob. dis betwn e- and nucleus. Find <r> and
Quantum numbers <V> by integration
nucleus attraction terms, add in correction for e-e Radial probability density Pnl(r)=r2(Rnl)2
principal qu. # ⇒ n = 1, 2,... ≥ l + 1; n = 1, 2,3, 4 ⇒ { K, L, M , N } terms. 2
⎡ 1 −ρ
⎤
{ }j 2. Independent Electron Model (Better) - each P21 ( r ) = r 2 ( R21 ) = r 2 ⎢ ρe 2 ⎥
2
orbital ang. qu. # ⇒ l = 0,1, 2,..., n −1; = 0,1,2,3 ⇒ s, p, d, f
⎣ 2 6a ⎦
3
azimuthal quantum number ⇒ ml = −l, −l + 1,...,l −1,l electron acts ind. w/ the nucleus with charge Z_eff 2
also called magnetic quantum number when B field applied (Zeeman effect)
e2 Zeff (r ) ⎡ 1 r 2−ar ⎤ r 4e− r / a
spin quantum number ⇒ ms = ±1 / 2 if Bext >> Bint , use ψ nlml ms , VM = µ B B ( ml + 2ms ) V= = r2 ⎢ e ⎥ =
4πε 0 r ⎣ 2 6a a
3
⎦ 24a 5
tot. ang. mom. qu. # ⇒ j = l ± 1 for l ≠ 0 j = 1 for l = 0 if Bext ∼ Bint , use ψ nljm j , VM = g µ B Bm j
2 2
there are only EVER two possible j states for non zero l where ⎡⎣ Zeff → Z as r → 0⎤⎦ and ⎡⎣ Zeff → 1 as r → ∞ ⎤⎦ ∞
⎡ 1 r 2−ar ⎤ ∞
r 5 −ar
2

m j = - j... j 2 j + 1 possible m j states j ( j + 1) − l ( l + 1) + 3 r = ∫ r3 ⎢ e ⎥ dr = ∫ e dr

where g = 1 + 4 Electron Configuration: ⎣ 2 6a a
3
⎦ 24a5
2 j ( j + 1)
0 0

S2 = 2s
( s +1) = 34 2 Alkalis: Li=[He]2s; Na=[Ne]3s; K=[Ar]4s 1
∞ −r
1
L2 = 2l
(l +1) Lz = ml Stern-Gerlach Experiment He has ground state electron config (1s)(1s) =
24a 5 ∫0
r 5e a dr =
24a 5
5!a 6 = 5a
Sz = ms s = 1
2 non-uniform Bz applies force on cl. bar magnet Excited state (1s)(nl) Q2: Show from direct calc. that all comp. of dipole transition vanish for nl =
J = L+ S J z = Lz + Sz = m j Cannot excite both above 1s because E > ionization 2,0 -> 1,0
∂Bz
J2 = j ( j + 1)
2 = L2 + 2L ⋅ S + S 2 Fz = µ z energy n=2, l=0, m=0 ==> n’=1, l’=0, m’=0
eg: 3P1/ 2 → n = 3;l = 1; j = 1/ 2 ∂z Radial Component will be non zero, then must show all angle components
Exclusion Principle zero.
Degeneracy Electron Spin (updated wave function) 2π π
1s 2s 2p 3s 3p (4s 4d ) 4p (5s 4d ) 5p...
Ψ nlml ms = Rnl ( r ) Ylm (θ , φ ) exp ( −iEnl t / ) ( ↑ or ↓ ) x − comp = ∫ Y00* sin θ cos φY00 d Ω = ∫ ∫ ⎣⎡sin θ cos φ ⎦⎤ dθ dφ = ... = 0
2

When a quantum system has two or more distinct Electron Antisymmetry 0 0

energy eigenfunctions with the same energy Spin-Orbital Interaction 2 2

Q3: Eval. Z-comp of dip. Trans. For 3p->2s
eigenvalue Ψ (1, 2, t ) = Ψ (2,1, t ) - chk: n=3, l=1 -> n’=2, l’=0 satisfies trans. rules
e2 - find radial comp. – find angular comp.
Parity Ylm (π − θ , π + φ ) = ( −1)l Ylm (θ , φ ) fine structure constant: α = exchange-symmetric: Ψ (1, 2, t ) = Ψ (2,1, t ) ∞

j j 4πε 0 c given R 31 and R20 eval: ∫ R31 R20 r 3dr and multiply by z-comp...
exchange-antisymmetric: Ψ (1, 2, t ) = −Ψ (2,1, t )
Observables energy level shift due to spin-orbit interaction:
0
z-component is non vanishing only for m=0 case ∴ ∫ Y00* cos θ Y10 d Ω
note:dτ = r 2 dr sin θ dθ dφ = r 2 drd Ω requirement of antisymmetry:
S ⋅L J −L −S 2 2 2 Assignment 9: Given B-ext >> B-int find energy shift
VSL = Zα = Zα
(ψ )
1 <VM>=magnitude of magnetic energy level shift. Strong B implies that we
Pnl ( r ) = r 2 Rnl ( r ) Ψ nlm = Rnl ( r ) Θlm (θ ) ψ (1, 2) = (1)ψ β (2) − ψ β (1)ψ α (2) or
2 2 2 2
2me 2 c r 3 4me 2 c r3 α may ignore the <V_SL> coupling term and use quantum numbers ml and
∞ ∞
2 ms
r = ∫ rPnl ( r ) dr ⇒ F ( r ) = ∫ F ( r ) Pnl ( r ) dr ⎡ 3⎤ 1
= Zα j ( j + 1) − l ( l + 1) − ⎥ 3 µB B
( ) ⎡⎣ LZ + 2 S Z ⎤⎦ = VM = µB B [ ml + 2ms ]
2
VSL 1
4me 2 c ⎣⎢
0 0
ψ (2,1) = ψ α (2)ψ β (1) − ψ β (2)ψ α (1) = −ψ (1, 2) VM = +
4⎦ r
( L2 ) = ⎡⎣ 2l ( l + 1) ⎤⎦
2 2 2
L2 = 2
3 ⇒ use LZ = ml ; S Z = ms
j ( j + 1) − l ( l + 1) − half-int. spin → fermions int. spin → bosons
= Lz 2 = [ m ] Z 4α 4 3 energy levels have 2 fold degeneracy.
2 2
Lz 4
VSL = me c 2 The Helium Atom Q2: Bext~Bint <VM>~<VSL>: must include fine structure shifts so use qu.#
ONE-ELECTRON ATOM 2n3 l ( l + 1)( 2l + 1) j , m . For l=2, the states are 3D_3/2 and 3D_5/2:
⎧⎪ψ S (r , r ) χ A (1, 2)
or ⎫⎪ j

Z 4α 2 E0 ψ (1, 2) = ⎨ A 1 2 S ⎬ For 3D_3/2:

Ze 2 spin-orbit splitting: δ ESL = ⎩⎪ψ (r1 , r2 ) χ (1, 2)
V (r) = − Ψ nlm ( r,θ , φ, t ) = Rnl ( r ) Ylm (θ ,φ ) e−iEnl t / ⎭⎪ j ( j + 1) + s ( s + 1) − l ( l + 1)
4πε 0 r n3l ( l + 1) antisym. and sym. spatial eigenfunctions: VM = g µ B Bm j where g = 1 +
2 j ( j + 1)
d 2 dR ⎡
2 2
⎤ ∴ nLl +1 / 2 state is higher than nLl −1 / 2
− r
2µ r 2 dr dr ⎣
+ ⎢V ( r ) +
2µ r 2
l ( l + 1) ⎥ R = ER ψ A (r1 , r2 ) =
1
(ψ α (r1 )ψ β (r2 ) − ψ β (r1 )ψ α (r2 ) and ) VM =
4
µB B [ 4 possible mj values]
⎦ total fine structure shift in energy for l ≠ 0 : 2 5
Assignment 10: Q1: For Alkali group, ionization energy is the energy
⎡ ⎤ 1
(ψ )
2
d2 2
ψ S (r1 , r2 ) = (r1 )ψ β (r2 ) + ψ β (r1 )ψ α (r2 )
− ( rR ) + ⎢V ( r ) + l ( l + 1 ) ⎥ R = ER Z 4α 4 ⎛ 2 3 ⎞ α required to remove the signle (ns) valence e-
2µ r dr 2 ⎣ 2µ r 2 ⎦ VSL + Krel = − me c 2 ⎜ − ⎟ 2 For Li. Valence electron = 2s, use approx: En=Z2E0/n2

r 4πε 0 2 F (ρ)
2n3 ⎝ 2 j + 1 4n ⎠ χ A (1, 2) =
1
(↑ ↓ − ↓1 ↑ 2 ) χ1S (1, 2) =↑1 ↑ 2
Q#2: X-Ray Lines for Tungsten:
define: ρ = ,a= , Rnl = e − ρ / n nl
1 2 k − abs − edge = λΚ
a Ze2 µ ρ Z 4α 2 ⎛ 2 3 ⎞ 2
Enj = En − 3 E0 ⎜ − ⎟ 1 1 1
µ Z2 n ⎝ 2 j + 1 4n ⎠ χ (1, 2) =
S
0
1
(↑ ↓1 2 + ↓1 ↑ 2 ) χ (1, 2) =↓1 ↓2
S
−1 λKLII
=
λΚ
−
λLII
and Enl = − 2
E0 = En Bohr 2
me n
S = S1 + S 2 ⇒ S12 = 2
s1 ( s1 + 1) = 3
4
2
= S 22
This lack of dependence on l is only valid for H
S1z = ms1 = ± S 2 z = ms 2 = ± ms = ms1 + ms 2
2 2