# COORDINATE SYSTEMS Spherical ( r ,θ ,φ

)
z
θ
r

n=

Na ρ [/ m3 ] ,A = atomic mass, [kg/mol] A
R
2

SCHRÖDINGER EQUATIONS
p2 +V = E , 2m
2 2

= =

p ( r ,θ ,φ )

φ
x

y

x = r sin θ cos φ y = r sin θ sin φ z = r cosθ

[ dA]det ( Rdθ )( R sin θ dφ ) = dΩ =
R
2

(p )
2

op

→−

2

∂2 ∂ , ( E )op → i ∂x 2 ∂t

y cos ( 2 y ) ⎤ 4a 2 ⎡ y 3 ⎛ y 2 1 ⎞ ⎢ + ⎜ − ⎟ sin ( 2 y ) + ⎥ 4 π3 ⎣ 6 ⎝ 4 8⎠ ⎦0

π /2

Energy of radiating wavelength
E= 1.24 × 104 [eV ⋅ A ]
o

MATH STUFF
4 Vsphere = π r 3 3 Asphere = 4π r 2

λ

, V=

E c , ν= q λ

− ∂ ∂ Ψ ( x, t ) + V Ψ ( x, t ) = i Ψ ( x, t ) ∂t 2m ∂x 2 2 2 − ∂ time ind. S.E.: ψ ( x ) + Vψ ( x ) = Eψ ( x ) 2m ∂x 2 probability: Ψ = Ψ *Ψ , normalize: 1 = ∫
2 ∞ −∞

a2 2 ⎡π 2 − 6 ⎤ = ( ∆x ) ⎦ 12π 2 ⎣ 2 a/2 ⎛ π x ⎞ ⎛ −π ⎞ ⎛ π x ⎞ p = ∫ cos ⎜ ⎟ ⎜ ⎟ sin ⎜ ⎟ dx = 0 [int. of odd fnc ] a −a / 2 ⎝ a ⎠i⎝ a ⎠ ⎝ a ⎠
∞ ∞ ⎛ π2 2 d2 ⎞ ψ ( x ) dx = ∫ ψ * ( x )( 2mE1 )ψ ( x ) dx = 2 p = ∫ ψ * ( x) ⎜ − 2 ⎟ −∞ −∞ a ⎝ dx ⎠

∫r e
n 0

r r0

dr = n!r0 n+1

Bohr Model mvr = n
rn = n 2 4πε 0 z e2 µ
2 2

Ψ ( x, t ) dx
2

consider elec. dipole em rad: ω = En − En '

Particle in a box V = ∞ at x = ± a / 2
= n 2 a0 ⎛ me ⎞ ⎜ ⎟ , a0 = 0.0529 nm z ⎝ µ ⎠
2

Pelec − e x = −e ∫ x Ψ ( x, t ) dx
2 −∞

Trig Functions
sin 2α = 2sin α cosα sin ( x ± y ) = sin x cos y ± cos x sin y cos ( x ± y ) = cos x cos y ∓ sin x sin y sin 2 x = (1 − cos 2 x ) / 2 cos ( 90 ± θ ) = ∓ sin θ cos2 x = (1 + cos 2 x ) / 2 sin ( 90 ± θ ) = cosθ

En = −

Eo ⎛ µ ⎞ mm z ⎛ e ⎞ µ = −z2 2 ⎜ ⎟ , µ = 1 2 ⎜ ⎟ n 2 ⎝ 4πε 0 ⎠ 2 2 n ⎝ me ⎠ m1 + m2
2

Complex Numbers
z = x + iy = reiθ = r ( cosθ + i sin θ ) z* = x − iy z = zz* = x2 + y 2 = r 2
2

Eo = −

Z 2 ⎛ e2 ⎞ µ = 13.6 eV ⎜ ⎟ n 2 ⎝ 4πε 0 ⎠ 2 2

2

− 2 ∂2 ψ ( x ) + Vψ ( x ) = Eψ ( x ) 2m ∂x 2 ∂2 2mE set: k = 2 ⇒ 2 ψ ( x ) + k 2ψ ( x ) = 0 ∂x ψ ( x ) = A cos kx + B sin kx inside: ka ka = 0 = B sin BC's: A cos 2 2 ka B = 0 : ψ = A cos = 0 2 ka =0 A = 0 : ψ = B sin 2 k = π n / a ⇒ n odd with cos, even with sin normalize to find that A = B = 2 / a

dipole transition amplitude: χ nn ' = ∫ xψ n* ( x )ψ n ' ( x ) dx
−∞

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

Harmonic oscillator em radiation
1⎞ mk 2 ⎛ x ∆E = ω , En = ⎜ n + ⎟ ω , ψ n = H n (ξ ) exp ( −ξ 2 / 2 ) , ξ 2 = 2⎠ ⎝

χ nn ' = ∫ H n ' (ξ ) ξ H n (ξ ) exp ( −ξ 2 ) d ξ
∞ −∞

transition from n k: hν = ∆E = z 2 E0 ⎛ ⎜

1 1⎞ − 2⎟ 2 n ⎠ ⎝k

from Herm. polynom. recurs. rel.: ξ H n = ⇒ χ nn '

phase θ where tan θ = y / x Re eiθ = cosθ =

(e

+ e −iθ ) 2

; Im eiθ = sin θ =

(e

− e −iθ ) 2

X-ray production Braking radiation results from deceleration of charged part.

1 [ H n+1 + 2nH n−1 ] 2 1 ∞ = ∫ H n ' ( ξ ) [ H n +1 + 2nH n−1 ] exp ( −ξ 2 ) dξ 2 −∞

Potential step V ( x < 0 ) = 0, V ( x ≥ 0 ) = V0
at x < 0 − 2 ∂2 2mE ψ = Eψ , k12 = 2 2m ∂x 2

BB, PE, RUTH., BOHR, CS, X-RAYS, UNC. PR. Ideal Gas Law
⎛ m ⎞ n ( v ) dv = 4π N ⎜ ⎟ ⎝ 2π kT ⎠ vm =
3/ 2

General solution
λmin
hc hc = = , Eγ = hν = Te − Te ' Te eV hc

consider V ≠ V ( t ) :

⎛ −mv 2 exp ⎜ ⎝ 2kT

⎞ 2 ⎟ v dv ⎠

at Te ' = 0, hν max = Te =

2kT 8 kT 3 ,v = , v 2 = kT m 3 m 2

λmin
n

Black Body Radiation Emittance W or Intensity I: M λ = P / A , where P = power, A = Area at thermal equilibrium: Eabs = Eemit
PBB = ∫ M λ d λ = M = σ T 4
0 ∞

X-rays from ionization: En = ( zeff 2 ) Compton Scattering

E0 n2

− 2 ∂2 ψ ( x ) + V ( x )ψ ( x ) = Eψ ( x ) 2m ∂x 2 2 ∂ 2m ⇒ 2 ψ ( x ) = 2 ⎡ E − V ( x ) ⎤ψ ( x ) ⎣ ⎦ ∂x 2m inside: ( x1 , x2 ) E > V ( x ) set k 2 = 2 ⎡ E − V ( x ) ⎤ ⎣ ⎦ ∂2 ψ ( x ) + k 2ψ ( x ) = 0 ⇒ ψ ( x ) = A cos kx + B sin kx ∂x 2 outside: ( x > x1 , x2 ) ⇒ ∂2 ⇒ 2 ψ ( x ) − k 2ψ ( x ) = 0 ⇒ ψ ( x ) = e − k x ∂x set boundaries equal

∂2 ψ + k12ψ = 0 ⇒ ψ = A cos k1 x + B sin k1 x ∂x 2 2m (V0 − E ) ∂2 at x > 0 k2 2 = ψ − k2 2ψ = 0 ψ = Ce − k2 x 2 ∂x 2 dψ make ψ , continuous at x = 0 dx dψ : Bk1 = − k2C ψ : A=C , dx ⎛ ⎞ k ⇒ x < 0 :ψ = C ⎜ cos k1 x − 2 sin k1 x ⎟ ⇒ x > 0 :ψ = Ce− k2 x k1 ⎝ ⎠

Potential barrier V = V0 in ( 0, a )
k1 as defined above for region before and after barrier k2 for barrier region (also as above)

σ = 5.67 × 10−8 [W / m 2 K 4 ]
I = M λ / aBB = M BB , because aBB = 1

Potential Well V = V0 at x > a / 2
inside: k12 = 2m
2

( −∞,0 ) :ψ = Aeik x + Be−ik x ( 0, a ) :ψ = Ce− k x + Dek x ˆ ˆ ˆ ( a, ∞ ) :ψ = Aeik x + Be−ik x ⇒ set B = 0 for no reflection from ∞
1 1 2 2 1 1

λmaxT = const = 2.90 × 10−3 [m° K ]
Jean’s #: # of allowed standing waves, nλ
Ψ λ = nλ Ewave = 8π
h h h x : = cos α + mv cos β , y : 0 = sin α − mv sin β λ λ' λ' h If e: ∆λ = λ '− λ = (1 − cos α ) , m = γ Lorentz mo mo c

E , outside k2 2 =

2m
2

(V0 − E )

continuity of ψ ,

λ

4

Emod e

⎧ kx ⎫ ⎧ A cos k1 x ⎫ ⎪ ⎪ ⎪Ce 2 ⎪ ψ inside = ⎨ ⎬ , ψ outside = ⎨ − k2 x ⎬ ⎪ ⎪ De ⎪ ⎩ B sin k1 x ⎪ ⎭ ⎩ ⎭ continuity at boundaries observe: a k 1 dψ ⎛V − E ⎞ ⇒ tan k1 = 2 = ⎜ 0 ⎟ ψ dx 2 k1 ⎝ E ⎠
1/ 2

dψ at x = 0, a dx x = 0: ψ : A + B = C + D dψ : ik1 ( A − B ) = −k2 ( C − D ) dx ˆ x = a : ψ : Ce − k2a + De k2a = Aeik1a dψ ˆ : − k2 ( Ce− k2a − Dek2a ) = ik1 Aeik1a dx

Ψ = energy density of EM field [ J/m3]

Where E is average energy Energy for each level: En = nhν Diff in E level (Energy quanta): ∆E = hν
c c c 8π hν M λ (T ) = Ψ λ = nλ E = ⋅ 4 ⋅ 4 4 4 λ exp ( hc / λ kT ) − 1 2 hc 1 = 2π 5 ⋅ λ exp ( hc / λ kT ) − 1 2π h ν3 Mν ( T ) = 2 c exp ( hν / kT ) − 1

m If scattered part atom: ∆λ = e λc (1 − cos α ) M
λc =
h = 0.00243nm me c

2 2 ma 2 π π π ⇒ tan E = ⇒ E1 = 2 2 2 2 2ma 2

V −E E = 0 E1 E

A =1+ ˆ A

2

B 1 ⎛ k2 k1 ⎞ 1 ⎛ k2 k1 ⎞ 2 2 ⎜ + ⎟ sinh k2 a , ˆ = ⎜ + ⎟ sinh k2 a 4 ⎝ k1 k2 ⎠ 4 ⎝ k1 k2 ⎠ A
2

2

2

Prob. Current density and T and R coefficients
j ( x, t ) = ⎛ * dψ dψ * ⎞ − ψ ⎟ , for above this results in: ⎜ψ 2im ⎝ dx dx ⎠

Franck-Hertz Experiment T fin = Tinit − ∆E

Harmonic Oscillator with V ( x ) =
arrange S.E.: ⇒ d 2ψ mk ⎛ 2 2 E ⎞ = 2 ⎜x − ⎟ψ dx 2 k ⎠ ⎝ d 2ψ ⎛ mk 2 2 E m ⎞ =⎜ x − ⎟ψ 2 ⎜ ⎟ k ⎠ mk dx ⎝ mk x2 , λ = 2E

k 2 x 2

( where Tinit > ∆E , VGA fixed)
Diffraction
1 λ Two slit: a sin θ max = nλ , sin θ min = ⎛ n + ⎞ ⎜ ⎟ 2⎠d ⎝

Planck’s derivation: En = nhν
E =

set: ξ 2 =

∑ E n ∑ E Ne
i =1 N i i

N

N

Ei / kT

∑n
i =1

=

i =1 N

i

i

∑ Ne
i =1

=

hν e hν / kT − 1

Ei / kT

Photoelectric Effect work function=binding energy=E to release e−

One slit: sin θ min ≈ λ / a Bragg Scattering Condition: 2d sin θ = nλ ,d = spacing between atoms, n = integer multiple Matter Waves
λ=
h h = → e- diffraction max at λ = 2d sin θ mv p

ω0

k1 2 k 2 A − 1 B = jinc + jrefl m m k ˆ2 x > 0 : j ( x, t ) = 1 A = jtrans m 2 2 2 2 ˆ ˆ j j A B B A = T = trans = R = refl = ˆ jinc A jinc A A A x < 0 : j ( x, t ) =

d 2ψ mk 2 E ⇒ = (ξ 2 − λ )ψ ⇒ ξ max 2 = =λ dξ 2 k dψ ψ (ξ ) exp ( −ξ 2 / 2 ) = exp ( −ξ 2 / 2 ) ⇒ = −ξ exp ( −ξ 2 / 2 ) dξ ⇒ d 2ψ = (ξ 2 − 1) exp ( −ξ 2 / 2 ) ⇒ satisfies if λ = λ0 = 1 dξ 2

2 Particles in 1D
Ψ ( x1 , x2 ) = ψ ( x1 )ψ ( x2 ) 2 identical particles: 1 ⎡ ψ ( x1 )ψ ( x2 ) + ψ ( x2 )ψ ( x1 ) ⎤ ⎦ 2⎣ 1 ⎡ asym. ψ A ( x1 , x2 ) = ψ ( x1 )ψ ( x2 ) −ψ ( x2 )ψ ( x1 ) ⎤ = −ψ ( x2 , x1 ) ⎦ 2⎣ sym. ψ S ( x1 , x2 ) =

⇒ E0 =

ν th = ν min

W c = o = h λmax

, when stopping V =0

Uncertainty Principle

λ0 = 0 2 2 eigenfunction gives normalized stationary-state wave fnc.
⎛ mk ⎞ Ψ 0 ( x, t ) = ⎜ 2 2 ⎟ ⎝π ⎠
1/ 8

ω0

ω

2 disting. part. in a box
Ψ n1n2 ( x1 , x2 ) = Ψ n1 ( x1 )Ψ n2 ( x2 ) eg : // Ψ11 =
S S Ψ12 = Ψ 21 =

Tmax = Vs e = hν − Wo

∆x∆p ≥

2

,

∆E ∆t , ∆ω∆t , ∆x∆k ≥
WAVE PACKETS

2

exp − mk x 2 / 2

(

) exp ( −iE t /
0

)

En1n2 =

γ / s = P / Eγ ,

E = hν = hc / λ

other solutions have: ψ (ξ ) = H (ξ ) exp ( −ξ 2 / 2 ) 1⎞ ⎛ can find that λn = 2n + 1 so En = ω0 ⎜ n + ⎟ 2⎠ ⎝

Rutherford Scattering ∆P ∆P 1 2 ze2 θ≈ = ∆P = P M α vα 4πε o Rv α

k2 p ⎛ dω ⎞ ω= , vgroup = ⎜ ⎟ = = v particle 2m ⎝ dk ⎠k =k m
⎧A , k − κ, k + κ ⎪ given A ( k ) = ⎨ 0 ⎪0 , otherwise ⎩ Ψ ( x) =
k +κ

2 ⎛πx ⎞ ⎛πx ⎞ cos ⎜ 1 ⎟ cos ⎜ 2 ⎟ a ⎝ a ⎠ ⎝ a ⎠

2 2 π ⎡ n12 n2 2 ⎤ ⎢ + ⎥ 2a 2 ⎣ m1 m2 ⎦ 2 ⎛ π x1 ⎞ ⎛ 2π x2 ⎞ Ψ12 = cos ⎜ ⎟ sin ⎜ ⎟ a ⎝ a ⎠ ⎝ a ⎠

(

)⎫ ⎪ ⎬
⎪ ⎭

Expectation Values
A = ∫ A ( x ) P ( x, t ) dx = ∫ Ψ* ( x, t ) A ( x ) Ψ ( x, t ) dx
−∞ −∞ ∞ ∞

1 2 ⎡ ⎛ π x1 ⎞ ⎛ 2π x2 ⎞ ⎛ π x1 ⎞ ⎛ π x2 ⎞ ⎤ ⎟ sin ⎜ ⎟ + cos ⎜ ⎟ cos ⎜ ⎟ ⎥ ⎢cos ⎜ 2 a⎣ ⎝ a ⎠ ⎝ a ⎠ ⎝ a ⎠ ⎝ a ⎠ ⎦ A A similarly: − Ψ 21 = Ψ12

1 particle in 3D box
2
2

k −κ

( ∫ A(k ) e

i kx −ωt )

dk

(change of vars ⇒ k = k − κ )

x = ∫ Ψ* ( x, t ) xΨ ( x, t ) dx ,
−∞ ∞ *

x 2 = ∫ Ψ * ( x, t ) x 2 Ψ ( x, t ) dx
−∞

Ψ ( x ) = A k ei kx ∫ ei(κ x−ωt ) dk
−κ

()

κ

∞ ∂ p = ∫ Ψ ( x, t ) Ψ ( x, t ) dx , p 2 = ∫ −Ψ * ( x, t ) −∞ −∞ i ∂x

V = ∫ Ψ* ( x, t )V ( x ) Ψ ( x, t ) dx ,
−∞

∂2 Ψ ( x, t ) dx ∂x 2 ∞ ∂ E = ∫ Ψ * ( x, t ) i Ψ ( x, t ) dx −∞ ∂t
2

⎡ ∂2 ∂2 ∂2 ⎤ ⎢ 2 + 2 + 2⎥= ∂y ∂z ⎦ ⎣ ∂x

2

∇2

2 ⎡ d ⎤ ⇒ ⎢− ∇ 2 Ψ + V ( x, y , z )Ψ = i Ψ ⎥ if V ≠ V (t ) dt ⎦ ⎣ 2m

dN = # part. that intersect(are detected) dN (θ ) D2 θ = n ⋅ dx ⋅ ⋅ csc4 ⋅ d Ω ,NB=Intensity(#part./s)
NB 16 2
D= 1 zZe 2 4πε o Tαo z → beam atomic # Z → target atomic #

Gaussian amplitude dist. where 2σ k 2 = κ and: A ( k ) = exp − k 2 / κ

( ∆x )

2

= x2 − x

2

,

( ∆p )

2

= p2 − p

2

(

2

) = exp ⎜⎜

⎛ − k −κ ⎞ ⎟ 2σ k 2 ⎟ ⎝ ⎠

(

)

for particle in a box with:
ψ1 ( x) =
2 ⎡π x ⎤ ⎛ −i ⎞ cos ⎢ ⎥ exp ⎜ E1t ⎟ a ⎣ a ⎦ ⎝ ⎠ E1 =
let y = π x / a

2m

∇ 2 Ψ ( x, y , z ) = E Ψ ( x, y , z )
2

time ind.

π2

2

Ψ ( x ) = ∫ A ( k ) eikx dk = π ⋅ κ exp − κ x / 2
−∞

(

(

))
2

2ma 2

x =

2 a/2 x cos 2 (π x / a ) dx = 0 a ∫− a / 2
3

n2 n2⎤ En1 n2 n3 = + 22 + 32 ⎥ ⎢ b c ⎦ 2m ⎣ a 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 ⎠

π 2 ⎡ n12

2⎛ a ⎞ =2 ⎜ ⎟ a ⎝π ⎠

π /2

0

y cos

2

2

( y ) dy

CENTRAL FORCES
pr 2 L2 + +V (r) = E 2µ 2µ r 2 pr 2 + Veff ( r ) = E 2µ L2 Veff ( r ) = V ( r ) + 2µ r 2 0 < θ < 180°; 0 < φ < 360°
∂ Lz → i ∂φ
2 2

Degeneracy d n = n 2 Probability distributions
2 2 2 Ψ nlm dτ = ⎡( Rnl ) r 2 dr ⎤ ⎡ Ylm d Ω ⎤ where dτ = r 2 drd Ω ⎣ ⎦⎣ ⎦

Spin-orbit splitting of the state nL j in the 1 electron atom Lyman α transition with fine structure energy levels: (Notice: 2p->1s is actually 2 transitions) Hyperfine Structure
nuclear spin quantum number 1 3 i = 0, ,1, ,... 2 2 grand total quantum number I2 =
2

s = 0 or s = 1; since ms = −s,..., s ms = 0 for s = 0 and ms = −1, 0,1 for s = 1 s = 0 denotes the antisymmetric singlet χ A
S s = 1 denotes the symmetric triplet χ ms

In spherical coordinates
L = Lx + Ly + Lz
2 2 2 2 2

⎧ 1 ⎡ l ( l + 1) ⎤ ⎫ ∞ ⎪ ⎪ r = ∫ rPnl dr = an 2 ⎨1 + ⎢1 − ⎥⎬ 0 n2 ⎦ ⎪ ⎪ 2⎣ ⎩ ⎭ 1 1 1 2 = 2 = 2 3 2 r an r a n ( 2l + 1) 1 2 = 3 3 r3 a n l ( l + 1)( 2l + 1)
∆ml = ∆m j = 0 or ± 1 ∆l = ±1 ( parity of state must change in el. dip. transition ) ∆j = 0 or ± 1 (but 0 → 0 ) /

EXAMPLES
Ass4 Q3: Given ψ and V(x)=(1/2)kx2 show soln of S.E.

1 ∂ ∂ ⎞ ⎛ ⎞ ⎛ ⎞ ⎛ 1 ∂ sin θ Lop 2 → ⎜ ⎟ Λ 2 = ⎜ ⎟ ⎜ + ⎟ ∂θ sin2 θ ∂φ 2 ⎠ ⎝i⎠ ⎝ i ⎠ ⎝ sin θ ∂θ Ψ ( r,θ , φ, t ) then satisfies the SE: − ∂ ⎛∂ 2 ∂ ⎞ r Ψ + Λ2Ψ ⎟ + V ( r ) Ψ = i Ψ = EΨ 2µ r 2 ⎜ ∂r ∂r ∂t ⎝ ⎠
2

Ze2 1 Ze2 =− V =− 4πε 0 r 4πε 0 an 2

⎛ x ⎞ Ψ in = Ax exp ⎜ − mk ⎟ ⇐ recognize time ind. 2 ⎠ ⎝
2

Electric dipole selection rules

k 1⎞ ⎛ this case: E = ⎜ n + ⎟ ω0 ; ω0 = m 2⎠ ⎝
i) sub in V(x) into Time independent S.E. ii) rearrange to form: (d2/dx2)ψ=Xψ iii) sub in ψ, E, evalulate LHS, RHS, solve for n Ass4 Q4: b) use SE to find E and V(x): i) Divide S.E. by ψ to isolate for E ii) Evalulate ψ’’(x) iii) Sub ii) into i) iv) use V(inf)=0 assumption and eval for E v) sub in iv) into i) and eval for V(x) Ass5 Q3: Reflectance/Transmittance of Step Potential: i) define the eigenvunction

Time independent Radial Wave Equation:
ψ ( r,θ , φ ) = Rnl ( r ) Ylm (θ , φ ) 2 Ylm (θ , φ ) = sph. harm.; 1= ∫ Ylm (θ , φ ) d Ω; dΩ = sin θ dθ dφ
all Ω

i ( i + 1)

eigenvalue formulas: − Λ 2Ylm = l ( l + 1) Ylm and

1 ∂ Ylm = mYlm i ∂φ

Rotational motion φ dependence (azimuthal)
r = R,θ → constant ∴ Ψ (φ, t ) and kin. E sole contrib. Lz 2 =E 2µ R 2
2

transition amplitude (components x,y,z) ⎧ Yl*m ' sin θ cos φYlm d Ω ⎫ ' ⎪∫ ⎪ ∞ ⎪ * ⎪ 2 ∫ Rn 'l 'rRnl r dr ⋅ ⎨ ∫ Yl 'm ' sin θ sin φYlm d Ω ⎬ 0 ⎪ ⎪ * ⎪ ∫ Yl ' m ' cos θ Ylm d Ω ⎪ ⎩ ⎭ Orthogonalilty:

F = S + I for l = 0 case F 2 = S 2 + I 2 + 2S ⋅ I = f =i± 1 2
2

f ( f + 1)

Ψ ( x) = Aeik1x + Be − ik1x x < 0 and Ψ ( x) = Aeik1 x + Be − ik1 x x > 0
ii) determine continuity @ ψ(0) and ψ’(0)

A + B = A (1) and k1 A − k1 B = k2 A (2)
iii) rearrange (1) and solve 2 in terms of one variable, particularly A^hat iv) Evalulate T & R from prob. current den. formulae Particle on a Ring (mass mu radius R): θ=π/2 azimuthal angle φ=free V=0 on the ring, inf else; kinetic energy is the sole contributor:

let Lz , E operate on Ψ

∫R

nl

Rn ' l ' r dr = 0 for n ≠ n '
2

nuclear g-factor g I , for proton is: = 2.792847386 2 spin-spin interaction ( l = 0 ) : VSS = 1⎫ ⎧ 2 i for f = i + ⎪ ⎛ ⎞ me 2 ⎪ ⎪ 2⎪ Rn 0 ( 0 ) ⎨ ⎜ ⎟ ⎬ ⎝ 2me c ⎠ M p ⎪ −i − 1 for f = i − 1 ⎪ ⎪ ⎪ 2⎭ ⎩ where n = 1 : e2 g S g I 4πε 0 3 VSS = Z 3α 4
3 4

∂2 ∂ − Ψ=i Ψ ⇒ Ψ = ψ (φ ) e −iEt / ∂t 2µ R 2 ∂φ 2 d 2ψ 2µ R 2 = − 2 Eψ dφ 2 Ae
± iλ (φ + 2π ) 2

SPIN AND MAGNETIC INTERACTIONS Orbital magnetic moments
2µ R 2
2

gp

µL = − g L µB
E

L

w/ g L = 1; µS = − g S µ B

S

w/ g S = 2

⇒ ψ = Ae± iλφ with λ 2 =

restriction ψ (φ + 2π ) = ψ (φ ) = Ae ± iλφ
2

µB =

e = 9.274 × 10−24 A ⋅ m2 = 5.788 × 10−9 eV/G 2me

⇒ e±2π iλ = 1 ⇒ λ = m

Em = Ψm =

2µ R 2 eimφ 2π

m normalize to get A = 1 / 2π e− iEmt / with m = 0, ±1, ±2,...

Zeeman Effect External magnetic field is applied, sharp spectral lines split into multiple closely spaced lines. Due to interaction between magnetic field and magnetic dipole moment.
µ z = − g µ B m VM = − µ z B
VM = + g µ B Bm j in "normal" case: δ EM = g µ B B ⇒ Enlm = En + mδ EM

p⊥ 2 L2 = Z = E L Z = only non zero component of L 2µ 2 µ R 2 sub operators: E → i ( ∂ / ∂t ) and L Z = ( / i )( ∂ / ∂φ ) 2 2 ∂2 ∂ m2 ( m=az. qu. # ) − Ψ =i Ψ... Em = 2µ R 2 ∂φ 2 ∂t 2µ R 2 exp ( imφ ) Ψm = exp ( −iEmt / ) where m=0, ± 1, ± 2... 2π
Rigid Rotator example: given hydrogen with R=0.075nm - r = constant therefore r-comp of p = 0 - setting V=0 (only kinetic energy) E=L2/2I; I = moment of inertia = L/ω = R2m

g S g I me 3 ⎡ ⎤ me c 2 ⎢ f ( f + 1) − − i ( i + 1) ⎥ 3 MP 4 ⎣ ⎦

Separation of variables
ψ ( r,θ ,φ ) = R ( r ) Y (θ ,φ )
d 2 dR µr2 radial r + 2 2 ( E − V ( r )) R = λ R dr dr 2 2 ⎡ ⎤ d2 − l ( l + 1) ⎥ ( rR ) = E ( rR ) ( rR ) + ⎢V ( r ) + 2m dr 2 2mr 2 ⎣ ⎦ R ( r ) = Ar l as r → 0 angular Ylm (θ , φ ) = Θlm (θ ) Φ (φ ) Φ (φ ) = eimφ

El =

2

g g m δ Ehf = Z α S I e me c 2 ( 2i + 1) 3 MP

Particle of mass m inside sphere of radius a, V=0 inside, V=inf outside.a) Find Radial Wave Equation.
0 l ( l + 1) − 21 d ⎛ 2 d ⎞ ⎡ R ⎟ + ⎢V (r) + ⎜r 2mr 2 2µ r dr ⎝ dr ⎠ ⎣ 2

2I

l (l + 1)

2l + 1 diff. wave func. per l value (degeneracy)

en. diff. from Bohr =δ EM = h ⋅ δν = h

λBohr + δλ =

hc ∆EBohr − δ EM

eB 4π me

COMPLEX ATOMS Helium:
− 2 ( ∇12 + ∇22 )ψ + Vψ = Eψ 2me V= Ze2 Ze2 e2 − + 4πε 0 r1 4πε 0 r2 4πε 0 | r1 − r2 |

⎤ ⎥ R = ER ⎦

Lowest E: smax , lmax , jmin

⇒ (assume ∆E >> δ EM ) δλ = λBohr

δ EM
∆EBohr

⎡ l ( l + 1) − 2 d2 ( rR ) + ⎢ 2 2µ dr 2 ⎣ 2mr

2

⎤ ⎥ rR = E ( rR ) ⎦

Normal Zeeman Splitting Energy Level E3 → E2 Obeys l and m selection rules
n = 1, 2,3, 4 ⇒ { K, L, M , N }

Quantum numbers
principal qu. # ⇒ n = 1, 2,... ≥ l + 1; orbital ang. qu. # ⇒ l = 0,1, 2,..., n −1; = 0,1,2,3 ⇒ s, p, d, f azimuthal quantum number ⇒ ml = −l, −l + 1,...,l −1,l
also called magnetic quantum number when B field applied (Zeeman effect)

{

}j
if Bext >> Bint , use ψ nlml ms , VM = µ B B ( ml + 2ms ) if Bext ∼ Bint , use ψ nljm j , VM = g µ B Bm j where g = 1 + j ( j + 1) − l ( l + 1) + 3 2 j ( j + 1) 4

Two approaches to modeling: 1. ignore coulomb rep. in potential term, solve for enucleus attraction terms, add in correction for e-e terms. 2. Independent Electron Model (Better) - each electron acts ind. w/ the nucleus with charge Z_eff
V= e2 Zeff (r ) 4πε 0 r

b) show that R(r)=Asin(kr)/kr is a solution - take two derivatives of given R function - sub into D.E. and solve for E - Equate E with previous expression for E - recall boundary condition, must vanish @ edges->R(r=a)=0 Q1: Given n=2, l=1 find most prob. dis betwn e- and nucleus. Find <r> and <V> by integration Radial probability density Pnl(r)=r2(Rnl)2
−ρ ⎡ 1 ⎤ 2 P21 ( r ) = r 2 ( R21 ) = r 2 ⎢ ρe 2 ⎥ 3 ⎣ 2 6a ⎦ −r ⎡ 1 r 2a ⎤ r 4e− r / a = r2 ⎢ e ⎥ = 24a 5 2 6a 3 a ⎣ ⎦ 2 2

spin quantum number ⇒ ms = ±1 / 2

tot. ang. mom. qu. # ⇒ j = l ± 1 for l ≠ 0 j = 1 for l = 0 2 2
there are only EVER two possible j states for non zero l

m j = - j... j L2 =
2l

2 j + 1 possible m j states

(l +1)

Lz = ml

S2 =

2s

( s +1) = 3 4

2

J = L+ S J2
2

= j ( j + 1) eg: 3P / 2 → n = 3;l = 1; j = 1/ 2 1

Sz = ms s = 1 2 J z = Lz + Sz = m j

Stern-Gerlach Experiment
non-uniform Bz applies force on cl. bar magnet Fz = µ z ∂Bz ∂z

= L2 + 2L ⋅ S + S 2

Degeneracy When a quantum system has two or more distinct energy eigenfunctions with the same energy eigenvalue Parity Ylm (π − θ , π + φ ) = ( −1)l Ylm (θ , φ )
j j

Electron Spin (updated wave function) Ψ nlml ms = Rnl ( r ) Ylm (θ , φ ) exp ( −iEnl t / Spin-Orbital Interaction
fine structure constant: α = e2 4πε 0 c
2

Electron Configuration: Alkalis: Li=[He]2s; Na=[Ne]3s; K=[Ar]4s He has ground state electron config (1s)(1s) Excited state (1s)(nl) Cannot excite both above 1s because E > ionization energy Exclusion Principle

where ⎡ Zeff → Z as r → 0⎤ and ⎡ Zeff → 1 as r → ∞ ⎤ ⎣ ⎦ ⎣ ⎦

∞ ∞ −r ⎡ 1 r 2a ⎤ r 5 −ar r = ∫ r3 ⎢ e ⎥ dr = ∫ e dr 3 24a5 ⎣ 2 6a a ⎦ 0 0

2

=

−r 1 1 r 5e a dr = 5!a 6 = 5a 24a 5 ∫ 24a 5 0

Q2: Show from direct calc. that all comp. of dipole transition vanish for nl = 2,0 -> 1,0 n=2, l=0, m=0 ==> n’=1, l’=0, m’=0 Radial Component will be non zero, then must show all angle components zero.
* x − comp = ∫ Y00 sin θ cos φY00 d Ω = 2π π

) ( ↑ or ↓ )

1s 2s 2p 3s 3p (4s 4d ) 4p (5s 4d ) 5p...
Electron Antisymmetry
Ψ (1, 2, t ) = Ψ (2,1, t )
2 2

∫ ∫ ⎡sin ⎣
0 0

2

θ cos φ ⎤ dθ dφ = ... = 0 ⎦

Observables note:dτ = r 2 dr sin θ dθ dφ = r 2 drd Ω
Pnl ( r ) = r 2 Rnl ( r )
∞ 0 2

energy level shift due to spin-orbit interaction:
2 2

exchange-symmetric: Ψ (1, 2, t ) = Ψ (2,1, t ) exchange-antisymmetric: Ψ (1, 2, t ) = −Ψ (2,1, t ) requirement of antisymmetry:

Q3: Eval. Z-comp of dip. Trans. For 3p->2s - chk: n=3, l=1 -> n’=2, l’=0 satisfies trans. rules - find radial comp. – find angular comp.

given R 31 and R20 eval: ∫ R31 R20 r 3dr and multiply by z-comp...
* z-component is non vanishing only for m=0 case ∴ ∫ Y00 cos θ Y10 d Ω 0

Ψ nlm = Rnl ( r ) Θlm (θ )
2 ∞ 0

VSL = Zα VSL

S ⋅L J −L −S = Zα r3 2me 2 c r 3 4me 2 c
2 2

2

ψ (1, 2) = ψ (2,1) =

1 2 1

(ψ (

α

(1)ψ β (2) − ψ β (1)ψ α (2) or

) )

r = ∫ rPnl ( r ) dr ⇒ F ( r ) = ∫ F ( r ) Pnl ( r ) dr L2 Lz
2

=

( L2 )

2

= ⎡ 2l ( l + 1) ⎤ ⎣ ⎦
2

2

2

= Lz 2 = [ m ]

ONE-ELECTRON ATOM
Ze 2 Ψ nlm ( r,θ , φ, t ) = Rnl ( r ) Ylm (θ ,φ ) e−iEnl t / V (r) = − 4πε 0 r
2 ⎤ d 2 dR ⎡ r l ( l + 1) ⎥ R = ER − + ⎢V ( r ) + 2µ r 2 dr dr ⎣ 2µ r 2 ⎦ 2 2 ⎡ ⎤ d2 − ( rR ) + ⎢V ( r ) + 2 l ( l + 1)⎥ R = ER 2µ r dr 2 2µ r ⎣ ⎦ 2

VSL

3⎤ 1 ⎡ j ( j + 1) − l ( l + 1) − ⎥ 3 = Zα 4me 2 c ⎢ 4⎦ r ⎣ 3 j ( j + 1) − l ( l + 1) − Z 4α 4 4 me c 2 = l ( l + 1)( 2l + 1) 2n3 Z 4α 2 E0 n3l ( l + 1)

Assignment 9: Given B-ext >> B-int find energy shift <VM>=magnitude of magnetic energy level shift. Strong B implies that we may ignore the <V_SL> coupling term and use quantum numbers ml and ms

ψ α (2)ψ β (1) − ψ β (2)ψ α (1) = −ψ (1, 2) 2 half-int. spin → fermions int. spin → bosons

VM = +

µB B

⎡ LZ + 2 S Z ⎤ = VM = µB B [ ml + 2ms ] ⎣ ⎦

⇒ use LZ = ml ; S Z = ms
3 energy levels have 2 fold degeneracy. Q2: Bext~Bint <VM>~<VSL>: must include fine structure shifts so use qu.# j , m . For l=2, the states are 3D_3/2 and 3D_5/2:
j

The Helium Atom
⎧ψ S (r , r ) χ A (1, 2) ⎪ ψ (1, 2) = ⎨ A 1 2 S ⎪ψ (r1 , r2 ) χ (1, 2) ⎩ or ⎫ ⎪ ⎬ ⎪ ⎭ antisym. and sym. spatial eigenfunctions: 1 2 1 2 1 2 1 2

spin-orbit splitting: δ ESL =

For 3D_3/2:

VM = g µ B Bm j where g = 1 +

∴ nLl +1 / 2 state is higher than nLl −1 / 2

total fine structure shift in energy for l ≠ 0 : VSL + Krel = − ⎛ 2 Z 4α 4 3 ⎞ me c 2 ⎜ − ⎟ 2n3 ⎝ 2 j + 1 4n ⎠

ψ A (r1 , r2 ) = ψ S (r1 , r2 ) = χ A (1, 2) = χ (1, 2) =
S 0

(ψ (ψ
1

α

(r1 )ψ β (r2 ) − ψ β (r1 )ψ α (r2 ) and (r1 )ψ β (r2 ) + ψ β (r1 )ψ α (r2 )
2

)

j ( j + 1) + s ( s + 1) − l ( l + 1) 2 j ( j + 1)

VM =

4 µB B [ 4 possible mj values] 5

α

)

define: ρ = and Enl = −

F (ρ) 4πε 0 2 r ,a= , Rnl = e − ρ / n nl ρ a Ze2 µ

µ Z2
me n
2

E0 = En Bohr

⎛ 2 Z 4α 2 3 ⎞ Enj = En − 3 E0 ⎜ − ⎟ n ⎝ 2 j + 1 4n ⎠

(↑ ↓ (↑ ↓
1

− ↓1 ↑ 2 + ↓1 ↑ 2
2

) )
3 4

χ1S (1, 2) =↑1 ↑ 2 χ (1, 2) =↓1 ↓2
S −1 2 2 = S2

Assignment 10: Q1: For Alkali group, ionization energy is the energy required to remove the signle (ns) valence eFor Li. Valence electron = 2s, use approx: En=Z2E0/n2 Q#2: X-Ray Lines for Tungsten:

k − abs − edge = λΚ 1

2

λKLII

=

1

λΚ

1

λLII

This lack of dependence on l is only valid for H

S = S1 + S 2 ⇒ S12 = S1z = ms1 = ± 2

s1 ( s1 + 1) =

S 2 z = ms 2 = ±

2

ms = ms1 + ms 2

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