hydrogen atom: center-of-mass and relative

2-particle problem (electron & proton)


~2 ~2
e p + V (|~re ~rp |) (~re , ~rp ) = E (~re , ~rp )
2me 2mp

separation in center-of-mass and relative coordinates

m e r e + m p rp
R= r = re rp
me + mp
me mp
M = me + mp µ=
me + mp

~ 2 ~2
R S(R) = ECM S(R) r + V (|~r |) (~r ) = EH (~r )
2M 2µ

~ (~r )
(~re , ~rp ) = S(R) and E = ECM + EH
 hydrogen atom: spherical separation

relative motion

~2
r + V (|~r |) (~r ) = EH (~r )
2µ

spherical symmetry
u(r )
(~r ) = Yl,m (✓, )
r
✓ ◆
~ d
2 2
~ l(l + 1)
2
e 2

2
+ 2
u(r ) = EH u(r )
2µ dr 2µ r 4⇡✏0 r

dimensionless units: ρ=κr with κ2=2m|E|/ħ2 and ρ0= 2me2 / (4πε0 ħ2 κ)

✓ 2
◆
d l(l + 1) ⇢0
+ 1 u(⇢) = 0
d⇢2 ⇢2 ⇢
 hydrogen atom: radial solution

ansatz (solve asymptotics)

u(⇢) = ⇢l+1 w (⇢) e ⇢

differential equation for L(s):

d 2w dw
⇢ 2 + 2(l + 1 ⇢) + (⇢0 2(l + 1))w = 0
d⇢ d⇢
1
X
ansatz: power series w (⇢) = ak ⇢k
k=0
2(k + l + 1) ⇢0
recursion for coefficients ak+1 = ak
(k + 1)(k + 2l + 2)

normalizability: recurrence must terminate at some finite k

n l +1
 radial functions unl(r) = r Rnl(r)
0.80 0.50
u1,0 u2,0
0.40 u2,1
0.70
0.30
0.60
0.20
0.50 0.10
0.40 0.00

0.30 -0.10
-0.20
0.20
-0.30
0.10 -0.40
0.00 -0.50
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
0.40 0.30
u3,0 u4,0
u3,1 u4,1
0.30 u3,2 u4,2
0.20
u4,3
0.20
0.10
0.10

0.00 0.00

-0.10
-0.10
-0.20
-0.20
-0.30

-0.40 -0.30
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
 radial functions Rnl(r)
2.00 0.80
R1,0 R2,0
1.80 0.70 R2,1
1.60 0.60
1.40
0.50
1.20
0.40
1.00
0.30
0.80
0.20
0.60
0.40 0.10

0.20 0.00
0.00 -0.10
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
0.40 0.25
R3,0 R4,0
0.35 R3,1 R4,1
R3,2 0.20 R4,2
0.30 R4,3
0.25
0.15
0.20
0.15 0.10
0.10
0.05
0.05
0.00
0.00
-0.05
-0.10 -0.05
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
 periodic table

1s 1s

2s 2p

3s 3p

4s 3d 4p

5s 4d 5p

6s 5d 6p

7s 6d

4f

5f
 atom in spherical mean-field approximation
6 2 0
Fe : [Ar] 3d 4s 4p
100

10
Zeff(r)

0.1
0 1 2 3 4 5 6 7 8
r in Å
 Atom- und Hybrid-Orbitale
z z z
s sp21 sp22

y y y

x x x

z z z z sp34 z
px py pz sp31

y y y y y

x x x x x

dxy z dyz z dzx z

y y y

x x x

d3z2-1 z dx2-y2 z

y y

x x
 numerical differentiation

task: evaluate f’(x), only knowing f(x) at some specified abscissae xi

idea: approximate f by a function that can be easily differentiated, e.g.,

a Taylor expansion. Then combine the f(xi) such that – except for the
desired derivative – as many terms as possible are cancelled.

example: first derivative

2
h h3 000
f (x0 + h) = f (x0 ) + h f 0 (x0 ) + f 00 (x0 ) + f (x0 ) + O(h4 )
2 6
f (x0 ) = f (x0 )
2
h h3 000
f (x0 h) = f (x0 ) h f 0 (x0 ) + f 00 (x0 ) f (x0 ) + O(h4 )
2 6

3
h
Then f (x0 + h) f (x0 h) = 2h f 0 (x0 ) + f 000 (x0 ) + O(h4 )
3
0 f (x0 + h) f (x0 h)
or f (x0 ) = + O(h3 )
2h
 numerical differentiation

differences of similar
numbers in numerator
& small denominator

100 O(hn) error from

approximation
10-5
abs(error)

10-10

10-15
-12 -10 -8 -6 -4 -2 0 ε/h error from finite
10 10 10 10 10 10 10
h machine accuracy ε
 method of undetermined coefficients
idea: given a set of abscissae xn, e.g., xn=x0+nh, n=-1, 0, 1, 2, make an ansatz with
undetermined coefficients, e.g.,:
0 1f (x 1 ) + 0f (x0 ) + 1f (x1 ) + 2f (x2 )
f (x0 ) =
h
determine the coefficients αi by requiring that the formula differentiates polynomials of
order, e.g., 0 to 3 exactly by solving the resulting system of linear equations
Maple session:
O with linalg :
O n d 1 : # formula for nth derivative
O mesh d x0Kh, x0, x0 C h, x0 C 2 * h ; p d nops mesh : # abscissae xi
mesh := x0 K h, x0, x0 C h, x0 C 2 h (1)
O f_x d array seq map x / x ^ k, mesh , k = 0 ..pK1 ; # evaluate monomials on mesh
1 1 1 1
x0 K h x0 x0 C h x0 C 2 h
f_x := 2 (2)
x0 K h x0 2 x0 C h 2
x0 C 2 h 2

3
x0 K h x0 3 x0 C h 3
x0 C 2 h 3

O der_f d array seq binomial k, n * n !* x0 ^ kKn , k = 0 ..pK1 ;

# derivative of monomials
2
der_f := 0 1 2 x0 3 x0 (3)

O coefficients d linsolve f_x, der_f ; # coefficients alpha i

1 1 1 1
coefficients := K K K (4)
3h 2h h 6h
 Numerov method

one-dimensional Schrödinger equation

u 00 (x) + k 2 (x)u(x) = 0 where k 2 (x) = 2m

~2 (E V (x))

numerical derivative
f (x0 + h) 2f (x0 ) + f (x0 h) h2 (4)
f 00 (x0 ) = f (x0 ) + O(h4 )
h2 12

two-point iteration of wave function u(xj):

uj+1 = (2 h2 kj2 ) uj uj 1 + O(h 4
)

Numerov trick:
remove leading error in derivative formula by using Schrödinger equation
2
h2 (4) 4 h2 d 2 2 4
kj+1 uj+1 2kj2 uj + kj2 1 uj 1
u (xj ) + O(h ) = + 2
k (xj )u(xj ) + O(h ) = + O(h4 )
12 12 dx 12

Numerov iteration:
2(1 5h2 kj2 /12)uj (1 + h2 kj⌥1
2
/12)uj⌥1 6
uj±1 = 2 2 + O(h )
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1 + h kj±1 /12
Numerov iteration close to eigenvalue

0.0

-0.2

-0.4

-0.6

-0.8

-1.0
-20 0 20
 (in)stability of Numerov iteration

0.0

-0.2

-0.4

-0.6

-0.8

-1.0
-20 0 20
 indistinguishability and statistics

N-particle systems described by wave-function with

N particle degrees of freedom (tensor space):
Ψ(x1, ..., xN)

introduces labeling of particles

indistinguishable particles: no observable exists to distinguish them

in particular no observable can depend on labeling of particles

consider permutations P of particle labels

P (x1 , x2 ) = (x2 , x1 ) with | (x1 , x2 )|2 = | (x2 , x1 )|2
P (x1 , x2 ) = e i (x1 , x2 )

when P2 = Id eiɸ = ±1 (Ψ (anti)symmetric under permuation)

antisymmetric: Ψ(x1, x2→x1) = 0 (Pauli principle)
 spin-statistics connection

bosons (integer spin): symmetric wave-function

fermions (half-integer spin): anti-symmetric wave-function

Feynman Lectures III, 4-1:

Why is it that particles with half-integral spin are Fermi particles whose amplitudes add
with the minus sign, whereas particles with integral spin are Bose particles whose
amplitudes add with the positive sign? We apologize for the fact that we cannot give
you an elementary explanation. An explanation has been worked out by Pauli from
complicated arguments of quantum field theory and relativity. He has shown that the
two must necessarily go together, but we have not been able to find a way of
reproducing his arguments on an elementary level. It appears to be one of the few
places in physics where there is a rule which can be stated very simply, but for which
no one has found a simple and easy explanation. The explanation is deep down in
relativistic quantum mechanics. This probably means that we do not have a complete
understanding of the fundamental principle involved. For the moment, you will just have
to take it as one of the rules of the world.
 permutations in lower dimensions

M. Berry et al.: spin-statistics connection from geometric phase

when permuting particles along paths?

x1 x2 x1 x2
2 dimensional 1 dimensional
P2 ≠ Id: braiding statistics: anyons fermions cannot pass
 2-particle wave-function: distinguishable
two particles in (different) ortho-normal single-particle states φa(x) and φb(x)

12 (x1 , x2 ) = 'a (x1 )'b (x2 ) or 21 (x1 , x2 ) = 'b (x1 )'a (x2 )

expectation value of particle distance: M = (x1-x2)2

⌦ 2
↵ ⌦ 2↵ ⌦ ↵ ⌦ 2↵
(x1 x2 ) = x1 2 x1 x2 + x2 normalized

⌦ 2↵ R R ⌦ ↵
x1 12 = dx1 x12 |'a (x1 )|2 dx2 |'b (x2 )|2 = x 2 a · 1
⌦ 2↵ R R ⌦ ↵
x2 12 = dx1 |'a (x1 )|2 dx2 x22 |'b (x2 )|2 = 1 · x2 b
⌦ ↵ R 2
R
x1 x2 12 = dx1 x1 |'a (x1 )| dx2 x2 |'b (x2 )|2 = hxia · hxib
⌦ ↵ ⌦ ↵ ⌦ ↵
(x1 x2 )2 12 = x 2 a + x 2 b 2 hxia hxib
⌦ 2
↵ ⌦ 2
↵
= (x2 x1 ) 12
= (x1 x2 ) 21

observable does not

distinguish particles
 2-particle wave-function: indistinguishable

symmetric / anti-symmetric wave-function

1
± (x1 , x2 ) = p 12 (x1 , x2 ) ± 21 (x1 , x2 )
2
observable does not
cross-terms between product wave-functions distinguish particles
1⇣ ⌘
hMi± = hMi12 ±h 12 |M| 21 i±h 21 |M| 12 i+hMi21 = hMi12 ±h 12 |M| 21 i
2
particle permutation: exchange-terms orthogonal
⌦ 2
↵ R 2
R ⌦ 2
↵
|x
12 1 | 21 = dx x '
1 1 a 1(x )' (x
b 1 ) dx 2 ' (x
b 2 )' (x
a 2 ) = x ab
· 0
⌦ 2
↵ R R 2
⌦ 2↵
12 |x2 | 21 = dx1 'a (x1 )'b (x1 ) dx2 x2 'b (x2 )'a (x2 ) = 0 · x ba
⌦ ↵ R R
12 |x1 x2 | 21 = dx1 x1 'a (x1 )'b (x1 ) dx2 x2 'b (x2 )'a (x2 ) = hxiab · hxiba

⌦ 2
↵ ⌦ 2↵ ⌦ 2↵ 2
(x1 x2 ) ±
= x a+ x b 2 hxia hxib ⌥ 2 |hxiab |
Bosons prefer company
Fermions keep their distance
 probability density for 2 particles in a box
5
4
distinguishable
3
2
φb(x) 1
0
φa(x)

1
0.8
0.6
x2 0.4 0.8 1
0.2 0.4 0.6
00 0.2 x1

symmetric anti-symmetric
5 5
4 4
3 3
2 2
1 1
0 0

1 1
0.8 0.8
0.6 0.6
x2 0.4 0.8 1 x2 0.4 0.8 1
0.2 0.4 0.6 0.2 0.4 0.6
00 0.2 x1 00 0.2 x1
 How about electrons on the moon?
in principle we need to antisymmetrize the
wave-function for all electrons in the universe

really?

product states of states with zero overlap will not give an exchange contribution
Z
h 12 |M| 21 i = dx1 dx2 'a (x1 )'b (x2 ) M(x1 , x2 ) 'b (x1 )'a (x2 )

zero overlap makes electrons actually distinguishable by their coordinate

in practice:
can exclude electrons with negligible overlap from antisymmetrization

more practical example: spin

need not antisymmetrize electrons of different spin
when we are only interested in observables that do not change spin