Atomic and Molecular Physics

PY4105 / CY4001
Eigenfunctions of the one-electron atom
Angular momentum and spin

Multi-electron atoms
Atoms in magnetic fields
Spectroscopic methods & line shapes
Molecules & quantum chemistry

Organization
Lecturer:
Times:

Andy Ruth, Room 118c, Kane (Science Building), a.ruth@ucc.ie

Tuesday 10-11, Thursday 1-2

Literature and Texts

Library (dewey) classification: 539.1 Atoms 539.6 Molecules
J.J. Brehm and W.J. Mullins, An Introduction to the Structure of Matter, Wiley 1985
R. Eisberg and R. Resnick, Quantum Mechanics of Atoms, Molecules, Solids,
Nuclei and Particles (2nd Ed.), Wiley 1985
H. Haken and H.C. Wolf, The Physics of Atoms and Quanta, (7th Ed.), Springer 2005
H. Haken and H.C. Wolf, Molecular Physics and Elements of Quantum Chemistry,
(2nd Ed.), Springer 2004
M. Mansfield and C. OSullivan, Understanding Physics, (2nd Ed.), Wiley 2011

Problem sets
Approximately one every 2 weeks. Supported by tutorials which are to be arranged.

E-Support
Lecture slides will be made available on Blackboard under PY4105 together with some
supplementary material !

Q: Why can't you trust an atom?

A: They make up everything.

The Heineken Uncertainty Principle:

You can never be sure how many beers you had last night.

The one-electron atom (H, He+, Li2+, H2+)

One-electron atom is a rare example of a real physics situation that can be analysed
rigorously and analytically. The hydrogen is still a test case for theory to this day.
The one-electron solutions are carried into the analysis and description of
multi-electron atoms, of molecules, of electron behaviours in solids and
of nuclei (shell model).
Arthur Schawlow (co-inventor of the laser):
The spectrum of the hydrogen atom has proven to be the Rosetta stone
of modern physics: once this pattern of lines had been deciphered much
else could also be understood.

Motion in a central field

- Hydrogen atom = 2 , , = 2 , ,

Laplace Operator in spherical coordinates

Time-independent Schrdinger-Equation (TISE) in 3 dimensions:

2
, , + 2 , , = 0

Explicit:
1 2
1

1
2
2

+ 2
sin
+ 2 2
+ 2 , , = 0
2

sin

sin 2

The wavefunction turns out to be separable: , , = ()()

Separation constants have the form: l(l+1) and ml
, , =

( quantum numbers)

()

Note: Radial dependence on n and l is relevant for the H-atom, not for a central field problem in general.

Separability leads to three differential equations:

(a) Azimuthal equation: -equation
2
+ = 0
2

Physically acceptable solutions take the form:

() = exp()

1
2

for = 0, 1, 2, 3,

Normalisation factor for -solution

Azimuthal functions
ml

-solution in complex form

1
2
2

ml is an integer:

1 =
2

2 =

2
1
2
1
2
1
2
1
2

2
2

= 0, 1, 2, 3

For H-atom the following condition holds:

= , + 1 , . , +

(b) Polar equation: -equation

1 1

sin
+ +1 2 =0
sin

sin

Physically acceptable solutions take the form:

The form of the solution depend on values of l and ml :

l = 0,1,2,3 is integer with condition: l
(1)
(cos) =
1 cos2

2 !

2 + 1 !
2
+ !

+ cos2 1
cos +

Associated Legendre
Polynomials

Normalisation factor for solution

Polar functions
l

ml

()-solution

00

10

+ 1, 1

11 =

20

+ 1, 1

21 =

+ 2, 2

22 =

= , + 1 , . , +
= 0, 1, 2, 3, , ( 1)

2
2
6
2
3
2
10
4
15
2
15
4

cos
sin
(3 cos2 1)
sin cos
sin2

Polar functions
z

No dependence. Symmetrical around z

z

l=0
ml = 0

00 = 0.5

x or y

x or y

l=1
ml = 1

10 = 1.5 cos

Length = value of ( )

l=1
ml = 0

11 = 0.75 cos

l=2
ml = 0

x or y

x or y

+
10 =

5/8 [3 cos2 1]

(c) Radial equation: R-equation (general central field)

1 2
2
( + 1)2

+ 2
=0
2

22
Note: General central field, i.e. V(r) unspecified, but assume V(r) 0 for r :
For E < 0 define:
For E > 0 define:

2
= 2

2
2 = 2

Physically acceptable solutions take the form:

1
For E < 0: = exp

1
For E > 0: = 1 exp + 2exp()

Quantum mechanical equivalent of

elliptical trajectory
hyperbolic trajectory

c, c1 and c2 are integration constants that serve normalization. Explicit values are given for
the case of V(r) being a Coulomb potential in the H-atom.

(c) Radial equation: R-equation

(Coulomb potential of one-electron atom with reduced mass mr)
1 2
2
( + 1)2

+ 2
=0
2

22
2 1
Coulomb potential: =
40
2 2
2
=

Define:
40 2
0

402
0 =
= 5.29 1011 m
2

Bohr radius

Physically acceptable solutions take the form:

=
2+1
+ exp

2
0

1 !
2 + ! 3

2+1
+

(1)+2+1

=
=0

1
2

2
Normalisation factor for R solution for H-atom

+ ! 2
1 ! 2 + 1 + ! !

Associated Laguerre
Functions

Radial functions

= 1, 2, 3,
= 0, 1, 2, 3, , ( 1)
n
1
2
2
3
3
3
4

l
0
0
1
0
1
2
0

(one-electron atom)

402
Bohr radius: 0 =
2

Rnl (r)-solution

20 =
0
10 =

21 =
0

30 =
0

32 =
0
31 =

40 =
0

3
2
3
2

3
2

2 2
1

3
2

2 6

3
2

9 3
1

3
2

9 6
1

3
2

exp
20

exp

exp
20

4 422
6
+
0
902

exp
30

2 2
30 30
2

30

exp
30

exp

2
9 30 30
1

24 18
+3
96
0
0

20

exp
40

Radial functions

3
2
15
10 m

(H-atom)

n=2
l=0

R20

R10

3
2
15
10 m

n=1
l=0

r / nm

3
2
15
10 m

r / nm
n=2
l=1

R21
r / nm

 = 1, 2, 3,
= 0, 1, 2, 3, , ( 1)
= , + 1 , . , +

n2
1

Bohr radius:

n l ml

, , =

1 0

2 1 1

3 0

3 11

3 2

3 21

3 22

2 0

The first 14 normalized wavefunctions of a one-electron atom

2 1

3 1

3
2

1
4 2

3
2

4 2 0
1
8

3
2

3
2

3
2

exp

20

exp

1
81

6
0 0

81 6

22
02

sin

2
81

20

exp
30

0 0

cos

18 222
27
+ 2
0
0
81 3

30

exp
30

sin cos

22
02

exp
30

3s

20
9

3p

30

1
162

2p

sin2

exp()
1
exp()
exp(2)

2s

20
4

cos
sin

1s

2p

(3cos2 1)

exp

exp()

assignment

20

30

22
02

20

1
20

20

exp

1
81

4
32 2 02

energy En

exp
20
exp

3
2

3
2

3
2

3
2

exp
0
2

0 =

()

3
2

402
0 =
2

20

9
20

9
2
0

9
20

3p
3d
3d
3d

Quantum numbers
Three integer (quantum numbers) emerge from analysis: n, l, ml
One for each degree of freedom.
n = 1, 2, 3 .

Is known as the principle quantum number.

It specifies the total energy of the atom.

l = 0, 1, 2, (n 1)

Is known as the orbital quantum number (l < n).

It specifies the orbital angular momentum of the atom.
Is known as the magnetic quantum number (ml l).
It specifies the orientation of the orbital angular momentum
of the electron in an external magnetic field.

ml = l, 1, 0, +1+l

Note: Even though many different values for l and ml are possible for a given value of n,
the energies (En) depend only on n.

For each n there are n values of l and for each of

these there are (2l + 1) values of ml. Eigenfunctions
are thus n2-fold degenerate (at this level of analysis!):

24 1
=
32220 2

l-values of a state of a one-electron atom are given in

spectroscopic notation:
l= 0
s
sharp

1
p

2
d

3
f

principle

diffuse

fundamental

4
g

5
h

6
i

1
=0

(2 + 1)

state label

Spectroscopic Notation (H-atom)

Coulomb Potential
0
20

10

E4

E3
E2

Important Note: The Coulomb

potential is spherically symmetric
for isolated hydrogen. There is no
preferred direction in space. The
zaxis was adopted as a
mathematical convenience for
analysis. n, l and ml cannot be
determined from experimental
observations for each electron in
each atom, because this would
require determination of the z
axis!

1
2

10

E1
15

[eV]

The total energy En

is independent of
the orientation in
space. Degeneracy
in ml occurs due to
the spherical
symmetry of the
one-electron atom.