Quantum Mechanics and the hydrogen atom

Since we cannot say exactly where an electron is, the Bohr picture
of the atom, with electrons in neat orbits, cannot be correct.
Quantum theory describes
electron probability distributions:
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Equation !"# goes here.
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$ydrogen %tom:
Schr&dinger Equation and Quantum 'umbers
(otential energy for the hydrogen atom:
)he time"independent Schr&dinger equation in three
dimensions is then:
MN

dR mr

1


)
*here does the quantisation in QM come from +
)he atomic problem is spherical so rewrite the equation in ,r,,-
x = r sin cos y = r sin sin

z = r cos
.ewrite all deri/ati/es in ,r,,-, gi/es Schr&dinger equation0
=
2

=

1
2

r
2m r


r 2m sin
sin +

2
2
+ V (r ) = E



sin

)his is a partial differential equation, with coordinates ,deri/ati/es-0
1se again the method of separation of /ariables:
(r, , ) = R(r )Y ( , )
Bring r"dependence to left and angular dependence to right ,di/ide by -:
QM
d
r + (E V (r ))R =

( )
MNW-L2

2
2
2
R

dr
dr

2
O Y ,

Y ( ,
=
Separation of
/ariables

2
*here does the quantisation in QM come from +

2
2

.adial equation
1

d
r
dR
+
2mr
(E V (r ))R

=
R

dr dr

2

1
sin
1
2
+ ,
O
QM
Y ( , )

sin
2

2
Y ( )
%ngular equation

=
=
sin

=
Y ( , ) Y ( , )

2
Y Y
= sin sin + sin Y

2

2nce more separation of /ariables:
Y ( , ) = ( )( )

2

3eri/e:
1 1
= sin sin + sin = m ,again arbitrary constant-


2

Simplest of the three: the a4imuthal angle0
=
2
(
)
2
( ) 0
MNW-L2

2 + m =
*here does the quantisation in QM come from +
% differential equation with a boundary condition
=
2
(
)
2
( ) 0

2
+ m =
and
( + 2 ) = ( )
Solutions:
( ) = e
im
Boundary condition0 ( + 2 ) = e
im( +2 )
= ( ) = e
im
e
2im
= 1
m is a positi/e or negati/e integer
this is a quantisation condition
5eneral: differential equation plus a boundary condition gi/es a quantisation
MNW-L2

+ ( ( ))

= ( + )


*here does the quantisation in QM come from +
6irst coordinate
( ) =
e
im
with integer m
,positi/e and negati/e-
angular
1
=

2

part
Second coordinate
sin
sin

+

sin
2

= 0

angular
.esults in

= ( + 1)
and
with
m = ,
= 0,1,2,
+ 1,,
1,
momentum

2

)hird coordinate
1 d
2
dR 2mr
r E V r R 1
2
R

dr dr


3ifferential
equation
.esults in quantisation of energy
radial
part
2 2

2

2
E =
Z
R =
Z
=
e


m
e
n
2

2
n n

4
0

2
MNW-L2
with integer n ,n78-

%ngular wa/e functions

2

1 1
2

Operators:
L =
i

sin
sin

+
sin
2

Angular momentum
L
z
=

i
L = (L
x
, L
y
, L
z
)
!ere "s a #lass o$ $un#t"ons t!at are s"multaneous e"gen$un#t"ons
L
2
Y
lm
( , ) = ( + 1)
2
Y
lm
( , )
L
z
Y
lm
( , ) = mY
lm
( , )
with =
0,1,2,
and
m = , + 1,, 1,
%p!er"#al !armon"#s (Bolfuncties)
Y
lm
( ,
)
&e#tor spa#e o$ solut"ons
1
Y
00
=
4
Y
11
=
3
sine
8
'
Y
lm

( ,
)
2
d( = 1
Y
*
Y
d( = ) )
Y
10
=

3
cos
4
'
lm

*ar"t+
l
'm'
ll
'
mm'
MNW-L2
Y
1,1
=
3
sin
8
e
i
P
op
,
lm
( , ) =
,(
, + ) = ()

,
lm
( , )

e =
2

)he radial part: finding the ground state

1

d
2
dR 2mr
2

R

dr
r
+
dr

2
(E V (r ))R

=

Prefactor for 1/r:

Ze
2
= 0
ma 4
0
Find a solution for
= 0, m = 0
Solution for the
2

2
length scale paramater
=

R"+
2
R'

Ze
R = ER
2m

r

4
0
r
a =

4
0

Bohr radius
Physical intuition; no density for r -
Ze
2
m
trial: R(r )
=
Ae
r / a
R' =
A
e
r /
a
a
=
R
a
Solutions for the energy
R =
A
r / a
R
2

2

2
"
a
2
a
2
E = =

= Z
2
=
e


m
e
2
=
2

1

=2

Ze
2
=
E
2ma

4
0

2
2
2m
a
2
ar

4
0
r
Ground state in the
Bohr model (n=1)
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must hold for all values of r
$ydrogen %tom:
Schr&dinger Equation and Quantum 'umbers
)here are four different quantum numbers needed to
specify the state of an electron in an atom.
#. )he principal quantum number n gi/es the total energy.
9. )he orbital quantum number gi/es the angular
momentum0
can ta:e on integer /alues from 8 to n " #.
. )he magnetic quantum number, m , gi/es the

direction of the electron;s angular momentum, and can

ta:e on integer /alues from < to =.
MNW-L2
$ydrogen %tom *a/e 6unctions
)he wa/e function of the ground state of hydrogen has
the form:
)he probability of finding the electron in a /olume dV
around a gi/en point is then ||
2
dV.
MNW-L2
.adial (robability 3istributions
%p!er"#al s!ell o$ t!"#.ness dr/ "nner ra0"us r
an0 outer ra0"us r=dr1
2ts 3olume "s d>?@r
2
dr
4ens"t+: A5A
2
d> ? A5A
2
@r
2
dr
!e ra0"al pro6a6l"t+ 0"str"6ut"on "s t!en:
(
r
?@r
2
A5A
2
5round state
MNW-L2
$ydrogen %tom *a/e 6unctions
)his figure shows the three probability distributions for n = 2 and
= 1 ,the distributions for m = +1 and m = -1 are the same-, as well
as the radial distribution for all n = 2 states.
MNW-L2
$ydrogen B2rbitalsC ,electron clouds-
(r

, t )
2
.epresents the probability to find a particle
%t a location r at a time t
)he probability density
)he probability distribution
Max Born
)he 'obel (ri4e in (hysics #!D@
Efor his fundamental research in
quantum mechanics, especially for his
statistical interpretation of the wa/efunctionE
MNW-L2

+
%tomic $ydrogen .adial part
Analysis of radial equation yields:
Z
2
E
nlm
= R

n
2
with
m e
4
R

=
e
8
0

3
!
Wave functions:

nlm
(r , t ) = R
nl
(r ),
lm
( , )e
iE
n
t /
For numerical use:
" (r
)
2Z
=
n 1 !

2Z7

+1
2 1
2Z7
R =
n
" (7 ) =
( )
Z7 / n

L


r
n
na
0
2n(n + 1)!
e

n

n 1

n

MN W-L2
7 / r
= 2Z / na
a =
4
0

2
/
8e
2
*
1
r
9uantum analog o$ ele#tromagnet"# ra0"at"on
:lass"#al ele#tr"# 0"pole ra0"at"on rans"t"on 0"pole moment
:lass"#al os#"llator 9uantum ;ump
#
rad

e

2
#
rad

'
5
1
er

5
2
2
d<
!e atom 0oes not ra0"ate =!en "t "s "n a stat"onar+ state >
!e atom !as no 0"pole moment
8
ii
=
'
5
*

5
1
d< = 0
8
2
2ntens"t+ o$ spe#tral l"nes l"n.e0
to ?"nste"n #oe$$"#"ent $or a6sorpt"on:
$
i
%
=
%i
6
0

2
MNW-L2
Selection rules
@at!emat"#al 6a#.groun0: $un#t"on o$ o00 par"t+ g"3es 8 =!en "ntegrate0 o3er spa#e
2n one 0"mens"on:

%
x

=
'

%
x
i
dx
=

'
% (
x)dx
% ( x) =
*
x
*
="t!
% i

'
% ( x)dx =

0
'
% ( x)dx +
'
0
0
% ( x)dx =
'

% ( x)d ( x)+
'
0

% ( x)dx =
'
0

% ( x)dx +
'
0
% ( x)dx

= 2
'
0
% ( x)dx A 0 "$
% ( x)
=
% (
x)

i
an0
%
oppos"te par"t+
= 0 "$ % ( x) = % (
x)

i
an0
%
same par"t+
?le#tr"# 0"pole ra0"at"on #onne#ts states o$ oppos"te par"t+ >
MNW-L2

r
r

r
%ele#t"on rules
0epen0 on angula r 6e!a3"or o$ t!e =a3e $un#t"ons
*ar"t+ operator
All Buantum me#!an"#al =a3e $un#t"ons
!a3e a 0e$"n"te par"t+

( r ) = C(r )

%

i
A 0
2$
%
an0

i
!a3e oppos"te par"t+
Pr = r Dule a6out t!e
Y

m
$un#t"ons
( x, y, z) - ( x, y, z)
(r, , ) - (r,

, + )
PY
m
( , ) =
()

Y
m
( , )
MNW-L2
$ydrogen %tom:
Schr&dinger Equation and Quantum 'umbers
B%llowedC transitions between energy le/els occur between states
whose /alue of differ by one:
2ther, Bforbidden,C transitions also occur but with much lower
probability.
Bselection rules, related to symmetryC
MNW-L2
%ele#t"on rules "n E+0rogen atom
2ntens"t+ o$ spe#tral l"nes g"3en 6+
*

8
%i
=
'

%
8
i
=

%
er
i
F) 9uantum num6er n
no restr"#t"ons
G) *ar"t+ rule $or

H = odd
Ialmer ser"es
J) Kaporte rule $or

Angular momentum rule:
K+man ser"es


%
=
i
+ 1 so 1
Lrom G1 an0 J1 H = C1
MNW-L2