Formula sheet

H=H 0 +H ' H ' =HH 0 E1= n|H '|n

2

ea x dx=
Addition of angular momenta a
J =L+ S dim ( j , m )=dim ( l ,m )+dim ( s ,m )|n1 = m n m|H '|n |m 2
1 3 5 ( n+1 )
E nEm x n ea x dx= n n+1
, n=0, 2, 4,
| j , m =|l , m |s , m [ J i , J j ]=i ijk J k 2
2
2 a 2

E2= m n
| m|H |n |'

J = j ( j+1 )m ( m 1 ) Gauss law for spherical symmetries

EnE m
Taylor expansion of relativistic kinetic Q enc
energy Harmonic oscillator ladder operators =4 r 2E(r )
0
1 +
v2
2 2
K Erel =m c m0 c = m0 c m 0 c =m0 c ( 1 2
c
2 2 2
( )2
1) a+a a+ = n+1
Electric potential energy from r

Taylor expansion of trial function,

1
x=

2 m
c a= n ; c
q E ( r ) dr
2
f ( x )=( 1x ) 1 : Variational method
Hydrogen atom expectation values by
3 5
| = cn Feynman-Hellman theorem (and other
1 13 Define trial function,
f ' ( x )= ( 1x ) ; f '' ( x ) =
2
( 1x ) ; 2 techniques)
2 22 2
|c n| E n Hdx

( )
v
2
f 2 =m0 c 2
c
1v 3v
2 (
+ 4 =
2c 8c
p 3 p
+
2

2 m 8 m3 c 2
+
4

)
2 4 E =
|c n|
2
=E ( p )=
dx Minimize
1
r
=
1
2
a0 n r
1
; 2 =
( )
1
1
l+ a20 n3
2
w.r.t. variable parameter, and find E( p0 )
Feynman-Hellman theorem

dE ( p ) dH ( p )
Linear variational method
1
r 3
=
1
1
( )
l ( l+1 ) l+ a30 n3
H ( p )| ( p ) =E ( p )| ( p ) = x
2
2
dp d (p) 2 d 2
H= + x 4 ; ( x ; )=e 2
2 m d x2
( )
1 1 1 1 Perturbation theory for relativistic
= , p=e ; 2 = , p=l 2 correction
r
2
2
1 2 3
( ) dx= =N
x
a0 n r
l+ a0 n e 2 4
2 3 p 3
H '= 3 2
E1 = 3 2 nlm| p4|nlm
8 m c 8m c
Perturbation theory x
2 2
x
E ()=


e
2
( 2 d2
2 m d x2 )
+ x4 e 2
dx p2 |
2m
nlm +V |nlm =E|nlm p4 =4 m2 ( EV )
2

2 3 dE 2 3 6 m 13 1 1
E=
( ) + =
4 m 4 2 d 4 m 2 3
=0 =
2 E = 2 mc 2 nlm|( EV ) |nlm
2
( )
Important and standard integrals (over all
space unless specified)
 1 1 1 2 2 2 Helium approximation
E 1= nlm|E 22 EV +V 2|nlm H '= ( J L S ) Thomas
4 0 me c r 2
2 2 2 3
2 mc p2 e2 1 1 1
1
=F 1
H helium=
2m 1
( + 2) +
(
4 0 r 1 r 2 |r 1r 2| )
precession factor is,
2 m c2 2 2
e
1 11 2 2 2 H helium=H 1hydrogen+ H hydrogen +
E22 E nlm|V |nlm + nlm|V 2|nlm H '= ( J L S )
2
4 0|r 1r 2|
4 0 me c r 2 2
2 2 3
E1 =F
H helium H hydrogen
1 + H hydrogen
2
2 2 1
(
E1=F E2 +2 E
e 1
+ e 1
4 0 r ( 4 0 )2 r 2 ) H '= 2 2 3
16 0 m e c r
( J 2L2 S 2 ) E=E1 + E2 ; ( r 1 , r 2 ) = 1 ( r 1 ) 2 ( r 2 )
2
2 2 J 2L2S 2
E gs
( ( ))
m Ze 2

( )
e 1 e 1 1 1
E1=F E2 +2 E 2
+ 2 E 1= nlm 3 ( |nlm ) 2 2 4 0
4 0 a0 n ( 4 0 ) 1
( )
2 2
l+ a20 n3 16 0 me c r
2 2(4 EH ; gs )=108.8 eV

2 n 3 1 e2 13.6
E 1=
1
(
2 j ( j1 ) l ( l+1 )
3
4 ) r1 E He;gs

( )
2 2 3
1
E =E 2 ,= = , En = 2 16 0 me c
n l+ 1 4 137 4 0 c n E gs;real =78.9 eV
2
3
1
2
E 1=
2 2
16 0 me c (
j ( j+1 )l ( l+1 )
4 ) Miscellaneous equations
E <0 E pert Bessels equation:
1
l 0
l ( l+1 ) l+ a30 n3
2 ( ) x2
d2 y
2
dy
+x + ( x2 n2 ) y=0, n C
Spin correction to hydrogen atom dx dx

( ( 34 +l ( l+1) j ( j+1) )
)
e 1 2
n Change of variables:
E= r^
Electric field of nucleus, 4 0 r3 E1=E n dy dy dr d 2 y d 2 y dr 2 dy d 2 r
Magnetic force experienced by electron,
n
2
1
2 l ( l+1 ) ( l+ )
2
Total
= ; =
dx dr dx d x 2 d r 2 dx
+ ( )
dr d x 2
v E
B= Radial wavefunction:
c2 correction
2

Magnetic moment of electron,

=
e
me
S Darwin term is,
2 n En
mc
2
2

, for l=0 2 m d r2
+ (
2 d 2 u l ( l+1 )
2m r 2 )
+V ( r ) u=Eu ,u=rR ( r )

1 Total correction to energy is, Spherical harmonics:

H ' = B= vr S n
2
3
4 0 me c 2 r 3

L=m E L S H ' =
1
2 2 3
4 0 me c r
LS
En 2
2

n j+ 1 4
( )
1
j max =n E < 0
 1 1 Other stuff:
Y lm ( , )=(1 )

|m|
m

2 l+1 ( l|m|) !

4 ( l+|m|) !
Plm ( cos ( ) ) e im Spin basis is, { , }
2 2
In relativistic correction,
3 1

8 8
3
( )
S 2= 2 1 0 ; S z = 1 0 ( )
|m|
d
Plm ( x )=( 1x ) 2 2
( ) dx
Pl ( x ) 4 0 1 2 0 1 Hydrogen atom

The normalized wavefunctions for hydrogen are

1 d l ( 2 )l
Pl ( x )= l ( )
2 l! dx
x 1 Sx =
0 1
( )
2 1 0

; S y = 0 i
2 i 0 ( )
given by,

Dirac notation and matrix form:

J =J x i J y J 2 j ( j+1 ) 2 ; J z m j List of hydrogenic wavefunctions
O = n|O|n n|m = nm s-orbitals
Dirac delta function:
p-orbitals
Angular momentum and spin matrices in
standard basis:

{1,1 ,1,0 ,1,1 } is basis for orbital

d-orbitals (above)

angular momentum

( ) ( )
1 0 0 1 0 0
L2=2 2 0 1 0 ; Lz = 0 0 0
0 0 1 0 0 1
'
n

( )
0 1 0 0
( )
1 0 ( xa ) f ( x ) ( xa ) dx=f ( a ) , n<a< n'
Lx = 1 0 1 ; L = 1 0 1
2 0 1 0 y i 2 0 1 0 n

0 , otherwise