Hydrogen-like Atoms

A hydrogen like atom consists of one nucleus of charge Ze and a single electron of charge
-e. The classical energy of this system is the sum of the kinetic energies of both particles
and their Coulombic attraction'

E=

1
1
Ze 2
mN rN2 + me re2
2
2
4 0 re rN

We can separate the center of mass motion from the internal motion by the
transformation
r = re rn and R = (me re + mN rN ) / mt
where mt = me + mn . From these we get

rN = R

me
m
r & re = R + N r
mt
mt

and the energy becomes

E=

1
1
Ze 2
mt R 2 + r 2
2
2
4 0 r

where =

Ecm =

me mN
is the reduced mass. The center of mass energy is
me + mN

1
mt R 2
2

while the internal or energy due to the relative motion is

Eint =

1 2 Ze 2
r
2
4 0 r

The Hamiltonian for the two particles is then

Pcm2 Pint2
Ze 2

H = H cm + H int =
2mt 2 4 0 r
The Schrodinger equation is then

J. F. Harrison

Michigan State University

H = E
and if we write ( R, r ) = ( R) (r ) the eigenvalue E can be written as the sum of the
center of mass energy and the internal energy, E = Ecm + Eint where
H cmcm ( R ) = Ecmcm ( R )

& H int int ( r ) = Eint int (r )

and
H cm =

2mt

2
cm
& H int =

Ze2
4 0 r

In the absence of an external field, the center of mass motion is that of a neutral free
particle. If the system is in free space (not bounded) the wave function is a plane wave
and the energy a continuous function of the particles momentum.

( R, k ) = Ceik i R & Ecm =

k2
where < k < +
2mt
Internal Motion

The Hamiltonian for the internal motion may be written in spherical polar coordinates as
H =

L 2
Ze2
2
r
+

2 r 2 r r 2 r 2 4 0 r
2

2
L 2
r
is
the
radial
kinetic
energy
operator
and
is the angular

2 r 2 r r
2 r 2
kinetic energy operator and L 2 is the orbital angular momentum operator

where

L 2 =

sin

sin

1 2

. The Schrodinger equation is then

+

2
2
sin

H = E where = ( r, , ) .
The Hamiltonian commutes with both L 2 and one of the components of the orbital

angular momentum operator, usually chosen to as L z = ih , so the eigenfunctions of

H are also eigenfunctions of L 2 & L . Accordingly

z

= R( r )Yl m ( , )

J. F. Harrison

Michigan State University

where L 2Yl m ( , ) =

l ( l + 1) Yl m ( , ) and L zYl m ( , ) = m Yl m ( , ) . l = 0,1, 2 ,

and

l m l . l is called the orbital angular momentum quantum number and m, the

magnetic quantum number.

The radial functions satisfy

2

2 l ( l + 1)

r
+
2
2 r 2
2 r r r

Ze 2
Rnl ( r ) = En Rnl ( r )
4 0 r

where they have the general form

( n l 1) !
Rnl (r ) =
3
2n [ (n + l )!]

1/ 2

2Z

na0

l + 3/ 2

rle

Zr

na0

2 Zr
L2nl++l1

na0

and L2nl++l1 is an associated Laguerre polynomial. The radial and angular functions are
discussed in detail in most Quantum Chemistry texts and for completeness we tabulate a
2Zr
and with the Bohr radius
few of the most commonly used below. Note that =
na0

given by a0 =

4 0

e2

The energy associated with the internal motion depends only on n and is
En =

Z 2e2
8 0 a0 n 2

n = 1, 2,3,

with the quantum number, 1 n < . Recall the constraints

while l = 0 ,1, 2,

,n 1 The eigenfunctions have the form

nlm (r ) = Rnl (r )Yl m ( , )

Radial Functions

n = 1, K shell:
= 0, 1s

R10 ( r ) = ( Z a0 ) 2 i2e

n = 2, L shell:

J. F. Harrison

Michigan State University

= 0, 2 s
= 1, 2 p

R20 ( r )

(Z
=

a0 ) 2

R21 ( r )

(Z
=

a0 ) 2

2 2

(2 )e

2 6

n = 3, M shell:
=0 ,3s
=1,3 p
=2,3d

R30 ( r )

(Z
=

a0 ) 2

R31 ( r )

(Z
=

a0 ) 2

R32 ( r )

(Z
=

a0 ) 2

9 3

(6 6 + ) e
2

9 6

( 4 ) e

9 30

These functions are all normalized to 1

Rnl2 ( r ) r 2 dr = 1

and are orthogonal within a particular l

Rnl ( r ) Rn'l ( r ) r 2 dr = nn'

The spherical harmonics have the form

Ylm ( , ) =

( ) m ( ) = m ( )

1 im
e
2

where
1

( 2 + 1) ( m ) ! 2 m
m ( ) = m
P ( cos ) ,
2 ( + m ) !
where Pl m (cos ) is an associated Legendre polynomial and m is a phase factor discussed
below. The first few spherical harmonics are:
s orbitals
Y00 =

J. F. Harrison

1
4

Michigan State University

p orbitals:
Y10 =

3
3 z
cos =
4
4 r

Y11 =

3
3 x + iy
sin ei =
8
8 r

d orbitals:
2
2
2
5
5 ( 2z x y )
2
Y =
( 3 cos 1 ) =
16
16
r2
15
15 ( x + iy ) z
Y21 =
cos sin ei =
8
8
r2
0
2

2
2

15
15 ( x + iy )
=
sin 2 e2i =
32
32
r2

and are orthonormal in the sense

sin d d Y

( , )Yl'm'* ( , ) = ll' mm'

Because the energy of a hydrogen like atom is independent of l & m we can take linear
combinations of the degenerate eigenfunctions and still have a valid solution to the
Schrodinger equation. A very common choice is to take linear combinations of the
complex spherical harmonics so that the angular eigenfunctions are real and still
eigenfunctions of L 2 but not of L z . Since Yl 0 are already real these dont change but we
will list them again for completeness:

s orbital :

1
4

p orbitals:
pz =

J. F. Harrison

3
cos
4

px =

Y11 Y1+1
3
=
sin cos
4
2

py =

Y11 + Y1+1
3
=
sin sin
4
i 2

Michigan State University

d orbitals:
d z 2 = Y20 =
d xz =

15
3 cos 2 1)
(
16

Y21 Y2+1
15
=
sin cos cos
4
2

Y21 + Y2+1
15
d xz =
=
sin cos sin
4
i 2
15
15
Y2+2 Y22
=
sin 2 sin cos =
sin 2 sin 2
d xy =
4
16
i 2
d x2 y 2 =

Y2+2 + Y22
15
15
=
sin 2 ( sin 2 cos 2 ) =
sin 2 cos 2
16
16
2

Pairing an angular and a radial function results in a valid hydrogen-like orbital. For
example

(Z
3d xy = R32 ( r )d xy ( , ) =

a0 ) 2

9 30

2e

15
sin 2 sin 2
16

etc.
Atomic Units

In atomic units one measures the length in multiples of a0 so 2SI = a02 2au and
rSI = a0 rau and the Schrodinger equation for the internal motion becomes
2

Ze 2
2
au

( rau ) = ESI ( rau )

4 0 a0 rau
2 a0
2

but

2 a02

e2
8 0 a0

so

1 2
Z
au
4 0 a0 2
rau
e2

1
Z
so 2au
rau
2

where Eau =

( rau ) = ESI ( rau )

( rau ) = Eau ( rau )

ESI 4 0 a0
e2

J. F. Harrison

Michigan State University

Since all terms in the Schrodinger equation are now in atomic units we neednt label the
terms and write it simply as
1 2 Z
(r ) = E (r
r
2

Note that the energy eigenvalues in atomic units are

Z2
. The angular eigenfunctions do not change but L 2 in atomic units is
2
2n
1

1 2
with eigenvalues l(l+1)
L 2 =
sin
+

sin 2 2
sin
En =

so L zYl m = mYl m
L 2Yl m ( , ) = l ( l + 1) Yl m ( , ) . L z becomes i

The radial ones are as listed above with =

2Zr
.
n

More Hydrogen-like Wave Functions

n m ( r , , ) = Rn ( r ) Ylm ( , ) = Rn ( r )

( ) m ( )

with the spherical harmonic written as a product of lm ( ) & m ( )

Ylm ( , ) =
m ( ) =

( ) m ( )

1 im
e ,
2
1

( 2 + 1) ( m ) ! 2 m
m ( ) = m
P ( cos ) ,
2 ( + m ) !
m is a phase factor which is not universally agreed upon. We will choose it to be
( 1 )m when m > 0 and +1 when m < 0 . This is often called the Condon-Shortly choice of
phase and is sometimes written as the requirement that Yl m = ( 1 )m (Yl m ) .
*

The radial functions are

J. F. Harrison

Michigan State University

2
3

( n 1) ! 2
2
Z

Rn ( r ) =
e
L2n++1 ( ) ,

3
na0 2n {( n + ) !}

in which

2Zr
na0

and
a0 =

4 0

e2

and L2n++1 ( ) is an associated Laguerre polynomial.

The functions in r , , and are separately normalized to unity and mutually orthogonal
2

*m ( ) m ( ) d = 1

0 lm ( ) sin d = 1

0
2

Rnl2 ( r ) r 2 dr = 1

r dr sin d n* m ( r , , ) n m ( r , , )d = nn mm

vanishing, except for n = n, = , and m = m.

The Wave Functions

( )

= 0, s orbitals:
00 ( ) =

= 1, p orbitals:

2
2

6
cos
2
3
11 ( ) =
sin
2
= 2, d orbitals:
10 ( ) =

J. F. Harrison

Michigan State University

10
3cos 2 1
4
15
sin cos
21 ( ) =
2
15 2
sin
2 2 ( ) =
4
= 3, f orbitals:
20 ( ) =

30 ( ) =

3 14 5

3
cos cos
4 3

31 ( ) =

42
sin 5cos 2 1
8

105 2
sin cos
4
70 3
33 ( ) =
sin
8
3 2 ( ) =

= 4, g orbitals:
40 ( ) =

9 2 35

4
2
cos 10 cos + 1
16 3

41 ( ) =
4 2 ( ) =

9 10
7

sin cos3 cos

8
3

3 5 2
sin 7 cos 2 1
8

3 70 3
sin cos
8
3 35 4
sin
4 4 ( ) =
16
43 ( ) =

= 5, h orbitals:

J. F. Harrison

Michigan State University

50 ( ) =

15 22 21 5
14

3
cos cos + cos
16 5
3

165
sin 21cos 4 14 cos 2 + 1
16
1155 2
sin 3cos3 cos
5 2 ( ) =
8
770 3
sin 9 cos 2 1
53 ( ) =
32
3 385 4
sin cos
5 4 ( ) =
16
3 154 5
sin
55 ( ) =
32
51 ( ) =

The Hydrogen like Radial Wave Functions

n = 1, K shell:
= 0, 1s

3
2

R10 ( r ) = ( Z a0 ) i2e

n = 2, L shell:
= 0, 2 s
= 1, 2 p

R20 ( r )

(Z
=

a0 ) 2

R21 ( r )

(Z
=

a0 ) 2

2 2

(2 )e

2 6

n = 3, M shell:
=0 ,3s
=1,3 p
=2,3d

R30 ( r )

(Z
=

a0 ) 2

R31 ( r )

(Z
=

a0 ) 2

R32 ( r )

(Z
=

a0 ) 2

9 3

(6 6 + ) e
2

9 6

( 4 ) e

9 30

n = 4, N shell:

J. F. Harrison

Michigan State University

10

= 0, 4s
= 1, 4 p
= 2 , 4d
= 3, 4 f

R40 ( r )

(Z
=

R41 ( r )

(Z
=

a0 ) 2

R42 ( r )

(Z
=

a0 ) 2

R43 ( r )

(Z
=

a0 ) 2

R50 ( r )

(Z
=

a0 ) 2

R51 ( r )

(Z
=

a0 ) 2

R52 ( r )

(Z
=

a0 ) 2

R53 ( r )

(Z
=

a0 ) 2

R54 ( r )

(Z
=

a0 ) 2

a0 ) 2
24 36 + 12 2 3 e 2
96
3

32 15

( 20 10 + ) e
2

96 5

(6 )

96 35

n = 5, O shell:

= 0 ,5s
= 1,5 p
= 2,5d
= 3,5 f
= 4 ,5 g

300 5

(120 240 + 120

20 +

(120 90 + 18
30

150

150

( 42 14 + ) e
70
2

300 70

(8 )

900 70

) e

)e

n = 6, P shell:

J. F. Harrison

Michigan State University

11

= 0,6s
= 1,6 p
= 2 , 6d
= 3, 6 f
= 4,6 g
= 5, 6h

J. F. Harrison

R60 ( r )

(Z
=

a0 ) 2

(Z

a0 ) 2

R61 ( r ) =
R62 ( r ) =
R63 ( r ) =
R64 ( r ) =
R65 ( r ) =

( 720 1800 + 1200

2160 6

432

(Z

(840 840 + 252

210
(336 168 + 24
105

a0 ) 2

( 72 18 + ) e
35
2

a0 ) 2

12960 7

(Z

300 + 30
3

28 +

a0 ) 2

2592

(Z

864

(Z

(10 )

a0 ) 2

12960 77

) e
2

) e

)e

Michigan State University

12