Indian Institute of Technology, Guwahati

Guwahati, INDIA 781 039

Department of Chemistry Date: 27 December 2021

CH101
Classes 6; Physical Chemistry

Hydrogenic Atoms

Hydrogenic atoms: Atoms (ions) with nuclear charge Ze, atomic number Z and single
electron.
Examples: H, He+, Li2+, Be3+, etc.

Both the nucleus and the electron are moving and the interaction between the nucleus
and the electron is Coulombic interaction.

Ze 2
Potential energy, V = −
4 0 r
The Hamiltonian for the electron with mass me and nucleus with mass mN is

ˆ ˆ ˆ 2 2 2 Ze 2
H = Ek , electron + Ek , nucleus + V = − e − N −
2
2me 2m N 4 0 r
r is the distance of the electron from the nucleus and ε0 is the vacuum permittivity.
The first two terms (the kinetic energy operator) in the Hamiltonian corresponds to the
coordinates of the electron and nucleus respectively, while the last term is the distance of
the electron with from the nucleus.
Overall, there are two kinds of motions- the motion of the atom as a whole (nucleus and
the electron) and the motion of the electron with respect to the nucleus. We need to
convert the above Hamiltonian into coordinates involving these motions and then
separate them.

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That is we need to first convert the Hamiltonian into motions involving centre of mass
and the motion of the electron with respect to that of the nucleus.
We have in essence

p 2e p 2N
E= + +V
2me 2m N
Where, pe = me xe and p N = mN x N

me m
The centre of mass is located at X = xe + N x N ; where, m = me + mN and the
m m
separation of the particles is x = xe − x N

One can work out a little algebra and show that

p 2c.m. p2
E= + + V ; where pc.m. signifies the momentum of the whole atom and p
2m 2
signifies the momentum of the electron with respect to nucleus and the reduced mass,
me m N
= .
me + m N
Thus one can rewrite the Hamiltonian as

2 2 2 2 Ze 2
H =−  c.m. −  − ; One can see that the first term of the
2m 2 4 0 r
Hamiltonian is independent of the relative position of the electron and nucleus and
defines the motion of the atom as a whole; while the second and third terms are
dependent on the relative positions of electron and nucleus.

Workout for the transformation of Cartesian coordinate of individual nucleus and

electron (Hamiltonian) to Centre of Mass coordinates.

p 2e p 2N
E= + +V
2me 2m N
Where, pe = me xe and p N = mN x N

2
 me m
The centre of mass is located at X = xe + N x N ; where, m = me + mN and the
m m
separation of the particles is x = xe − x N

One can work out further

mN m
xe = X + x and x N = X − e x
m m
mm mm
pe = me xe = me X + e N x and p N = mN x N = mN X − e N x
m m
2
p 2e p 2N 2
1  2 1 2 p c.m. p
It follows that + = mX + x = +
2me 2mN 2 2 2m 2

p 2c.m. p2
E= + + V ; where pc.m. signifies the momentum of the whole atom and p
2m 2
signifies the momentum of the electron with respect to nucleus and the reduced mass,
me m N
= .
me + m N
Thus one can rewrite the Hamiltonian as

2 2 2 2 Ze 2
H =−  c.m. −  − ;
2m 2 4 0 r
One can then use the principle of separation of variables and write
total = c.m. and Etotal = Ec.m. + E ; where the first terms in the two equations
relate to the total motion of the atom (wavefunction and energy) while the second terms
relate to the relative motion.
One can finally write

2 2
−  c.m.c.m. = Ec.m. . This is the Schrödinger wave equation corresponding to
2m
the total motion of the atom and does not concern us at this moment (we want to find out
the energy states of electron) and

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 2 2 Ze 2
−  −  = E . This is the Schrödinger wave equation corresponding
2 4 0 r
to the motion of electron relative to nucleus and interaction between them and concerns
us at the moment. The above equation will help us find the energy states of the electron
in hydrogenic atoms.
If one looks carefully at the potential energy expression in the above wave equation, one
sees that the interaction between the electron and nucleus depends on the distance of
separation between the two and is centrosymmetric (independent of angle). Hence, it is
easier to solve the equation if one converts the equation from Cartesian coordinate system
to spherical polar coordinate system.
One can write the laplacian in spherical polar coordinate as

2 2  1
 = 2+
2
+ 2 2 ;
r r r r
Where the legendrian,  , is
2

1 2 1  
 =
2
+ sin 
sin 2   2 sin   
One can write (r ,  ,  ) = R(r ) ( ,  )

The Schrödinger wave equation can then be written as,

2 2 2  1 2
− + +  R + VR  = ER
2  r 2 r r r 2
or
2 d 2 R 2 dR R 2
−  2 + +   + VR  = ER
2 dr r dr r 2

r2
We multiply both sides by , then we get
R
2 2
2 d R dR 2 2
− r + 2r + Vr −
2
  = Er 2
2R dr 2
dr 2

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The third term in the above equation is independent of r and depends on the angular
coordinates only.

2  2l (l + 1)
=
2
2  2
One can write ; (In order to get this one needs to

solve the angle dependent wavefunctions called spherical harmonics and beyond the
scope of the present class).
Then Schrödinger wave equation can then be written as,

2 d 2R dR  2l (l + 1)
− r 2 2 + 2r + Vr 2 − = Er 2
2 R dr dr 2
or
 2 d 2 R 2 dR
− + + Veff R = ER
2  dr 2 r dr
where
Ze2  2l (l + 1)
Veff = − −
4 0 r 2 r 2

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The general solution for the radial wavefunctions for an electron with quantum numbers
n and l are the real functions and written as


l
Rn.l (r ) = N n.l   Ln,l (  )e −  / 2n
n
Here L is a polynomial in  called an associated Laguerre polynomial.

2 Zr
Hydrogenic Radial Wavefunctions; Some examples; Here =
a0
Orbital n l Rn.l
1s 1 0 3/ 2
Z 
2  e−  / 2
 a0 
2s 2 0 3/ 2
1 Z  1
  (2 −  )e −  / 4
2(2)1 / 2  a0  2
2p 2 1 3/ 2
1 Z 
 
1/ 2 
e −  / 4
4(6)  a0 
3s 3 0 3/ 2
1 Z  1
  (6 − 2  +  2 )e −  / 6
9(3)1 / 2  a0  9
3p 3 1 3/ 2
1 Z  1
  ( 4 −  ) e −  / 6
27(6)1 / 2  a0  3
3d 3 2 3/ 2
1 Z 
   2e −  / 6
81(30)1 / 2  a0 

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 The Spherical Harmonics, l , ml ( ,  )
l m l , ml ( ,  )
0 0 1/ 2
 1 
 
 4 
1 0 1/ 2
 3 
  cos 
 4 
±1 1/ 2
 3 
  sin e  i
 8 
2 0 1/ 2
 5 
  (3 cos 2  − 1)
 16 
2 ±1 1/ 2
 15 
  cos  sin e  i
 8 
2 ±2 1/ 2
 15 
  sin 2 e  2i
 32 
3 0 1/ 2
 7 
  (5 cos3  − 3 cos  )
 16 
3 ±1 1/ 2
 21 
  (5 cos 2  − 1) sin e  i
 64 
3 ±2 1/ 2
 105 
  sin 2  cos e  2i
 32 
3 ±3 1/ 2
 35 
  sin 3 e  3i
 64 
The energy of the hydrogenic orbit is given by

Z 2 e 4
En = − with n = 1, 2, 3….
32 2 2  2 n 2
0