HYDROGENIC ATOMS

Hydrogenic atom- H, He+, Li2+, C5+, U91+ etc.

One-electron atom or ion of general atomic
number z Hydrogenic atom

For Hydrogenic atoms and H
Schrdinger equation can be solved exactly

These concepts are used to describe structures
of many-electron atoms and molecules

Balmer The wavenumbers of the light in the

visible region of electromagnetic spectrum fit the
expression

1 1
= RH 2 2
2 n

n= 3, 4,.
RH = 109 677cm-1

This is the Balmer series

Rydberg noted

1
1
= RH 2 2
n1 n2

n1 =1 Lyman, n1 =2 Balmer,
n1=4 Brackett, n1=5 Pfund

n1= 1, 2,
n2= n1+1, n1+2,.
RH=Rydberg constant
n1=3 Paschen,

Discrete spectroscopic lines

electron energy in H-atom is quantized

When a transition from one to another state takes place

E = h

Bohr frequency condition

To derive detail information

solve Schrdinger by using proper boundary
conditions
Ze 2
The potential energy(V)= 4 r
0
2
2
h 2
Ze

= E
2
4 0 r
The solution for allowed energy levels

hcRZ
En =
2
n

n=1,2,3

e 4
hcR =
2 2
2
32 0 h
is the reduced mass

n is principal quantum number

En values are all negative

me mN
=
me + mN


n=1, E1=-hcRz2

negative sign means
ground state lies hcRz2 below
the energy of the infinitely
separated electron and nucleus

n=2, E2=-1/4 hcRz2

hcR hcR
E = 2 2 in a transition
n2
n1
This energy is carried away by a photon of energy
hc which gives = R 1 1
n2
1

n2
2

Energy needed to remove an electron completely

From an atom is ionization energy I=hcRH

Quantum Numbers
Principal Quantum number (n)
Quantization of energy
Orbital angular momentum Quantum number (l)
L = l (l + 1)h

l = 0,1, 2,.., n-1

Magnetic Quantum number (ml)

Lz = ml h

ml = l , l 1, l 2,............,l
(2l + 1) values

Atomic orbitals can be written as the product of

two functions
R(r)-Radial function
Y(,) angular function
R depends on n and l independent of ml
Y(,) depend on l and ml

n ,l ,m (r , , ) = Yl ,m ( , ) Rn ,l (r )
l

S orbitals
The solution of Schrdinger equation gives
1/ 2

4
1s =
1/ 2
3
( 4 ) a0
1

r / a0

1
1
3 2

r
a0

( a )
0

n = 1, l = 0, ml = 0

4 0 h
a0 =
2
me e
Bohr radius

1s orbital is spherically symmetrical

This wavefunction decays exponentially towards
1
zero from
maximum value at the nucleus
1
3 2

(a )
0

Radial distribution function

Probability of finding the electron between two
spherical shells of thickness r and r+r is
2

4r r = P (r )r
P(r) is the radial distribution function
More general form for orbitals not spherically symmetrical

p(r ) = r 2 R(r )2

Other s orbitals
2s orbital (n=2, l=0, ml=0) is also spherical
Wavefunction has nonzero value at nucleus
It passes through zero (radial node) before
commencing its experimental decay towards
zero at large distances
2s orbital has one, 3s orbital has two, 4s orbital
has three radial nodes

s orbitals have non-zero finite value at nucleus

p and d orbitals
On the nodal plane zero probability density for electron
Zero probability of finding electron at the nucleus

2pz orbital
Y ( , )

R(r)
1/ 2

1/ 2

1 1
cos 3
2 6a0

3
=
4

1/ 2

1
=
5
32 a0

r cos e

r / 2 a0

r r / 2a 0
e
a0

Boundary surfaces of d orbitals

Electron spin
Spin of an electron is an intrinsic angular momentum
Quantum mechanical phenomenon -no classical
counterpart
Electron spin is described by spin quantum number(1/2)

Analogue of orbital angular momentum

Spin can be clockwise or counterclockwise
Described by spin magnetic quantum number
ms (+1/2 or -1/2)

ms=+1/2

electron

ms=-1/2

electron

Two allowed spin states of electron

The magnitude of the spin angular momentum is (31/2/2)
Directions of spin are opposite