TOPICS

ATOMIC PHYSICS

Atomic spectra of gases

Early models of the atom
Bohrs model of the
hydrogen atom
The quantum model of
the hydrogen atom
The wave functions for
hydrogen
Physical interpretation of
the quantum numbers

Text Book
PHYSICS for Scientists and
Engineers with Modern
Physics (6th ed)
By Serway & Jewett
MIT- MANIPAL

TOPICS

The X-ray spectrum of

atoms
X-rays and the
numbering of the
elements
Lasers and laser light

Text Book
PHYSICS, 5TH Edition Vol 2
Halliday, Resnick, Krane

BE-PHYSICS-ATOMIC PHYSICS-2010-11

ATOMIC SPECTRA OF GASES

Emission spectra: All objects emit thermal radiation

characterized

by

continuous

distribution

of

wavelength (continuous spectrum).

When a gas at low pressure is subjected to an
electric discharge

it

emits

radiations

of

discrete

wavelengths (line spectrum).

No two elements have the same line spectrum. This
principle is used in identifying the element by
analyzing its line spectrum.

H
Hg

Absorption spectra:
by

passing

white

An absorption spectrum is obtained

light

from

continuous

source

through a gas or a dilute solution of the element being

analyzed.

The absorption spectrum consists of a series

of dark lines superimposed on the continuous spectrum

of the light source.
SOLAR SPECTRUM
FRAUNHOFER LINES

The wavelengths of the Balmer series lines in the

hydrogen spectrum are given by the equation
n = 3, 4, 5, . . .

1
1
1
RH 2 2

n
2

Rydberg constant RH= 1.097 x 10 /m

7

VISIBLE
HYDROGEN
SPECTRUM
BALMER SERIES LINES
H (656.3 nm)
H (656.3 nm)

H (656.3 nm)
H (656.3 nm)

The wavelengths of the other series lines in the

hydrogen spectrum are given by the equation
Lyman
Series
n 1= 2,

3, 4, . . .
1
RH 1 2

Paschen
Series
1 n =14, 5, 6, . . .
1
RH 2 2

3
n

Brackett
Series
5, 6, 7, . . .
1 n =1
1
RH
2
2

n
4
Although no theoretical basis existed for these
equations,

they

are

experimental results.

in

agreement

with

the

EARLY MODELS OF THE ATOM

EARLY MODELS OF THE ATOM

EARLY MODELS OF THE ATOM

[1] (a) What value of n is associated with the 94.96nm spectral line in the Lyman series of Hydrogen ?
(b) Could this wavelength be associated with the
Paschen or Balmer series ?
SOLUTION:
(a)Lyman Series

1
1
RH 1 2

1
7

1
.
097
x
10
94.96 x10 9
n5

1
1 2
n

(b) Paschen Series

1
1
1
RH 2 2

n
3

1
1.097 x107

1
1

2
9 n

The shortest wavelength for this series corresponds to n =

for ionization. For n = , gives = 820 nm. This is larger than
94.96 nm, so this wave length cannot be associated with the
Paschen series

Balmer Series

1
1
1
RH 2 2

n
2

1
1.097 x107

1
1

2
4 n

with n = for ionization, min = 365 nm. Once again the

shorter given wavelength cannot be associated with the
Balmer series

BOHRS MODEL OF THE HYDROGEN ATOM

In his semi classical model of the
H-atom Bohr postulated that[1] The electron moves in circular

+e

orbits around the proton under

e
me
v

the influence of the electric force

of

attraction

as

shown

in

the

[2]
Only certain electron orbits are stable (stationary
figure
states).

When in one of the stationary state, the atom

does not radiate energy.

Hence the total energy of the

atom remains constant in a stationary state.

[3] When the atom makes a transition

from

higher

energy

energy

state

lower

state
(Ef)

(Ei)
[ie,

to
the

electron makes a transition from a

stable orbit of larger radius to that
of

smaller

emitted.

radius],

radiation

is

The frequency (f) of this

radiation (photon) is given by

Ei Ef = h f .
The

frequency

emitted

is

of

the

independent

photon
of

the

frequency of electrons orbital motion.

+e

e
me
v

[4] The angular momentum of the

electron in any stable orbit is
+e

quantized
mev r = n

e
me

n = 1, 2, 3, . . .
me = mass of the electron
v = speed of the electron in the
orbit
r = radius of the electrons orbit

h
2

Electric potential energy of the Hatom is

2

kee
U
r

ke= Coulomb constant

+e

The total energy of the H-atom is

2

e
me
v

mev
kee
EK U

2
r
ND

Apply Newtons

law to the electron, the electric

force exerted on the electron must be equal to the

product of mass and its centripetal acceleration (a=v2/r)
2

kee
r2

mev
r

mev2
K

kee2
2r

The total energy of the H-atom is

9ao

kee2
kee2
EK U

2r
r

4ao

e
ao
+e

kee
E
2r

From Newtons 2ND law equation and orbit quantization

equation
2 2

n
v

2 2
mer
2

kee
mer

2 2

n
rn
mekee2

n = 1, 2, 3, . . .

Thus the electron orbit radii are quantized

Bohr radius

ao

2
52.9 pm
2
mekee

rn= n2 ao

Energy quantization
Substitute

En

rn= n2 ao in the total energy equation

kee2
kee2 1
2


2r
2 ao n
13.606eV
En
,
2
n
E1= 13.606 eV

E1
En 2
n

n = 1, 2, 3, . . .

n 1, 2, 3, . . .

Ionization energy = minimum energy required to ionize

the atom in its ground state
= 13.6 eV for H-atom
From the equation Ei Ef = h f
Frequency of the photon emitted during transition of the
atom from state i to state f is

kee 1
Ei Ef
1
2 2
f

h
2 aoh nf
ni
2

Use c = f

1
1
1
RH 2 2

ni
nf

kee2
2 aoh c

1
1
2 2
ni
nf
RH

RH = 1.097 x

kee2
2 aoh c

Extension of Bohrs theory to other one-electron

atoms - Nuclear charge = + Z e

radius

Energy

rn n

En

ao
Z

kee2 Z2
2

2 ao n

n 1, 2, 3, . . .

Limitations of Bohrs theory:

When spectroscopic techniques improved, it was
found that many of the lines in the H-spectrum
were not single lines but closely spaced groups of
lines.

The lines appear split when the H-vapour

was kept in magnetic field.

Bohrs correspondence principle:

Quantum
when

the

physics

agrees

difference

with

between

becomes vanishingly small.

classical
quantized

physics
levels

PROBLEMS

[1] Spectral

lines

from

the

star

-Puppis: Some

mysterious lines in 1896 in the emission spectrum

of the star -Puppis fit the empirical equation

1
1
RH

nf

1
ni

2

Show that these lines can be explained by the

Bohrs theory as originating from He+.

SOLUTION: The ion He+ has z=2,

Thus allowed energy

levels are given by

ke e 2
En
2 ao

Z2

n 1, 2, 3, . . .
2
n
f

Ei E f
h

ke e 2 4
2
En
2 ao n

ke e 2 4
4

2
2
2 ao h n f
ni

ke e
1
1
f

2
2

2 ao h n f 2
ni 2

2
kee
1
f
1
1

2
2

c
2 ao h n f 2
ni 2

2
ke e
whereR H
2 ao h c
2

[2] (A) The electron in a H-atom makes a transition from

the n=2 energy level to the ground level (n=1).

Find the

wavelength and the frequency of the emitted photon.

(B) In interstellar space highly excited hydrogen atoms
called Rydberg atoms have been observed.

Find the

wavelength to which radioastronomers must tune to detect

signals from electrons dropping from n=273 level to n=272.
(C) What is the radius of the electron orbit for a Rydberg
atom for which n=273 ?
(D) How fast is the electron moving in a Rydberg atom for
which n=273?
(E) What is the the wavelength of the radiation from the
Rydberg atom in part (B) if treated classically ?

SOLUTION(A)

1
1
1
RH 2 2

ni
nf
1
RH

12 2 2

3 RH

3RH

1.215 x10 m 121.5nm (ultraviolet )

7

c
15
Frequency f 2.47 x10 Hz

SOLUTION(B)

1
1
1
RH 2 2

ni
nf
1
RH

1
1

272 2 2732

0.992m
SOLUTION(C)

rn= n2 ao= 2732 (0.0529nm)

r273=3.94m

ao

2
52.9 pm
2
mekee

SOLUTION(D)

v
2

ke e
me r

(8.99 x109 )(1.60 x10 19 ) 2

(9.11x10 31 )(3.94 x10 6 )

kee 2
me r

v 8.01x103 m / s

SOLUTION(E)

1
v
f

T
2r
We have speed v and radius r from (C) and (D)

1
v
f

3.24 x108 Hz
T
2r
c

0.926m
f

[3] According

to

classical

physics,

charge

moving with an acceleration a radiates at a rate

dE
1 e 2a 2

dt
6o c 3
(a) Show that an electron in a classical hydrogen
atom spirals into the nucleus at a rate

dr
dt

e4

122 o2r 2m2ec 3

(b) Find the time interval over which the electron

will reach r = 0, starting from ro = 2.00 x 1010 m

SOL:A The total energy is given by

ke e
E
2r

1
where ke
4 0

e2
E
8 o r

dE
e 2 dr
1 e2a 2

2
dt 8 o r dt
6 o c 3
2

dr
1 ea

dt
6 o c 3

8 o r

2
e

dr
8r 2 a 2

dt
6c 3

The centripetal acceleration a is given by

ke e 2
me v 2
sin ce 2 F
r
r
dr
8r 2 a 2

dt
6c 3

dr
e4
Therefore

dt
12 2 o2 r 2 me2 c 3

SOL:B

dr
dt

e

2 2 2 2 3
12 or mec

12

r m c dr e
2 2
o

2 3
e

2.00 x10 10

2
o
4

dt
0

10
2
.
00
x
10
3

12 m c r
e
3
2

2 3
e

[4] A hydrogen atom is in the first excited state (n = 2).

Using the Bohr theory of the atom, calculate
(a) the radius of the orbit
(b) the linear momentum of the electron
(c) the angular momentum of the electron
(d) the kinetic energy of the electron
(e) the potential energy of the system and
(f) the total energy of the system.

[5] A photon is emitted as a hydrogen atom undergoes

a transition from the n = 6 state to the n = 2 state.
Calculate
(a) the energy
(b) the wavelength
(c) the frequency of the emitted photon.
Solution b:

Solution a:

Solution c:

[6] (a) Construct an energy-level diagram for the He + ion

(Z = 2). (b) What is the ionization energy for He + ?
Solution a: The energy levels of a hydrogen-like ion whose
charge number is Z are given by

Thus for Helium (Z = 2), the energy

levels are

(b) What is the ionization energy for He+ ?

Solution b: For He+ , Z = 2 , so we see that the ionization
energy (the energy required to take the electron from the n =
1 to the n = state) is

THE QUANTUM MODEL OF THE HYDROGEN ATOM

The potential energy function for the H-atom is

2
ke = 8.99 x 109 N.m2/C2
kee
U(r)
is Coulomb constant
r
r = radial distance of electron from proton [Hnucleus]
(at r = 0)
The time2
2
2
2

independent

2 2 E
2
schrodinger equation 2m x
y
z

in 3-dimensional
Since
to
space U
is has sperical symmetry, it is easier
z
solve the schrodinger equation in spherical polar
P
r
coordinates (r, , ):

2
2
2
r

z
y
where

is the angle between z-axis and

r
x

36

 is the angle between the x-axis and the projection of

onto
r

the xy-plane. It is possible to separate the

variables r, , as follows:
(r, , ) = R(r) f() g()
By

solving

the

three

separate

ordinary

differential

equations for R(r), f(), g(), with conditions that the

normalized and its first derivative are continuous and
finite

everywhere,

one

gets

three

different

quantum

numbers for each allowed state of the H-atom. The

z
quantum numbers are integers and
P
correspond to the three independent
degrees of freedom.

The radial function R(r) of is associated with the principal

quantum number n. From this theory the energies of the
allowed states for the H-atom are

k ee2
2 ao

13.606 eV

, n 1, 2, 3, . . .
2

n
which is in agreement with Bohr theory.

En

1
n2

The polar function f() is associated with the orbital

quantum number l.
The azimuthal function g() is associated with the
orbital magnetic quantum number ml.
The application of boundary conditions on the three
parts of leads to important relationships among
the three quantum numbers:
[1] n can range from 1 to .
[2] l can range from 0 to n1 ; [n allowed values].
[3] ml can range from l to +l ; [(2l+1) allowed

All states having the same principal quantum

are said to form a shell. All states having the
same values of n and l are said to form a
subshell:
n = 1

shell

l=0 s

subshell

n = 2

shell

l=1 p

subshell

n = 3

shell

l=2 d

subshell

n = 4

shell

l=3 f

subshell

n = 5

shell

l=4 g

subshell

n = 6

shell

l=5 h

subshell

..

..

..

..

..

..

..

..

THE WAVE FUNCTIONS FOR HYDROGEN

The potential energy for H-atom depends only on the
radial distance r between nucleus and electron. some
of the allowed states for the H-atom can be represented
by wave functions that depend only on r (spherically
symmetric function). The simplest wave function for Hatom is the 1s-state (ground state) wave function

(n = 1, l = 0):

1s (r)

1s

1
a3o

3
ao

r
ao

2r

ao

ao = Bohr radius.

| 1s|2 is the probability

density for H-atom in 1s-state.

The radial probability density P(r) is the probability

per unit radial length of finding the electron in a
spherical shell of radius r and thickness dr.
P(r) dr is the probability of finding
the electron in this shell.
P(r) dr = ||2 dv = ||2 4r2 dr

P(r) = 4r2 ||2

Radial probability density for H-atom in its ground

state:

4r
P1s (r)
3
ao

2r
ao

Plot of the probability of finding the electron as a

function of distance from the nucleus for H-atom in the
1s (ground) state.
radius).
Cross-section

of

P1s(r) is maximum when r = ao (Bohr

the

spherical

distribution of H-atom in 1s-state

rMOST PROBABLE
= ao
rAVERAGE
= 3ao/2

electronic

charge

The next simplest wave function for the H-atom is the

2s-state wave function (n = 2, l = 0):

2s (r)

rMOST PROBABLE = 5ao

4 2

ao

3
2

r
2

ao

r
ao

2s
is
spherically
symmetric (depends
only on r).
E2 = E1/4 = 3.401 eV
(1ST excited state).

[1] - SJ-Example-42.3: For a H-atom, determine the number

of allowed states corresponding to the principal
quantum number n = 2, and calculate the energies of
these states.

Solution:
When n= 2, l can have the values 0 and 1.
If l=0, ml can only be 0.
If l=1, ml can be -1, 0, or +1.
Hence, we have a 2s state with quantum numbers
n= 2, l=1, ml =0

All these states have the same principal

and three 2p states for which the quantum numbers are
quantum number, n=2, they also have the
n= 2, l=1, ml =-1 same energy, E =(-13.66eV) Z2 /n2
n

n= 2, l=1, ml =0

E2 =-(13.66eV)/22=-3.401eV

[2] SJ-Example-42.4.Calculate the most probable value of

r (= distance from nucleus) for an electron in the ground
state of the H-atom.

Also calculate the average value r

for the electron in the ground state.

Solution:
The most probable distance is the value of r that makes the
radial probability P(r) a maximum. The slope here is zero, so
the most probable value of r is obtained by setting dP/dr= 0
and solving for r.

4r
P1s (r)
3
ao

2r
ao

dP1s (r ) d 4 r

dr
dr ao3

2r

ao

dP1s (r ) d 4 r

dr
dr ao3

2r

ao

2r ao d (r )
2 d (e
e
r
2

dr

2r a

o)

dr

2r ao
2r ao
2
2re
r ( 2 a o )e
0
2 r ao
2re
[1 r a o ] 0
The expression is satisfied if

r ao

r
1 0
ao

The most probabale value of r is the Bohr radius

The expectation value is given by

x dx

The average value of r is the expectation value of r

HereP (r )
*

r dx

4r
rav r rP (r )dr r
3
a

o
0
0

4 3
3 r e
ao 0
4
rav 3
ao

r e
3

2r
ao

4
dr 3
ao

3
rav ao
2

2r
ao

2r
ao

dr

dr

3
3

ao
4
2
2 / ao

[3] SJ-Example-42.5 Probabilities for the electron in H-atom:

Calculate the probability that the electron in the ground state
of H-atom will be found outside the Bohr radius.
Solution:
The probability is found by integrating the radial probability
density for this state, P1s(r), from the Bohr radius a0 to .

4r
P1s (r)
3
a
o

2r
ao

 4r
P1s (r)
3
a
o

2r

ao

We can put the integral in dimensionless form by changing

variables from r to z = 2r/a0. Noting that z=2 when r=a0,
and that dr=(a0/2)dz, we get

This is about 0.677, or 67.7%.

[5] SJ-Problem-42.16: A general expression for the

energy levels of one-electron atoms and ions is

ke2 q12 q22

En
2 2n2
where ke is the the Coulomb constant, q1 and q2 are
the charges of the electron and the nucleus, and
m1m2
is the reduced mass, given by
m1 m2
The wavelength for n = 3 to n = 2 Transition of the
hydrogen atom is 656.3 nm (visible red light). What
are the wavelengths for this same transition in (a)
positronium, which consists of an electron and a
positron, and (b) singly ionized helium ?

Solution:
The reduced mass of positronium is less than hydrogen,
so the photon energy will be less for positronium than
for hydrogen. This means that the wavelength of the
emitted photon will be longer than 656.3 nm.
On the other hand, helium has about the same reduced
mass but more charge than hydrogen, so its transition
energy will be larger, corresponding to a wavelength
shorter than 656.3 nm.

All the factors in the given equation are constant for this
problem except for the reduced mass and the nuclear charge.
Therefore, the wavelength corresponding to the energy
difference for the transition can be found simply from the
ratio of mass and charge variables.

so the energy of each level is one half as large as in

hydrogen, which we could call protonium. The photon
energy is inversely proportional to its wavelength , so for
positronium,

so the transition energy is 22 = 4 times larger than hydrogen.

[6] SJ-Problem-42.17: An electron of momentum p is at

a distance r from a stationary proton. The electron has
a kinetic energy

p2
2me

2
k
e
The atom has a potential energy U e
and total
r

energy E = K + U. If the electron is bound to the proton

to form a H-atom, its average position is at the proton,
but the uncertainty in its position is approximately equal
to the radius r of its orbit.

The electrons average

vector momentum is zero, but its averaged squared

momentum is equal to the squared uncertainty in its
momentum, as given by the uncertainty principle.

An electron of momentum p is at a distance r from a

stationary proton. Treating the atom as
one-dimensional system,
(a) estimate the uncertainty in the electrons momentum
in terms of r.
(b) Estimate the electrons kinetic, potential, and total
energies in terms of r.
(c) The actual value of r is the one that minimizes the
total energy, resulting in a stable atom. Find that
value of r and the resulting total energy. Compare
your answer with the predictions of the Bohr theory.

[5] SJ-Problem-42.21: For a spherically symmetric

state of a H-atom the schrodinger equation in
spherical coordinates is

2 2 2
kee2

E
2
2m r
r r
r
Show that the 1s wave function for an electron in
H-atom

1s (r)

1
a3o

r
ao

satisfies the schrodinger equation.

Solution:

1s ( r )

3
o

2 2

wehave

2
2m r
r r
2

r
ao

ke e

E
r

This is true , so the schrodinger equation is satisfied