|





‡ Atomic spectra of gases



‡ The X-ray spectrum of atoms

‡ Early models of the atom
‡ X-rays and the numbering of
‡ Bohr¶s model of the hydrogen
the elements
atom ‡ Lasers and laser light
‡ The quantum model of the
hydrogen atom
‡ The wave functions for
hydrogen
‡ Physical interpretation of the
quantum numbers.

 
   







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Emission spectra: All objects emit thermal radiation
characterized by a 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. 

|   An absorption spectrum is obtained by
passing white light from a 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.
a
a

  
a

The wavelengths of the Balmer series lines in the hydrogen

spectrum are given by the equation

Ô  Ô Ô  n = 3, 4, 5, . . . a
   a

      

 aa
a
     r   

   
Rydberg constant RH= 1.097 x 107/m
The wavelengths of the other series lines in the
hydrogen spectrum are given by the equation
O

     
  
[ 


 
      !"
  [ 
[ 
 

#$
      !"%
  [ 
[ 
 

Although no theoretical basis existed for these
equations, they are in agreement with the experimental
results.
r
r 
r

r
r 
r

r
r 
r

m1] (a) What value of n is associated with the 94.96-nm
spectral line in the Lyman series of Hydrogen ? (b)
Could this wavelength be associated with the Paschen
or Balmer series ?

O 
&
'(O
 
Ô  Ô 

  Ô  
   
   




  [ 


   j 

jß
' (   
        


  [ [ 

  [ 
›   j  › 
j 
The shortest wavelength for this series corresponds to n = ’ for
ionization. For n = ’, gives Ȝ = 820 nm. This is larger than 94.96
nm, so this wave length cannot be associated with the Paschen
series.

#)
 
        


  [ [ 

  [ 
›  [ j  ›   j 
with n = ’ for ionization, Ȝ min = 365 nm. Once again the shorter
given wavelength cannot be associated with the Balmer series.
 á
 r 
r 
 r


  
 ))
*) +  

1
,
#  -)*  , Y

·
./0 The electron moves in circular º

orbits around the proton under the 
influence of the electric force of
attraction as shown in the figure.

.0 Only certain electron orbits are stable (stationary 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.
.0 When the atom makes a transition
from higher energy state (Ei) to lower
energy state (Ef) mie, the electron makes
a transition from a stable orbit of larger 1
Y

radius to that of smaller radius], ·
 º
radiation is emitted. The frequency (f)

of this radiation (photon) is given by
 1 +  +
The frequency f of the photon emitted
is independent of the frequency of
electron¶s orbital motion.
 ±e
.0 The angular momentum of the me
Y
·
electron in any stable orbit is +e v
quantized r

L=mev r = n
n = 1, 2, 3, . . .
$
me = mass of the electron

Y
v = speed of the electron in the
orbit
r = radius of the electron¶s orbit
Electric potential energy of the H-
atom is k e qq[ ke e[ 1
U



r r Y
·
$-)
  º

) + ,

& %   

" '

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Apply Newton¶s 2ND law to the electron, the electric force
exerted on the electron must be equal to the product of mass
and its centripetal acceleration (º2(
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Vonization 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

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#1 1#& )
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Extension of Bohr¶s theory to other one-electron atoms
- Nuclear charge = + Z e
*-
§
#
ß
[ 

  [
M 
[

 
ß  [ 
ß Ô [    
[  

O
 + # 9   
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.
# 9 * )
:--
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;    *++ ; 4-5* )º)

 º ) 
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mÔ apectral lines from the star ȟ-Puppis: aome
mysterious lines in 1896 in the emission spectrum of
the star ȟ-Puppis fit the empirical equation
 
 
    
ß   [ [ 
 
)  
  
  
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ahow that these lines can be explained by the Bohr¶s

theory as originating from He+.
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wereRH ß
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.0 '|( 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) Vn interstellar space highly excited hydrogen atoms called
Rydberg atoms have been observed. Find the wavelength to
which radio-astronomers 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 ?

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 v
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T [Yr
* º*º **- +
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[  z


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ß ß 
[ 
.0 According to classical physics, a charge e moving
with an acceleration a radiates at a rate
d 1 e 2a 2


dt Y o c
'(  ;    )   )) *

)    -)-   

r



t Y r 
 X

' ( Find the time interval over which the electron will
reach r = 0, starting from ro = 2.00 x 10±10 m

O|  )   º

ke e [  e [
E
ereke
ß

[r YV  YV o r
[ [ [
dE e dr  e



d@ YV o r d@
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  2  
Y 
[ [ [
 dr r [  [
ß  

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 2[  d@  

   !" #$# $ #!%#!&'!( )*

ke e [ e v [
i e [ ß
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dr e
È X
Tere ore ß
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 X

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[ [ [ [  
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e  †
m  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.
m 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.
a%$+!%)
a%$+!%#

a%$+!%
m 'a) Construct an energy-level diagram for the He+ ion (Z
= 2). (b) What is the ionization energy for He+ ?

a%$+!%# The energy levels of a hydrogen-like ion whose

charge number is Z are given by

-+)-
'=(  

)º)
' ( *     5  + 

a%$+!% ) 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

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h      

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  z 

/
 . .& $#+
aince U has spherical symmetry, it is easier to solve the
schrodinger equation in spherical polar coordinates (r, ș, ij):
r is the radial coordinate is the radial distance from the origin.
<
-$# r
x 2  y 2  z 2 Y
r
ș

Ü

Angular coordinate ș specifies the angular position
Y relative to the
z-axis. ș is the angle between z-axis and r

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

onto the xy-plane.

Ô
Vt is possible to separate the variables r, ș, ij and their
corresponding wave functions can be written as

(r, ș, ij) = R(r) f(ș) g(ij)

By solving the three separate ordinary differential equations

for R(r), f(ș), g(ij), 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.
Principal quantum number (n):The radial function R(r) of  is
associated with orbits: the principal quantum number n. The
quantum numbers are integers and correspond to the three
independent degrees of freedom.
From this theory the energies of the allowed states for the
H-atom are
 k ee 2  1 1X . e
En
  2

2
, n
1, 2 , X , . . .
 2 ao  n n
-$!$   1#& - $ $# $#
#*  ;. .& .&*# 
$ ,# ).!  )6ș7   !  - $ $ #* 
;. .& .&*# 
1 ! ;. .& .&*# &
$ <&. $ ).!  16 7   !  - $ $ #* 
&1 ! ;. .& .&*# &
Hence, in quantum model wave function of H atom, can be
written as

(r h ¢ ß
j

(r h ¢

$ ,,!  ) *.# !   $ $# ,#

)    &,#  #  $, &1 $ $#
;. .& .&*# +

=Ô  ! #1 )#& Ô  

=  ! #1 )#& /  ±Ô > = - %. 
= & ! #1 )#& ±  ? > =6?Ô7 -
%. 
   $%1 $ &,#!,;. .&#  
)#& $   $%1 $ &%. )
#  )#& .* $+

2Ô  " $  2/  .* $

2   $  2Ô , .* $
2   $  2  .* $
2   $  2 ) .* $
2   $  2 1 .* $
23   $  2 $ .* $
 
  

r r 
 

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** )   
*) *  ; -)- * ) 

+   ));*  +   ,
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) ;º +- + ,

   Ô&&# ' %+- &#  .#( +!% 6 2
Ô  2 /7+


#
 6# 7 ß     #  *-
Y 

[# >/>      )

[   

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* + ,
 /,
Y  
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 4Yr2 dr
P(r) = 4Yr2 ||2
Radial probability density for H-atom in its ground state:

[#
 @#
[


 6# 7 ß    

  
Plot of the probability of finding the electron as a function of
distance from the nucleus for H-atom in the 1s (ground)
state. Probability (P1s(r)) is maximum when r equals to (Bohr
radius). r= ao


 
2
A
Cross-section of
25
the spherical
electronic charge
distribution of H-
atom in 1s-state.
  ? 
) ;º +- +   ,
  
, ;º +-  / 01  / 2
     [
# 
#
 [ 6# 7 ß    [
  

@ [Y      

2s is spherically
symmetric (depends only
on r).

  2 E2 = E1/4 = ±3.401 eV
(1aT excited state).
  

a



2
./0 , @,?
),: 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.
)-
When n= 2,  can have the values 0 and 1.
Vf =0, m can only be 0.
Vf =1, m can be -1, 0, or +1.
ao, we have a 2s state with quantum numbers   6
 6
and three 2p states for which the quantum numbers are
  /
 ,/
All these states have the same principal
  /
 6
quantum number, j


  /
  /

 j En =(-13.66eV) Z2 /n2
E2 =-(13.66eV)/22=-3.401eV
.0 @,?
),! 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.
)-
The probability is found by integrating the radial probability density
for this state, P1s(r), from the Bohr radius a0 to Ú .

[#
 @#[


 6# 7 ß    

  
 #
 #


Ô 6# 7
   
  

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

 -6"%%"%%A
.0 @,?
),)-)  
   ) º)- +
 ' * +
-)-( +  )    -*
 +   ,

)-
The most probable distance is the value of r that makes the radial
probability P(r) a maximum. The most probable value of r is
obtained by setting dP/dr= 0 and solving for r.

[# [r
 @#
[



6# 7 ß     dP˜  r ¢ d   r
[
 ao
 ß    e ß
   dr dr  ao 
 [r
dP˜  r ¢ d   r [


ao
ß    e ß
dr dr  ao 

[r a
e
[

[ r a o  r ¢
r [  e o¢
ß
r r
[r o [r o
[re  r  [ o ¢
[
e


[r ao
[re 
r a o  ß 
r
?+*+ 

o
r
o

  )º)-+ # *-
.!0a3 %)$  0Ô|)?+ 
 )º)+,)
*
  k e[ q[ q[[
Ej

[ [j[
where ke is the the Coulomb constant, q1 and q2 are the
charges of the electron and the nucleus, and ȝ is the
mm[
reduced mass, given by  
m  m
 [
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 ?
)-
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.
    +  )º)   )+  )  
* ;  ; -)* )) B-
   
  º) )   ;º)   +
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)  *

."0 a3 %)$  0Ô An electron of momentum p is at a
distance r from a stationary proton. The electron has a
kinetic energy  ß G[
[ 

The atom has a potential energy ' ß and total energy
#
E = K + U. Vf 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 electron¶s 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 electron¶s momentum in
terms of r.
(b) Estimate the electron¶s kinetic, potential, and total
energies in terms of r.

  [
ß

#

[ [ [

[m e [m e m er [
[
k ee [

 
[

m er r
.!0 a3 %)$  00Ô For a spherically symmetric
state of a H-atom the schrodinger equation in spherical
coordinates is
h[   [  [    [
 [  
r
[  # # #  #
ahow that the 1s wave function for an electron in H-
atom
Ô #

Ô 6# 7

Y 


satisfies the schrodinger equation.

)- 
r
ao

˜  r ¢ ß 
e
Y a o

h[   [
[ 
 kee [
weave
 [ 

ß r

[  r r r  r

-  *4-+*

 › 
r
›
r

 
r 

ár


=Ô % )!#$ 4+#+ +) 

According to quantum mechanics, an atom in a state
whose principal quantum number n can take on the
following discrete values of the
-* +  
 ) -)

-
+

ß u
6u 7 h uß   [    


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-
 &
The energy U of the electron with a magnetic moment
Y Y Y Y
C in a magnetic field # is '
C ï # According to
quantum mechanics, there are discrete directions allowed for
Y
the magnetic moment vector C with respect to magnetic field
Y
vector # Y    Y
C ß
  O
aince  [  
Y
one finds that the direction of O is quantized. This means
Y
that LZ (the projection of O along the z-axis mdirection
Y
of # ] can have only discrete values. The orbital magnetic
quantum number 0^ specifies the allowed values of the z-

component of the orbital angular momentum. O=  & c

 Y
O
$;. < ) $, *#   )- $
Y
# ,!   #&1 !)
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;. < ·-1%! #&
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The quantum numbers n, ), m) are generated by applying
boundary conditions to solutions of the schrodinger equation.
The )  does not come from the schrodinger
equation. The experimental evidence showed the necessity
of the spin magnetic quantum number
 which describes
the electron to have some intrinsic angular momentum. This
originates from the relativistic properties of the electron.
There can be only two
directions for the spin angular
Y
momentum vector  spin-up and
spin-down as shown in the figure:
apin is an intrinsic property of a particle, like mass and
charge. The spin angular momentum magnitude a for the
electron is expressed in terms of a single quantum number
(spin quantum number), s = ½ :

aß §  hß h
Y [
a is quantized in space as
described in the figure:
Vt can have two orientations
relative to a z-axis, specified by
the spin magnetic quantum
number ms = ½. The z-
Y
component of  is :
= 
c  c2 30
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 )# ,-!  Y
& Y
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a
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O= &c
 c  c  c /c  c  c
L mu mu
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O u
u¢ [ 
a37#"$  08·# & #& $;. .&
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 + D,
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r
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When a beam of fast moving electron strikes on solid target an

invisible and high penetrating radiation is produced.

These radiations are called X ± rays. i.e.$ # # & 

*  &   #1 -$ $  & # *&*#
- $ $1$ #1 ! # 

 
 4:
To examine the motions of electrons that lie deep within
multi-electron atoms, one needs to consider the x-ray
spectrum of atoms, shown in the figure below:
The x-ray spectrum has two parts: continuous spectrum
and characteristic spectrum. aharply defined cutoff
wavelength (8&) is a prominent feature of the --
?, -
.
A+ 8'
H'A+
E 2
Ȝ
 2,&



,

r
›r

 

%!+%+&&"  +
Consider an electron accelerated through a potential
difference of ¨V (x-ray tube voltage) , hitting a target atom.
The electron¶s initial kinetic energy is K = e ¨V. The electron
loses its kinetic energy by an amount ¨K = hf, which
appears in the form of x-ray photon energy (Bremsstrahlung:
Breaking radiation). ¨K can have any value from 0 to K.
Thus the emitted x-rays can have any value for the
wavelength above ȜMVN in the continuous x-ray spectrum.
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the vacancy in the inner shell is filled up by an electron
from the outer shell (energy = En, n = integer).

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A Kr x-ray results due to the transition of the electron from
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the electron from M-shell to K-shell. When the vacancy
arises in the L-shell, an L-series (Lr, L , L
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aimilarly, the origin of M-series of x-rays can be explained.
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two collisions, determine the wavelengths of the resulting
photons. Neglect the recoil of the heavy target atoms.

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spectrum is also found, due to an impurity in the target.
The wavelengths of the Kr lines are 1789 pm (cobalt) and
1435 pm (impurity). What is the impurity ?
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