Lecture 9 :Title : Interpretation of wavefunction and modification for

Alkali atoms

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Objectives

In this lecture
Born interpretation of the wavefunction is discussed

Radial probabilities of finding the electron in different orbit of hydrogen atom are
elaborated

The angular part of the wavefunction for different orbital is shown

The departure in the spectra of alkali atom from hydrogen such as lithium, sodium is
emphasized in the next lecture
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The wavefunction calculated for the hydrogen atom in the previous lecture is complex
quantity (includes e iml ).

This can not be measured by any actual physical instrument. However, it contains all
the information which the uncertainty principle allows us to know about the associated
electrons.

The connection between the properties of the wavefunction ( x, t ) and the behavior of
the electron is expressed in terms of the probability density P ( x, t )

P ( x, t ) is the probability per unit length of finding the particle near the coordinate x at
time t.

According to Max Born, 1962, the probability density P ( x, t ) =

* ( x, t ) ( x, t ) where
* ( x, t ) represents the complex conjugate of ( x, t )
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Born interpretation of the wavefunction:

If at any instant of time t, a measurement is made to locate the electron with the
wavefunction ( x, t ) , the probability P ( x, t )dx of finding a particle at a position
between x and x+dx is proportional to ( x, t ) dx .
2

P ( x, t ) =
* ( x, t ) ( x, t ) =
( x, t )
2
9.1

It implies that sign of the wavefunction has no direct physical significance. In the figure-
9.1, the wavefunction has changed its sign but the probability of finding the electron is
symmetric with respect to the nucleus at r/a0 = 0

1.0

0.5

x
Px

0.0

0.5

1.0
6 4 2 0

2
normalized radial distance r a0
4 6

Figure-9.1
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If the wavefunction changes sign as shown in the figure-9.2, it is called node

( ( x, t ) =
0 ). The probability of finding the electron (figure-9.3) at node is zero because
P ( x, t ) =
* ( x, t ) ( x, t ) =
( x, t )
2
9.2

Node

Wavefuntion of the electron

Figure-9.2

Node

Probability of finding the electron

Figure-9.3
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In the previous lecture, we have evaluated the wavefunction of the electron in Hydrogen
atom as

2 ( n 1) ! r n a0 2r 2 +1 2r
3

n , ,ml = e Ln 1
na0 2n {( n + ) !}
3
na0 na0

( 2 + 1) ( m )! P m Cos
( )

4 ( + m ) !
9.3

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

Where n principal quantum number = 1, 2, 3, 4,.

l azimuthal quantum number = 0, 1, 2, .., n-1
and ml magnetic quantum number = -l, -l+1, -2,-1,0, 1, 2, .,l+1=2l+1 values
Z 2 e4 1 13.6 eV R
And the Energy En = = = 9.4
( 4 0 ) 22 n
2 2 2
n n2
The energy depends only on n, but the functional form of R(r) depends on both n and l,
and so we write the radial wavefunction as Rn,l(r) and angular part Y depends on l and ml.
Following table provides the energy and the nomenclature of the states.

Principal Magnetic
Orbital quantum
quantum nomencleture quantum Energy
no.
no. no.
n=1
l = 0 (s subshell) 1s state ml = 0 -13.6 eV
(K shell)
l = 0 ( s subshell) 2s state ml = 0
n=2 2p state ml = -1
-3.4 eV
(L shell) l = 1 ( p subshell) 2p state ml = 0
2p state ml = 1
l = 0 ( s subshell) 3s state ml = 0
3p state ml = -1
l = 1 ( p subshell) 3p state ml = 0
3p state ml = 1
n=3
3d state ml = -2 -1.51 eV
(M shell)
3d state ml = -1
l = 2 ( d subshell) 3d state ml = 0
3d state ml = 1
3d state ml = 2
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In the following figure-9.4, we plot the radial functions Rn ,l (r ) , the reduced radial
functions U n ,l (r ) = r Rn ,l (r ) , and the radial probability densities Pnrad
,l ( r ) = (U n ,l ( r )) for
2

different states of hydrogen atom. We will also see the plot for different orbitals of
hydrogen atom.

The first orbit n = 1, l = 0 and ml = 0, the K shell

In this plot we can see the effect of the factor r in U1s (r ) = r R1s (r ) . Here, R1s(r) goes
to 2 a0 (Bohr radius) at r = 0, while U1s(r) goes to zero. The factor of r in U1s(r) also
introduces a peak at 1 a0.
There is no node for 1s state.
The probability density P1rad
s ( r ) goes to zero at r = 0, it means that the probability of

finding the electron at the nucleus is zero. P1rad s ( r ) shows also a peak at 1a0 which is the
same as Bohr radius and the peak value is 0.54.
Conceptually, peaks in Pnrad ,l ( r ) are radii near which an electron in a state n,l,ml is

most likely to be found.

Because of the gradual decay of Pnrad ,l ( r ) on the large-r side of this peak, the calculated

mean radial position turns out to be larger than the location of the peak
Following figure is the 1s orbital

2.0
R1s
U1s
1.5
P rad 1s

1.0

0.5

0.0
0 1 2 3

4
normalized radial distance r a0
5 6
1s orbital

Figure-9.4 Figure-9.5
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The second orbit n = 2 ( L shell), l = 0, ml = 0 and l = 1, ml = 0, 1

The 2s radial function in the figure-9.6 decays as r more gradually than U1s(r).
Moreover, the 2s radial probability density has two peaks: one at 0.76 a0 and next one at
5.24 a0.

The height of the peak nearest the nucleus, 0.052, is much smaller than that of the
outer peak, 0.19. The presence of a small peak in P2rad
s ( r ) relatively near the origin is
called penetration.
0.8

0.6 R2s
U2s
0.4
P rad 2s
0.2

0.0

0.2

0.4

0.6
0 5 10 15 2s orbital
normalized radial distance r a0

Figure-9.6

The 2p functions in this figure-9.7 differ

0.5
strikingly near the origin from the 1s and 2s R2p

functions. Because of the l = 1 barrier term 0.4 U2p

P rad 2p
in the r radial equation, P2rad
p ( r ) rises from 0.3

zero. 0.2
U2p(r) has a classically forbidden region
near the origin. 0.1

Following figures are three px, py and pz

0.0
0 5 10

normalized radial distance r a0
15

orbitals. Figure-9.7

py orbital
px orbital
Figure-9.8
pz orbital
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To compare the differences between the functions U n ,l (r ) = r Rn ,l (r ) and

,l ( r ) = (U n ,l ( r )) for the n = 1 and n = 2 states of hydrogen, they are plotted on the
Pnrad 2

same graph as shown in the following figures-9.9 and 9.10.

The increase in l by 1 from 2s to 2p states means that neither U2p(r) nor P2rad
p ( r ) have

nodes. Asymptotically, both functions decay at the same rate as their 2s counterparts,
because the decay constant for a pure- Coulomb potential energy doesn't depend on l.

The sole peak in P2rad

p ( r ) occurs at r = 4 a0, where its value is 0.19. Interestingly, the

mean radius of 2p state = 5 a0 is 1a0 smaller than that of the 2s state.

In the plots of reduced radial functions U1s(r), U2s(r) and U2p(r), note the differences
in these functions rise from 0. The functions U1s(r) and U2s(r) rise like r, in which U1s(r)
is faster than U2s(r) while U2p(r) rises like r2.

Radial Probability densities

Reduced Radial functions 0.6
0.8
1s
0.6 1s 0.5 2s
radial probability density

2s
2p
reduced radial function

0.4 2p 0.4
0.2
0.3
0.0
0.2
0.2

0.4
0.1

0.6 0.0
0 5 10 15 20 25 0 2 4 6 8 10 12 14
normalized radial distance r a0 normalized radial distance r a0

Figure-9.9 Figure-9.10

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 The third orbit n = 3 ( M shell), l = 0, ml = 0 and l = 1, ml = 0, 1 and l = 2, ml = 0, 1, 2

The general features are from the following graphs in figure-9.11:

U3s(r) has two nodes, U3p(r) has one, and U3d(r) has none.

The 3s radial probability density has two regions fairly near the origin where there is a
small but nonzero chance of finding the electron.

The 3s state is the most penetrating, because its radial function is unaffected by a
barrier, while the 3d, which suffers the strongest barrier, is the least penetrating.

Since the number of nodes = n - l 1 decreases with increasing l, small l radial

functions have the most nodes.

Since these nodes are radii where the probability density is zero, radial probability
densities for low- l are characterized by small regions of non-zero probability very near
the nucleus.

2.0 0.4
R3s R3p
1.5 U3p
U3s
0.2
1.0 P rad 3s P rad 3p

0.5 0.0

0.0
0.2

0.5

1.0 0.4
0 5 10 15 20 25 0 5 10 15 20 25
normalized radial distance r a0 normalized radial distance r a0

0.4
R3d
U3d
0.3
P rad 3d

0.2

0.1

0.0
0 5 10 15

20
normalized radial distance r a0
25 30

Figure-9.11

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 The following graphs in figure9.12 show the comparison of reduced radial functions and
probability densities of n = 3 states

The n = 3 states show that as l increases, the outermost peak moves inward, to smaller
radial distance.

The magnitude of each peak increases as the radial distance increases. This increase
occurs because as l increases by one unit, the probability density, which must remain
normalized to unity, looses one inner peak.

In spite of all these variations, the energies of all these n = 3 states is the same, E3 =
1:51 eV.

The range of r values required to plot all of the radial probability density for the n = 3
states is more than twice for states with n < 3.

Reduced Radial functions Radial Probability densities

0.4 0.12
3s 3S
3p 0.10 3P
radial probability density
reduced radial function

0.2 3d 3D
0.08

0.0 0.06

0.04
0.2

0.02

0.4 0.00
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
normalized radial distance r a0 normalized radial distance r a0

Figure-9.12

The five d orbitals are shown in figure-9.13

dxy orbital dyz orbital dxz orbital

 d z 2 orbital

Figure-9.13

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 Following graphs in figure-9.14 show the comparison of the probability densities for n =
1, 2, 3, 4 states.

All s-state radial probability densities for n = 1, 2, 3, and 4 behave the same way near
the origin. None suffer the l barrier, so all have peaks near the origin.

Because the number of nodes in an s state function increases by one with each unit
increase in n, the number of peaks also increases by one.

Only for the 1s state has a large peak near the origin; the magnitudes of the near-origin
peaks in radial probability density for n > 1 decrease rapidly with increasing n.

Consequently the probability of finding the electron far from the nucleus increases
appreciable as n increases.

0.6 0.20
2p
0.5 1s
3p
2s 0.15
Probability density
Probability density

0.4 3s 4p
4s
0.3 0.10

0.2
0.05

0.1
0.00
0.0 0 10 20 30 40
0 10 20 30 40
normalized radial distance r a0
normalized radial distance r a0

Figure-9.14

Main features to remember

l = 0, s-states do not vanish at r = 0.

l 0, states vanish at r = 0 and have their maximum probability amplitude further out
with increasing l.

The size, position of peak probability, scales with ~ n2.

The l = 0 function crosses the axis (n 1) times i.e. it has (n 1) nodes.

l = 1 has (n 2) nodes and so on.

Maximum l = n 1 has no nodes (except at r = 0)

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Stern-Gerlach Experiment

In 1922, Stern and Gerlach launched a beam of Silver (Ag) atoms through a non-uniform
magnetic field and detected them at a screen as shown in the figure-9.15.

Silver atom Beam splits

source into two

Magnet Screen Gerlach's postcard, dated 8 Feb,

1922, to Niels Bohr showing a
photograph of the beam splitting,
Figure-9.15

Classical physics does not predict distinct spots. Distinct spots mean the magnetic
moment is quantized.

This can not be due to orbital magnetic moment because orbital magnetic quantum
number is odd, we would expect odd number of spots.

This marked the discovery of the electron spin. A new type of angular momentum,
with a quantum number that can take on only two values:
s = 1 , ms = 1
2 2
This new kind of angular momentum is known as SPIN.
This spin sometimes visualize by the classical spin picture as shown in figure-9.16.

However, this spinning ball picture

shown in figure-9.16 is not realistic,
because it would require that the tiny
electron be spinning so fast that parts
would travel faster than c.
So the spin is another type of angular
momentum. ms = -1/2
So, we need FOUR quantum numbers ms = +1/2
to specify the electronic state of a
hydrogen atom
n, l, ml, ms (where ms = -1/2 and +1/2) Figure-9.16
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Recap

In this lecture, we have learnt

Born interpretation of the wavefunction is that the wavefunction has no direct physical
significance, only the probability of finding the electron is important.

Radial probabilities of finding the electron in different orbit of hydrogen atom are
different, s orbits is the most penetrating.

Electron in an atom can be designated by FOUR quantum numbers.

n, l, ml, ms (where ms = -1/2 and +1/2)