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o Alkali atom spectra.

o Central field approximation.
o Shell model.
o Effective potentials and screening.
o Experimental evidence for shell model.
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o Alkali atoms: in ground state, contain a set of completely filled subshells with a single valence
electron in the next s subshell.
o Electrons in p subshells are not excited in any low-energy processes. s electron is the single
optically active electron and core of filled subshells can be ignored.
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o In alkali atoms, the l degeneracy is lifted: states with the same principal quantum number n
and different orbital quantum number l have different energies.
o Relative to H-atom terms, alkali terms lie at lower energies. This shift increases the smaller l
is.
o For larger values of n, i.e., greater orbital radii, the terms are only slightly different from
hydrogen.
o Also, electrons with small l are more strongly bound and their terms lie at lower energies.
o These effects become stronger with increasing Z.
o Non-Coulombic potential breaks degeneracy of levels with the same principal quantum
number.
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o For multi-electron atom, must consider Coulomb interactions between its Z electrons and its
nucleus of charge +Ze. Largest effects due to large nuclear charge.
o Must also consider Coulomb interactions between each electron and all other electrons in
atom. Effect is weak.
o Assume electrons are moving independently in a spherically symmetric net potential.
o The net potential is the sum of the spherically symmetric attractive Coulomb potential due to
the nucleus and a spherically symmetric repulsive Coulomb potential which represents the
average effect of the electrons and its Z - 1 colleagues.
o Hartree (1928) attempted to solve the time-independent Schrdinger equation for Z electrons
in a net potential.
o Total potential of the atom can be written as the sum of a set of Z identical net potentials V( r),
each depending on r of the electron only.
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o Hartree theory results in a shell model of atomic structure,
which includes the concept of screening.
o For example, alkali atom can be modelled as having a valence
electron at a large distance from nucleus.
o Moves in an electrostatic field of nucleus +Ze which is
screened by the (Z-1) inner electrons. This is described by the
effective potential V
eff
( r ).
o At r small, V
eff
(r ) ~ -Ze
2
/r
o Unscreened nuclear Coulomb potential.
o At r large, V
eff
(r ) ~ -e
2
/r
o Nuclear charge is screened to one unit of charge.
+Ze
-(Z-1)e
r
-e
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o The Hamiltonian for an N-electron atom with nuclear charge +Ze can be written:
where N = Z for a neutral atom. First summation accounts for kinetic energy of electrons ,
second their Coulomb interaction with the nuclues, third accounts for electron-electron
repulsion.
o Not possible to find exact solution to Schrodinger equation using this Hamiltonian.
o Must use the central field approximation in which we write the Hamiltonian as:
where V
central
is the central field and V
residual
is the residual electrostatic interaction.

!

H =

H
kinetic
+

H
elec"nucl
+

H
elec"elec
= "
!
2
2m
#
i
2
"
Ze
2
4$%
0
r
i i=1
N
&
i=1
N
&
+
e
2
4$%
0
r
ij i> j
N
&

!

H = "
!
2
2m
#
i
2
"V
central
(r
i
)
$
%
&
'
(
)
i=1
N
*
+V
residual
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o The central field approximation work in the limit where
o In this case, V
residual
can be treated as a perturbation and solved later.
o By writing we end up with N separate Schrdinger equations:
with E = E
1
+ E
2
+ + E
N

o Normally solved numerically, but analytic solutions can be found using the separation of
variables technique.
!
V
central
(r
i
)
i=1
N
"
>> V
residual

!
" ="
1
( r
1
)"
2
( r
2
)"
N
( r
N
)

!
"
!
2
2m
#
i
2
"V
central
(r
i
)
$
%
&
'
(
)
*
i
( r
i
) = E
i
*
i
( r
i
)
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o As potentials only depend on radial coordinate, can use separation of variables:
where R
i
(r
i
) are a set of radial wave functions and Y
i
(!
i
, "
i
) are a set of spherical harmonic
functions.
o Following the same procedure as Lectures 3-4, we end up with three equations, one for each
polar coordinate.
o Each electron will therefore have four quantum numbers:
o l and m
l
: result from angular equations.
o n: arises from solving radial equation. n and l determine the radial wave function R
nl
(r )
and the energy of the electron.
o m
s
: Electron can either have spin up (m
s
= +1/2) or down (m
s
= -1/2).
o State of multi-electron atom is then found by working out the wave functions of the individual
electrons and then finding the total energy of the atom (E = E
1
+ E
2
+ + E
N
).
!
"
i
( r
i
) ="
i
(r
i
,#
i
,$
i
) = R
i
(r
i
)%
i
(#
i
,$
i
)
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o Hartree theory predicts shell model structure, which only considers gross structure:
1. States are specified by four quantum numbers, n, l, m
l
, and m
s
.
2. Gross structure of spectrum is determined by n and l.
3. Each (n,l) term of the gross structure contains 2(2l + 1) degenerate levels.
o Shell model assumes that we can order energies of gross terms in a multielectron atom
according to n and l. As electrons are added, electrons fill up the lowest available shell first.
o Experimental evidence for shell model proves that central approximation is appropriate.
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o Periodic table can be built up using this shell-filling process. Electronic configuration of first
11 elements is listed below:
o Must apply
1. Pauli exclusion principle: Only two electrons with opposite spin can occupy an atomic
orbital. i.e., no two electrons have the same 4 quantum numbers.
2. Hunds rule: Electrons fill each orbital in the subshell before pairing up with opposite spins.
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o Below are atomic shells listed in order of increasing energy. N
shell
= 2(2l + 1) is the number of
electrons that can fill a shell due to the degeneracy of the m
l
and m
s
levels. N
accum
is the
accumulated number of electrons that can be held by atom.
o Note, 19th electron occupies 4s shell rather than 3d shell. Same for 37th. Happens because
energy of shell with large l may be higher than shell with higher n and lower l.
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o 4s level has lower energy than 3d level due to penetration.
o Electron in 3s orbital has a probability of being found close to nucleus. Therefore
experiences unshielded potential of nucleus and is more tightly bound.
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Radial probabilities for 4s 3d
4s - red
3d - blue
Note: Movies from http://chemlinks.beloit.edu/Stars/pages/radial.htm
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Radial probabilities for 1s 2s 3s
1s - red
2s - blue
3s - green
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Radial probabilities for 3s 3p 3d
3s - red
3p - blue
3d - green
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o Alkali are approximately one-electron atoms: filled inner
shells and one valence electron.
o Consider sodium atom: 1s
2
2s
2
2p
6
3s
1
.
o Optical spectra are determined by outermost 3s electron.
The energy of each (n, l) term of the valence electron is
where #(l) is the quantum defect - allows for penetration
of the inner shells by the valence electron.
o Shaded region in figure near r = 0 represent the inner n
= 1 and n = 2 shells. 3s and 3p penetrate the inner shells.
o Much larger penetration for 3s => electron sees large
nuclear potential => lower energy.
!
E
nl
= "
R
H
[n "#(l)]
2
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o #(l) depends mainly on l. Values for sodium are
shown at right.
o Can therefore estimate wavelength of a transition via
o For sodium the D lines are 3p ! 3s transitions. Using
values for #(l) from table,
=> $ = 589 nm
!
1
"
= R
H
1
[n
f
#$(l
f
)]
2
#
1
[n
i
#$(l
i
)]
2
%
&
'
'
(
)
*
*
!
1
"
= R
H
1
[3#$(3s)]
2
#
1
[3#$(3p)]
2
%
&
'
(
)
*
=1.0967757 +10
7
1
1.627
2
#
1
2.117
2
%
&
'
(
)
*
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o Consider sodium, which has 11 electrons.
o Nucleus has a charge of +11e with 11 electrons
orbiting about it.
o From Bohr model, radii and energies of the electrons
in their shells are
o First two electrons occupy n =1 shell. These electrons
see full charge of +11e. => r
1
= 1
2
/11 a
0
= 0.05 and
E
1
= -13.6 x 11
2
/1
2
~ -1650 eV.
o Next two electrons experience screened potential by
two electrons in n = 1 shell. Z
eff
=+9e => r
2
= 2
2
/9 a
0

= 0.24 and E
2
= -13.6 x 9
2
/2
2
= -275 eV.
!
r
n
=
n
2
Z
a
0
!
E
n
= "
13.6Z
2
n
2
and
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o Ionisation potentials and atomic radii:
o Ionisation potentials of noble gas elements are
highest within a particular period of periodic
table, while those of the alkali are lowest.
o Ionisation potential gradually increases until
shell is filled and then drops.
o Filled shells are most stable and valence
electrons occupy larger, less tightly bound orbits.
o Noble gas atoms require large amount of energy
to liberate their outermost electrons, whereas
outer shell electrons of alkali metals can be
easily liberated.
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o X-ray spectra:
o Enables energies of inner shells to be
determined.
o Accelerated electrons used to eject core electrons
from inner shells. X-ray photon emitted by
electrons from higher shell filling lower shell.
o K-shell (n = 1), L-shell (n = 2), etc.
o Emission lines are caused by radiative transitions
after the electron beam ejects an inner shell
electron.
o Higher electron energies excite inner shell
transitions.
Wavelength (A)
40 keV
80 keV
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o Wavelength of various series of emission lines are found to obey Moseleys law.
o For example, the K-shell lines are given by
where % accounts for the screening effect of other electrons.
o Similarly, the L-shell spectra obey:
o Same wavelength as predicted by Bohr, but now have
and effective charge (Z - %) instead of Z.
o %
L
~ 10 and %
K
~ 3.
!
1
"
= (Z #$
K
)
2
R
H
1
1
2
#
1
n
2
%
&
'
(
)
*
!
1
"
= (Z #$
L
)
2
R
H
1
2
2
#
1
n
2
%
&
'
(
)
*
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o Assume net charge is ( Z - 1 )e.
o Therefore, the potential energy is
o Total energy of orbit is
o Modified Bohr formula taking into account screening.
o Can therefore easily show that
( )
n
n
r
e Z
V
0
2
4
1
!"
#
# =
( ) ( )
2
2 2
0
0
2
2
0
2
2 '
) 1 (
4
4
1
4
1
2
1
2
1
e Z m
n
e Z
n
e Z
m V mv E
n n n
!
!
!
"
"
#
$
%
%
&
' !
= + =
! ! ()
()
()

!
= "
Z "1 ( )
2
me
4
2 4#$
0
( )
2
n
2
!
2
!
"E
n
= #
13.6(Z #1)
2
n
2
!
1
"
= (Z #1)
2
R
H
1
1
2
#
1
n
2
$
%
&
'
(
)
PY3P05
o Electrons in orbitals with large principal quantum
numbers (n) will be shielded from the nucleus by inner-
shell electrons.
Z
eff
= Z - %
nl
.
o %
nl
increases with n => Z
eff
decreases with n.
o %
nl
increases with l => Z
eff
decreases with l.
n=1
n=2
n=3
n=4
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o In hydrogenic one-electron model, the energy levels
of a given n are degenerate in l:
o Not the case in multi-electron atoms. Orbitals with the
same n quantum number have different energies for
differing values of l.
o As Z
eff
= Z - %
nl
is a function of n and l, the l
degeneracy is broken by modified potential.

!
E
n
= "
Z
2
e
4
(4#$
0
)
2
2!
2
n
2
3s 3p 3d

!
E
n
= "
Z
eff
2
e
4
(4#$
0
)
2
2!
2
n
2
3s 3p 3d
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o Wave functions of electrons with different l are found to have different amount of penetration
into the region occupied by the 1s electrons.
o This penetration of the shielding 1s electrons exposes them to more of the influence of the
nucleus and causes them to be more tightly bound, lowering their associated energy states.
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o In the case of Li, the 2s electron shows more penetration inside the first Bohr
radius and is therefore lower than the 2p.
o In the case of Na with two filled shells, the 3s electron penetrates the inner
shielding shells more than the 3p and is significantly lower in energy.