Physical Chemistry Homework Help

1. Hydrogenic Systems.
In each of the following cases, state which of the two quantities is larger. Justify
your answers. You do not need to do any integrals here. Some equations on page
333 of McQuarrie might be helpful.
A. The average value of r for a 2s electron versus a 2p electron.
Solution:
The average value of hri is larger for a 2s electron than a 2p electron.

B. The average value of 1/r for a 2s electron versus a 2p electron.

Solution:
is for both the 2s and 2p cases. We can confirm this since we have derived an
expression for
from the virial theorem in Question 4, and have proved that it is independent
of the /! value.
C. The average value of r for a 2s electron in He + versus a 1s electron in H.
Solution:
r for 2s He is 3a and for 1s Hydrogen it’s a . It makes
sense that r of the electron in the
+ 3
0 0
2
He + 2s would be double the distance (on average) than that of the 1s electron.
D. The average value of r for a 3d electron in Fe25+ versus a 1s electron in C 5+ .

Solution:
r for the 3d electron of Fe25+ is ≈ 0.4a0, whereas for the 1s electron of C 5+ it is
0.25a0. It is expected that, although the nucleus of Fe25+ has a larger positive
charge and would therefore pull its electron in the 3d shell closer, it’s still not as
close to the nucleus as the 1s electron of C 5+ .
E. The number of radial nodes in an 8g orbital versus the number of angular
nodes in an 8g orbital.
Solution:
The number of radial nodes is given as n − ` + 1 while the number of angular
nodes is given by `.

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 Therefore 8g has 3 radial nodes and 4 angular nodes.
F. The spacing between the radial nodes for a 14s orbital versus the spacing
between the radial nodes for a 16d orbital.
Solution:
Both have the same number of nodes, but in general since the 16d electron will
have a larger hri
value, we can expect that the node spacing should be larger for this case.
NOTE: Atomic properties such as the relative n` orbital energies, En` , and radii,
hrnin`, atomic ionization energy and electron affinity, and the dependence of
these properties on electron con- figuration are explained by the systematic
shielding of the +Z nuclear charge experienced by an electron in the n` atomic
orbital by all of the electrons in the other occupied n0`0 atomic orbitals. One
computes the effective nuclear charge experienced by an electron in the n`
orbital due to n`
effective nuclear charge is inserted in the standard hydrogenic
formulas for orbital energy, En` ,
shielding by all of the other electronsn in the electronic configuration, Z eff
(configuration). This
orbital radius, hri
n` n`
, and other integer powers of r, hr i . The Periodic Table
is explained by
shielding! A table of these inter-orbital shielding effects, sometimes known as
Burns’ rules, is given in a paper by Gerald Burns, “Atomic Shielding
Parameters,” J. Chem. Phys. 41, 1521-1522 (1964),
2. Spin 3/2 Periodic Table
Consider a universe where the electron has spin 3/2 instead of spin 1/2.
A. Draw the periodic table (up to Hafnium) in this alternate universe.
Solution:
If the electron were to have s = 3/2, then there would be four possible ms
values, ms = +3/2, +1/2, −1/2, −3/2, instead of the usual two. This means that
each atomic orbital can be occupied by four electrons and still satisfy the Pauli
exclusion principle (anti-symmetrization). s–orbitals can hold 4, p–orbitals can
hold 12, etc. We build up the periodic table in the same way we are used to,
adding electrons to shells as we go. The modified table (up to Hf) is shown in
Figure 1.

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I II III IV (III) (IV) (V) (VI) (VII) (VIII) (IX) (X) (XI) (XVI
(XII)
(I) (II) (III) (IV) V VI VII VIII IX X XI XII XIII
(XIII) (XIV) (XV) )XIV XV XVI
s block d block p block
1H H Li B
2 e e
3
4
B CNO F N N M AlSi P S CAK C
e a g l r a
Sc Ti V C MF C N C ZG G A S Br K
r ne o i u na e s e r
R Sr Y Z N MT R R P A C I S S T I X C B L C P N P S E G T D H ET Y L H
b r b o e u h d g d n n b e e s a a e r d mmu d b y o r mb u f
Figure 1: One reasonable ordering for a spin-3/2 periodic table.

That the 3d block should come after the 4s block isn’t obvious (and may
not even be true for a spin 3/2 table). In the real table, this lower energy
for 4s rather than 3d occurs because e-e repulsion is significantly
reduced for 4s electrons (which are much further from the core electrons),
than for 3d electrons. Even though the one-electron orbital energy for 4s
levels is higher than 3d levels, this reduction in e-e repulsion in many-
electron atoms causes the reordering. We assume the same trend will
exist here. There are 3 radial nodes for 4s and zero radial nodes for 3d.

B. Which elements would be “noble gases”? Which would be alkaline

earth elements? Which elements would be in the same period as carbon?
Solution:
The analog of the “noble gases” would be those with complete n–shells,
namely Be, Ca, Kr, and Hf. With regard to the “alkaline earth metals,”
we could argue that any element with an incomplete s–shell would count,
which includes groups I-III. You might argue that only (ns)1
configurations should count, in which case you consider only group I
elements. In the real table, there is no ambiguity because the only
incompletely filled s–shells have 1 electron anyway. For S = 3/2, carbon
is in the second period, along with elements with Z = 5 − 20 (B through
Ca).
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 C. What would the bond order of He2 be in this universe? What about O2 ?
Solution:
Since each MO can also be filled with 4 electrons now, the bond order of
He2 would be 4(!). O2 , on the other hand, now has a bond order of 0 (the two
σ and two σ∗ orbitals from the O 1s and 2s orbitals are each completely filled
with 16 electrons). You should be realizing just how
important the electron’s spin is in determining the chemical structure and
patterns of the universe.
D. What would the equivalent of the octet rule be in this alternate universe?
[NOTE: you could spend a lot of time answering this last question. It is
intended to be fun. When it stops being fun, your answer is long enough.]

Solution:
The octet rule is based on having complete n-shells. It should be clear that the
simplest analog in the spin 3/2 table is the “hexadectet” rule, i.e. n = 2 and 3
orbitals prefer to have 16 electrons in their outer shells (4 in s and 12 in p).

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 3. Rydberg States of a Many-Electron Atom.

The subject of this problem is potassium, which has a closed-shell ion-core:

K(1s22s22p63s23p6)n∗`

The ionization energy (in cm − 1 units) from the “4s” electronic ground state is
35009.78 cm − 1 . The Rydberg constant for K is < = 109737.32cm− 1 .
A. Why is it reasonable to ignore the anti-symmetrization requirement for
Rydberg states of this 19 electron atom?
Solution:
We approximate the K atom as a K + core and an electron. As the K + core is
complete (all filled shells), anti-symmetrization between the core and the single
valence electron has a negligible effect, so we ignore it.
B. Consider three consecutive members of the ns, np, and nd
Rydberg series:
n s-series n p-series n d-series
8 31764.95 40 34934.97 9 33572.11
cm − 1 cm − 1 cm − 1
9 32648.17 41 34938.72 10 33851.76
cm − 1 cm − 1 cm − 1
10 33214.39 42 34942.20 11 34056.90
cm − 1 cm − 1 cm − 1

Compute n∗-values for all 9 of the tabulated energy levels. Do the n∗ levels
increase in steps of ∼1.00?
Solution:
We are provided with excitation energies from the ground state. To convert to
energies under ionization, we use En∗ = Eionization − Estate . We combine this with
E n∗0 n∗2
Thus
n∗ =
Esta te − Eionization
Plugging in the tabulated values, .

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 ns n* δs np n* δp ns n* δs
8 5.815 2.185 40 38.3001.700 9 8.737 0.263
9 6.817 2.183 41 39.2971.703 10 9.735 0.265
10 7.818 2.182 42 40.2971.703 11 10.7310.269

C. The quantum defects, δ`, are defined as n − n∗ . Compute the approximately

n-independent quantum defects for the s, p, and d series of K.
Solution:
See above table. δ` = n − n∗ . We see that the defect for ns is about 2.2, for np
is about 1.7, and for nd is about 0.3.

D. Suggest a reason why δs » δp > δd.

Solution:
s orbitals penetrate further into the inner core than orbitals with higher angular
momentum. From this we expect δs » δp » δd ≈ 0.

E. The n∗ values you have determined from real spectroscopic data may be
considered “experi- mentally measured.” But the tabulated integer n quantum
numbers are not measured. They are inferred from some sort of physical
argument. Can you suggest what this argument is?
[HINT: the lowest s, p, and d states of K are called 4s, 4p, and 3d.]

Solution:
The quantum defects above are correct, even down to the 4s, 4p, and 4d states,
to within 0.1. We don’t record n∗ because, to an excellent approximation, it
increases in steps of 1.
4. Two Electron Wavefunctions: Spin.
For two electrons, the total z component of the spin angular momentum
for the system is
while the total spin operator is
given by

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 A. Show that
1 1sα(1) 2sβ(1) 1
both ψ αβ = √ 2 1sα(2) 2sβ(2)
≡ √ (2sα(1)2sβ(2) − 2sβ(1)1sα(2))
2
an
1 1sβ(1) 2sα(1) 1
d
are antisymmetric.ψ βα = √ 2 1sβ(2) ≡ √
2sα(2) (1sβ(1)2sα(2)
2 − 2sα(1)1sβ(2))

Show also that ψαβ and ψβα are eigenfunctions of S z, total. What are the eigenvalues
in each case?
Solutio
Ψαβ = √ 1[1sα(1)2sβ(2) − 2sβ(1)1sα(2)]
n: 2

switching 1 and 2 by the Pˆ12 permutation operator

Pˆ12Ψ=αβ √ [1sα(2)2sβ(1) 1
− 2sβ(2)1sα(1)]
2
1
= − √ [2sβ(2)1sα(1) − 1sβ(1)1sα(2)]
2

= −Ψαβ .

This indicates that Ψαβ is anti-symmetric:

1
Ψ β α = √ [1sβ(1)2sα(2) − 2sα(1)1sβ(2)]
2
switching 1 and 2 by
1
Pˆ12 Pˆ12Ψ βα [1sβ(2)2sα(1) − 2sα(2)1sβ(1)]
= √ 2
1

= − √ [2sα(2)1sβ(1) − 1sβ(2)2sα(1)]= −Ψβα .

2

This indicates that Ψβα is anti-symmetric. Now the

S z, total = S z1 + S eigenvalue for Ψαβ :
z2
Sz, total
Ψ =
αβ S + S Ψ
l
= √ S z1 {1sα(1)2sβ(2)
1z1 z2 −
αβ2sβ(1)1sα(2)} + S z2 {1sα(1)2sβ(2) − 2sβ(1)1sα(2)}
2

1
= √ 1sα(1)2sβ(2)
2 − − 2sβ(1)1sα(2)
2 2
2sβ(1)1sα(2)
+ − 2 1sα(1)2sβ(2) − 2
= 0

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 Now the eigenvalue for
Ψ βα :
Sz, totalΨ βα= Sz1 + S z2 Ψ βα

1 l
= √ S z 1 {1sβ(1)2sα(2) − 2sα(1)1sβ(2)} + S z2 {1sβ(1)2sα(2) − 2sα(1)1sβ(2)}
2
1
2sα(1)1sβ(2)
= √ − 1sβ(1)2sα(2) − 2
2 2
=0 + { 1sβ(1)2sα(2) − − 2sα(1)1sβ(2)
2 2

This indicates that both Ψαβ and Ψβα are eigenfunctions of S z, total, both with
eigenvalues of 0.
B. Show that, while ψαβ and ψβα cannot be written in the form ψspaceψspin, the
combinations of
ψαβ ± ψβα can both be cast in the form ψspaceψspin.

1
Solution: Ψ αβ = √ [1sα(1)2sβ(2) − 2sβ(1)1sα(2)]
2
1

= √ [(1s(1)2s(2)α(1)β(2)) − (2s(1)1s(2)β(1)α(2))]
2
/ = ΨspinΨspace
1
Ψ β α = √ [1sβ(1)2sα(2) − 2sα(1)1sβ(2)]
2
1

= √ [(1s(1)2s(2)β(1)α(2)) − (2s(1)1s(2)α(1)β(2))]
2

Howev / = ΨspinΨspace.
er 1
Ψ αβ + Ψ β α = √ [1sα(1)2sβ(2) − 2sβ(1)1sα(2) + 1sβ(1)2sα(2) − 2sα(1)1sβ(2)]
2
1

= √ [{ 1s(1)2s(2)α(1)β(2)} − { 2s(1)1s(2)β(1)α(2)}
+ { 1s(1)2s(2)β(1)α(2)}
2 − { 2s(1)1s(2)α(1)β(2)} ]
1
= √ { 1s(1)2s(2) − 2s(1)1s(2)} { α(1)β(2) + β(1)α(2)}
2
1

= √ Ψ space · Ψ spin .
2

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 Similarly,

1
Ψ αβ − Ψ β α = √ [1sα(1)2sβ(2) − 2sβ(1)1sα(2) − 1sβ(1)2sα(2) + 2sα(1)1sβ(2)]
2
1

= √ [{ 1s(1)2s(2)α(1)β(2)} − { 2s(1)1s(2)β(1)α(2)}
—{ 1s(1)2s(2)β(1)α(2)}
2 + { 2s(1)1s(2)α(1)β(2)} ]
1
= √ { 1s(1)2s(2) + 2s(1)1s(2)} { α(1)β(2) − β(1)α(2)}
2
1

= √ Ψ space · Ψ spin .
2

C. Verify that the total spin operator can be re-written in terms of raising and
lowering operators: 2 2 2
Stotal= S 1+ S +2 2S Sz z
1 2 + S 1 + S 2− + S 1 − S 2+ .

Solution:
=2 (S + S1 )(S 2 + S
Stotal 1 ) = 2S + S
2
1 S 1+ 2S S 2+ 1S
2
2

= S +11 S +
2
2 2(S S1 )2

= S + 1S2 + 22(S
2
xS + 2S yS 1 y+2 S S
1x z 1 )z 2
I( ( l
+S1 + S− 1 S +2 + S− 2 +S1 —S− 1 S +2 − S − 2
= S 1+2 S +
2
2 2S S
z 1 z+ 2 +
2
2 2 2i 2i
1
= S +12S +222S Sz1 +
z2 + 1S +2S + S+ 1 −2 S + −S1 +2
S + −S1 −S2 − S+ 1 +2 S + +S1 −S2
l 2
+S− 1 S+2 − S − 1 S− 2
2 2
= S + 1S + 22S S z1 +z 2(S +1S − 2 + S − 1 S +2 )

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 D. Show that neither ψ is an eigenfunction of S Total. That is to say, show
nor ψ that neither
2
of these wavefunctions is a total spin eigenstate.
αβ βα

2
l
S total Ψ αβ= S 1+2 S 2+2 2S zS1 z+2 S + 1 S − 2+ S − 1 S +2 Ψ αβ
Solution: 3 2 3
S 2Ψ = Ψ 2
S Ψ = 2
Ψαβ
1 αβ 4 αβ 2 αβ 4
2
2sβ(1)1sα(2)
2S z 1 S z 2 Ψ αβ = √ Sz1 − 1sα(1)2sβ(2) − 2
2 2

= −√ 21sα(1)2sβ(2) + − 2sβ(1)1sα(2)
2 2 2
= − Ψ αβ
2
l
I
1 3 1
S + 1 S − 2Ψ αβ = √ S+ 1 0 − + 2sβ(1)1sβ(2)
2 4 4
3 1
= −√ · + 2sα(1)1sβ(2)
2 4 4
2

I
= − √ 2sα(1)1sβ(2) l
12 3 1
S − 1 S +2 Ψ αβ = √ S − 1 + 1sα(1)2sα(2) + 0
2 4 4

= √ · 1sβ(1)2sα(2)
2
2

= √ 1sβ(1)2sα(2)
2

Therefore, summing over all the terms

gives 2 2
S total Ψ αβ = 2
Ψ +αβ √ [1sβ(1)2sα(2)
2 − 2sα(1)1sβ(2)]
2
= [Ψαβ + Ψβα ]

Repeating similar steps for Ψ βα gives

2
S Ψβ α
total = 2
[Ψαβ + Ψ βα ].

2
Therefore, neither
αβ nor βα of S
is an eigenfunctiontotal
Ψ Ψ .

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 2
± ψαβare βα
E. Finally, show that the combinations ψ both S and Stotal
eigenfunctions z,oftotal .

Solution:
Sz, total√1 αβ βα √ 1
(Ψ2 ± Ψ ) = 2(0 ± 0) = 0
2 1
Stotal √ αβ βα √ 2 (Ψ + Ψ + Ψ + Ψ )
(Ψ
2 + Ψ)= 2 αβ βα αβ βα
2 1
= 2 √ (Ψαβ +
2 1
2
Stotal αβ
√2 — ΨΨ
βα 2 αβ βα αβ βα
)=
βα )√2
+ Ψ −Ψ −Ψ )
(Ψ =(Ψ0
F. Note that ψαβ , ψβα, and ψαβ ± ψβα are all degenerate states within the non-
interacting electron picture. Comment on why your work above shows that ψαβ ±
ψβα are more realistic eigenstates of the Hamiltonian.
Solution:
We note that S and S correspond to the magnitude squared of the spin and its
projection onto
the z–axis, and therefore
2
z it would be more realistic if our wavefunctions are
1 1
eigenfunctions of(Ψthese
+ Ψ ) and (Ψ − Ψ ) are in fact eigenfunctions of our
operators. operators,
√ √

Since 22 αβ βα 2 αβ βα
they are more realistic than either Ψαβ or Ψ βα (which are not eigenfunctions
of S 2 and S z .
5. Independent Particle Model.
The following concern the independent particle mode. You may find the following
set of Coulomb and exchange integrals useful (energies in eV):
J 1s1s = 17.0 J1s2s = 4.8 K1s2s = 0.9 Z J2s2s = 3.5
Z Z Z
J1s2p = 6.6 K1s2p = 0.5 J2s2p = 4.4 Z K2s2p =
Z Z 0.8 Z
J2pi,2pi = 3.9 J2pi,2pk = K2pi,2pk = 0.2 Z
Z 3.5 Z i =/ k

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 A. Using the independent particle model discussed in class, what is the energy
difference between the 1s2px2 configuration and the 1s22s2 configuration? How do
you justify your result?
Solution:
We are asked to calculate the enregy difference between a 1s22p2 and a 1s22s2
configuration. Let’s x
compute the energy for each using the independent particle model
i>j
2 2
E[1s 2p
x ] = i+ Jij − ij
i i,j EK
1sα,1sβ 1sα,2p α 1sα,2p β 1sβ,2p α 1sβ,2p β 2p α,2p β
= 2E 1s + 2E2p — —K x −K x —K x −K x − Kx x

K (5.1)
+ J 1sα,1 sβ + J 1 sα,2px α + J 1 sα,2px β + J 1 sβ ,2px α + J 1 sβ ,2px β + J
= 2E 1s + 2E2p + J 1s,1s + 4J1s,2p + J2pi,2pi − 2K 1s,2p (5.2)
2px α,2px β

E[1s22s2] = 2E 1s + 2E 2s + J 1s,1s + 4J1s,2s + J2s,2s − 2K 1s,2s

⇒ ∆ E = 4(J1s,2p − J 1s,2s) + (J2pi,2pi − J2s,2s) − 2(K 1s,2p − K 1s,2s )
(5.3)
= Z[4(6.6 − 4.8) − (3.9 − 3.5) − 2(0.5 − 0.9)]
= +7.6Z eV
B. What is the energy difference between the ground state of Lithium and the
spin polarized 1s↑2s↑2pz↑ state? Is this energy about the size you expected?
Solution: E[1s22s1 ] = 2E 1 s + E 2s + J1 s1s + 2J1 s2s
2
− K 1 s2s Z 2 1(27.2 eV ) + Z(17.0 + 2 · 4.8
= 2− 12 + 22
= −3 (9/8)(27.2)
2 + 3(25.7) =
− 0.9) (5.4
−198.3 eV
E[1s↑2s↑2p↑x] = E 1s +2 E 2s + E2p + J 1s2s + J1s2p + J2s2p − K 1s2s − K 1s2p −)
Z 1 (27.22 eV ) + Z(4.8 + 6.6 + 4.4 − 0.9 −
K2s2p =2 − 1 2
+
2 2
= −3 (3/4)(27.2)
2 0.5 +− 0.8)
3(13.6) = (5.5
−142.8 eV
⇒ ∆E = −142.8 + 198.3 = 55.5 eV )
Consulting the NIST Atomic Spectra Database [physics.nist.gov/cgi-bin/ASD], (5.6 we
find that the high-spin 1s2s2p state lies 57.469 eV above the ground )state. Our
IPM prediction is remarkably close given we’ve only included first order e-e
repulsion corrections!

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 C. Use the IPM To compute the ionization potential of B (Boron): IP = E(B + ) −
E(B). Compare your boron result with the ionization potential of Lithium within
the IPM. Does this agree with periodic trends?
Solution:
No solution given.
D. Finally, compare the ionization potentials computed in part C. with the
experimental results [IP(Li) = 5.4eV, IP(B) = 8.3eV] and the answer you would
have gotten if you had assumed that the electrons do not interact.
Solution:
First, we calculate the ionization energy of Be:
E[Be →21s 2s ] =2 2E 1 s + 2E 2s + J1 s1s + 4J1 s2s +
J2s2s − 2K 1 s2s
Z 2 2 (27.2
2 eV ) + Z(17.0 + 4 × 4.8 + 3.5 −
= 2− 12 + 22
= −4 (5/4)(27.2)
2 2 × +0.9)
4(37.9) = (5.7
−392.4 eV
+ 2 )
E[Be → 1s 2s] = 2E1s + E2s + J 1s1s + 2J1s2s
2
− K 1s2s Z 2 2(27.2 eV ) + Z(17.0 + 2 × 4.8
= − 2 12 + 22
= −4 (9/8)(27.2)
2 +
− 0.9) (5.8
4(25.7) = −386.8 eV
)
(5.9
⇒ IE = ∆E = −386.8 + 392.4 =
theeVsame for Li. Note the ground state for Li is the same as) Be + with
Now, we do5.6
Z = 4 → Z = 3.
E[Li + → 1s2 2] = 2E 1s2 +
E[Li → 1s 2s] Z=2 −32 (9/8)(27.2) + 3(25.7) = −198.3 eV (5.10)
J 1s1s (27.2 eV ) + Z(17.0) = (5.11
=−
2 12−193.8 eV )
⇒ IE = ∆ E = −193.8 + 198.3 = 4.5 eV
(5.12)
The experimental IEs for Be and Li are 9.32 and 5.39 eV, respectively (NIST
ASD). Though the IPM values are significantly off in magnitude, they reproduce
the correct periodic trend: elements in the same period have increasing IEs from
left to right.
In the absence of e-e interactions, the IEs would be the energies of the vacated one-
electron orbitals. In each case this is a 2s orbital. The energy for Be would be
42/2(22) × 27.2 = 54.4 eV and for Li,

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 32/2(22) × 27.2 = 30.6 eV. These values are extremely high! Even though the IPM
predictions are not quantitatively correct, we see that they do account for the
majority of the effects caused by e-e interactions.
E. Within the IPM, what is the energy difference between a closedx shell 1s22s22p2

configuration
and a high spin 1s22s↑2p↑x2p↑y 2p↑z configuration for carbon? Does this agree with
your intuition?

Solution:

Our final problem is comparing closed-shell and high-spin configurations for

carbon,
Z = 6. E[1s22s2 2px 2 ] = 2E 1 s + 2E 2s +
2E 2p + J 1s1s + 4J1s2s + 4J1s2p + J2s2s + 4J2s2p +
—2K 1s2s
2 − 2K 1s2p −
J2px2pZx 2 4 (27.2 eV ) +
=
2K−2s2p +
2 12 22Z(83.2)
= 969.6 (5.13
eV )
E[1s22s↑2p↑x2p↑y 2pz↑] = 2E 1s + 1E2s + 3E2p

+ +J 1s1s + 2J
K 1s2s 1s2s + 6J1s2p + 3J2s2p + 3J2pi2pk
2 − 3K 1s2p − 3K 2s2p −
Z 2 4 (27.2 eV ) +
= −
3K 2pi22p=
k 12
+ 2 eV
−961.8 (5.14)
2 Z(84.5)

⇒ E[high spin] − E[closed shell] = ∆E = 7.8 eV. (5.15)

This agrees with our chemical intuition, where we expect closed shell configurations
to be the most stable.

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