CM1502

Q1. Without referring to any figures, sketch signed boundary

surfaces on appropriate axes of the following AO:
1s, 3s, 2p
x
, 2p
y
, 3d
z2
, 3d
yz
.

1s and 3s look like a sphere:
The radial nodes are inside the
sphere of the 3s AO.

2p
x
and 2p
y

3d
z2

3d
yz

Q2.Give all possible values for the missing hydrogen atom
quantum number in each case:

a. n = 3, l = 2, m
l
= ?
2, 1,0

b. n = 5, l = ?, m
l
= 0
4, 3,2,1,0

c. n = 4, l = ?, m
l
= -2
3, 2
d. n = ?, l = 2, m
l
= 1
3,4,5,6

e. n = 10, l = 0, m
l
= ?
0
3. For the cases in (2), give the corresponding AO labels.

All the 3d AOs, so 3d
xy
, 3d
x2-y2
, 3d
zx
, 3d
zy
, 3d
z2
respectively.

5g
z4
, 5f
z3
, 5d
z2
, 5p
z
, 5s.

4f
(x,y combination)
, 4d
xy
and 4d
x2-y2

3d
xz
and 3d
yz
, 4d
xz
and 4d
yz
, 5d
xz
and 5d
yz
, 6d
xz
and 6d
yz
,

10s
4. What is the ionization energy in eV of a hydrogen atom
in a 4p state and (1,0,0) state? Use the formula
2
2
2
0
4 2
1
8
n
h
e Z
E
n
c

=
where e = 1.602 x 10
-19
C, m
proton
= 1.673 x 10
-27
kg,
m
electron
= 9.109 x 10
-31
kg,
is the reduced mass = m
electron
m
proton
/(m
electron
+m
proton
).
h = 6.626 x 10
-34
Js, e
0
= 8.854 x 10
-12
C
2
J
-1
m
-1
.

Substituting all the numbers into the above formula
gives -2.178 x 10
-18
J = -13.59 eV for n = 1.

For n = 4, our answer must be
2
of -13.59 eV, that
is, -0.849 eV.

The ionization energy is the difference E

-
En
, so for
(100) we have i.e. = 0 - -13.59 = 13.59 eV.

For n = 4, l=1 (or l=3,2,0) we have 0 - -0.849 = 0.849 eV.

5. Arrange the following elements in order of increasing
ionization energy IE. You may refer to a periodic table.


1.Ne Ba Ga F S
Ba < Ga < S < F < Ne
1.Cl I Br Te Ar
Te < I < Br < Cl < Ar
1.Mg Cs N Si Al
Cs < Al < Mg < Si < N
Mg has a higher IE than Al because the 3p AO
is higher in energy than the 3s.
Mg [Ne]3s
2
, Al [Ne]3s
2
3p
1
.
6. Arrange the sequences of (4) in order of
increasing atomic radius. You may refer to a
periodic table.
Atomic radii are related to n
2
/Z
eff
. The trend is
just the reverse of the IE, except much fewer
anomalies are observed due to the chemical
bond distances being used to obtain the radii,
and in chemical bonds AO can be strongly mixed
together thus obliterating any subtle differences
in AO energies. Thus the ordering for (a) and (b)
is just the reverse of 1a and 1b. The order for (c)
is N < Si < Al < Mg < Cs.
7. Nb possess the anomalous electronic configuration
[Kr]5s
1
4d
4
. State why it is an anomaly, and provide an
explanation to account for it.
Nb is considered an anomaly because its configuration
should be: [Kr]5s
2
4d
3
. This is because significant
electron-electron repulsion is introduced into the atom
by removing an electron from the 5s AO and dropping it
down into the more stable 4d AO. However, in the case
of Nb, in the configuration [Kr]5s
1
4d
4
, all the electrons
have parallel spin (Hunds rule of maximum multiplicity),
thus significantly reducing electron-electron repulsion
and therefore making this configuration more stable than
[Kr]5s
2
4d
3

8. A laser beam operating at 600 nm has a power of
1mW. What is the energy of a single photon from this
laser? The laser is shone onto a surface for 1 ns, how
many photons hit the surface?
E = hc/, so E = 6.626 x 10
-34
x 2.998 x 10
8
/ 600 x
10
-9
= 3.311 x 10
-19
J
Power is energy used per second. The power of the
laser is 1 mW, so in 1 s, 1 mJ of energy is used.
In 1 ns we must have used 1 mJ x 10
-9
= 10
-12
J.
Each photon contains 3.311 x 10
-19
J, so to have 10
-
12
J total energy in the beam of photons, we must
have 10
-12
/3.311 x 10
-19
= 3.02 x 10
6
photons
about 3 million photons.

9.Atomic absorption lines were observed in the
spectrum of a gas sample in an atomic absorption
spectrometer. The spectrum appeared very similar to
that of H, but was not the same. The highest energy
absorption was observed well into the UV and it began
at 13.51 nm. Identify the atom in the sample.
2
2
2
0
4 2
1
8
n
h
e Z
E
n
c

=
The observed spectrum is similar, but not the same as H, so
we will assume that the spectrum is that of a hydrogenic
atom.
The highest energy absorption series is from n = 1 to n > 1.
The start of this series is from n = 1 to n = 2.
The transition energy is given by E
2
E
1
,
Where m
1
is the mass of the unknown nucleus and m
2
is the
mass of the electron. However, the nuclear mass is at least
1500 times more massive than the electronic mass,
so we have m ~ m
e
.
4
3
8
1
1
2
1
8
2
2
0
4 2
2 2
2
2
0
4 2
1 2
h
e Z
h
e Z
E E
c

=
|
.
|

\
|
=

c

c
c

c

3
2 4
3
16 2
32
3 1
32
3
2
0
4
2
2
0
2
3
2
0
4
2
2
2
0
4 2
hc
e
h
Z
e
hc h
Z
c h
e
Z
h
e Z hc
E
=

=
=
= = A
So Z = 3.
The atom is Li, and the
chemical giving rise to the
spectrum is Li
2+
.
10.Can an electron ever be at rest, i.e., possess zero
kinetic energy, if it is confined to exist in some specific
region in space, and nowhere else? Explain.


An electron can never be at rest if confined. The
Heisenberg uncertainty principle sates that as we
restrict Dq, the uncertainty in momentum increases.
This increased uncertainty equates to an increased
kinetic energy of the electron.