Electron configuration

and chemical periodicity.

1
Chapter 2
CM1502
1
Need to now solve:
( ) ( ) ( )
2 1 2 1 2 1
, , ,

r r r r r r + = + E H
Our wavefunction now depends on r
1
and r
2
,
i.e., (x
1
, y
1
, z
1)
and (x
2
, y
2
, z
2
)
Consider the He Atom
If a second electron is added to our atom (eg: H
-
or He), two new
interactions come into existence.
1. Attraction of the second electron to the nucleus, and
2. repulsion of the second electron by the first.
The Hamiltonian should include these interactions.
K.E. for e 1
( )
(

+ + + =
12
2
2
2
1
2
0
2 1
2 2
4
1

r
e
r
e
r
e
K K H
tc
K.E. for e 2
P.E. e 1 to nuc
P.E. e 2 to nuc
P.E. e-e rep
Adding a Second Electron
2
No Exact Solution
1here ls no exacL soluLlon Lo Lhls equaLlon, !"# %!"
"&'&( )&.
LxacL soluLlons can only exlsL for sysLems wlLh one
elecLron, &*+*, P, Pe
+
, Ll
2+
, P
2
+
, eLc.
1hls ls a Lhree-body problem, [usL llke Lhe orblL of Lhe
Sun-LarLh-Moon sysLem, Lhere ls no exacL soluLlon Lo
Lhelr orblLs elLher.
- ls Lhls a problem?
3
Solving the Schrdinger Equation
lor small aLoms and molecules, we can do Lhls now for all
pracLlcal degrees of preclslon, uslng compuLers
A slmple approxlmaLlon Lo help solve Lhe Schrdlnger LquaLlon ls
Lhe so-called ,"#&-&"#&". -!(.,%/& 01#&/.

1haL ls, we wrlLe: +(r
1
,r
2

1
(r
1
)
2
(r
2
).

Pere y
1
ls Lhe aLomlc orblLal of elecLron 1 LhaL moves as lf,
elecLron 2 ls noL presenL.
So when you wrlLe 1s
2
for Lhe conflguraLlon of Pe, whaL you are
acLually wrlLlng ls: +(r
1
,r
2
1s(r
1
) 1s(r
2
)
4
Atomic Orbital(AO) Energy and Total
Electronic Energy
Solution to Schrdinger equation for systems with more than one electron
(using computers) results in two types of energies,
1. AO energies and
2. the total electronic energy.

For the H atom, the energy of an AO is equal to the total electronic energy
of the H atom since it has only 1 electron.
Energy of a electron in a particular AO depends on several factors,
the three relevant ones here are

The attraction felt by the electron between itself and the
nucleus. i.e., the effective nuclear charge that the electron
experiences, Z
eff.
The repulsion of the electron with remaining electrons in the
atom. e-e repulsion
Orbital Shape

This means the energy of an electron in 4s AO in one atom, is different to
the energy of an electron in the 4s AO of another atom.


5
Z
eff
and Screening
Consider He

electron 1 blocks out some of the positive
charge of the nucleus so that electron 2
does not get to see the full +2 charge (and
vise versa).

Because of screening the effective nuclear
charge, Z
eff
, of He is 1.69 instead of 2.


It is illustrated in this movie (ILVE workbin-
videos-Effective nuclear charge)
6
7
LffecLlve nuclear charge depends on

1. nuclear charge

2. Shleldlng by Lhe elecLrons ln Lhe same energy level

3. Shleldlng by Lhe elecLrons ln Lhe lnner energy level
Z
eff
and Screening
For the H atom, the 2s and 2p orbital have the same energy.
Screening occurs when there is more than 1 electron (cf. He).
The third electron in Li occupies 2s sublevel rather than 2p.
Why?
Z
eff
is larger for the 2s than 2p, but why?
We have to consider orbital shapes, that is radial probability
distributions.
8
Orbital Penetration
2p orbital (orange curve) is slightly closer
to the nucleus than the maxima of the 2s
orbital (blue curve).

But small portion of 2s radial probability
distribution peaks with the 1s region.

Thus an electron in the 2s orbital spends
part of its time penetrating very close to
the nucleus.


9
10
Penetration has two effects:

It increases the nuclear attraction for a 2s electron over
the 2p electron
It decreases the shielding of a 2s electron by the 1s
electron.

As a result an energy level splits into sublevels of differing
energy. The lower the / value of the sublevel, the
penetration is higher and hence greater the attraction
to the nucleus. Order of sublevel energies: s<p<d<f

Because the extent of AOs increases as n increases for the
same value of / we also have e1s < e2s < e3s , e2p < e3p
< e4p , e3d < e4d < e5d, etc.
Electron spin quantum number
This is the property of an electron and not the orbital.
Each electron behaves like a spinning charge and generates a
tiny magnetic field.
The two fields have opposing directions.
So half of the electrons are attracted by the large external
magnetic field while other half is repelled.
This gives rise to the spin quantum number m
s
with allowed
values of +1/2(spin up) or -1/2 (spin down)


11
Paulis Exclusion Principle
no Lwo elecLrons ln a glven aLom can have Lhe exacL
same seL of quanLum numbers.

lor Lhe Pe aLom, Lhe conflguraLlon 1s
2
means LhaL
one elecLron has Lhe quanLum numbers
" = 1, / = 0, 0
/
= 0, 0
2
= +x, and Lhe oLher
" = 1, / = 0, 0
/
= 0, 0
2
= -x.

Ll could noL have Lhe conflguraLlon 1s
3
, slnce Lhe
Lhlrd elecLron would have Lo geL Lhe same seL of
quanLum numbers as one of Lhe oLher Lwo.
12
The Aufbau Principle
ls a rule for flndlng Lhe lowesL energy
elecLron conflguraLlon for aLoms.
lL sLaLes LhaL you musL !## .3& &/&%.(1"24
1"& !. ! .,0&4 ,".1 .3& 1(),.!/2 .3!.
516/# 0!7& .3& !.10 012. 2.!)/&4 )6.
1)&8,"+ .3& 9!6/, &:%/62,1" -(,"%,-/& !.
!// .,0&2.
8y mosL sLable" we mean lowesL value
Lo LoLal elecLronlc energy,L.

13
Stable Electronic Configurations
1he order of fllllng AC ls besL
remembered by plcLurlng Lhe
perlodlc Lable ln your mlnd.
1he Lable Lo Lhe rlghL lllusLraLes
Lhls.
1s
2s 2p
3s 3p
4s 3d 4p
5s 4d 5p
6s 4f 5d 6p
7s 5f 6d 7p
Orbitals Filled
You should be able to give
ground state (most stable
state) electronic
configurations for any
element in the periodic table
given the Z only.
14
Hunds Rule of Maximum Multiplicity
arL 1: uegeneraLe orblLals (/ > 0) are always fllled wlLh slngle
elecLrons before any of Lhem are doubly occupled.
- 1hls reduces elecLron-elecLron repulslon.

arL 2: LlecLrons prefer Lo flll Lhe separaLe orblLals wlLh Lhelr
spln's allgned (same value of 0
2
).
- LlecLrons wlLh Lhe same value of 0
2
naLurally keep furLher
away from each oLher compared Lo Lhose palrs where Lhelr
splns are opposlLe.
- 1hls leads Lo even less elecLron-elecLron repulslon.
- Allgnlng Lhe splns as much as posslble leads Lo 0!:,060
06/.,-/,%,.8*
15
Orbital Occupancy Diagram
The species with unpaired electrons
exhibits paramagnetism; it is attracted by
an external magnetic field.
The species with all of its electrons
paired exhibits diamagnetism; it is not
attracted by an external magnetic field.

16
17















Distribution of electrons
The electron configuration
n l
# of electrons in the sublevel
as s, p, d, f
The orbital diagram (box or circle)
1here are Lwo common ways Lo lndlcaLe Lhe dlsLrlbuLlon of elecLrons.
These configurations actually
represent electronic wave
functions i.e., approximate
solutions to the Schrdinger
equation.

The electronic configurations
and AO stability is responsible
for the periodic properties
observed in the elements.
The method of writing the electronic configuration
is illustrated in this movie (ILVE workbin-videos-Electronic configuration)
18
A periodic table of partial, ground-state electron
configurations.
19
Stability of AOs with different n and l

why does k and Ca occupy Lhe 4s AC before Lhe 3d?
4s peneLraLes beLLer lnLo Lhe 1s
2
2s
2
2p
6
3s
2
3p
6
core Lhan any 3d AC does.
why are elecLrons removed from Lhe 4s AC upon lonlzaLlon of a LranslLlon
meLals ln Lhe 4
Lh
perlod,
&*+* le
2+
has Lhe conflguraLlon [Ar]4s
0
3#
6
?
1he 3d AC ls rapldly becomlng more sLable for furLher elemenLs. Why?
- 8y addlng 1 elecLron Lo Lhe 4s ln k, we flnd LhaL Lhls hardly screens Lhe 3d
(3d maxlmum closer Lhan Lhe 4s maln maxlmum), so any 3d e would galn an
almosL full lncrease of +1 for lLs ;
eff
.
- lor Lhe same reason, addlng a second elecLron Lo Lhe 4s ln Ca, hardly
screens any elecLron LhaL mlghL be found ln Lhe 3d
- Lhus Lhe 3d orblLal drops sLlll furLher ln energy.
- llnally aL Sc, Lhe 3d AC )&%10&2 !"#$ 2.!)/& .3!"
Lhe 4s AC, and remalns so for Lhe resL of Lhe
enLlre perlodlc Lable.
20

Why isnt the lowest energy electronic
configuration of Sc [Ar]4s
0
3d
3
?

The answer to this question lies
in electron-electron repulsion.

The extent of an n = 3 AO is
significantly less than n = 4 AO.

Electrons in the 3d AO repel
each other more than electrons
in a 4s AO.
e
repulsion
(3d,3d) > e
repulsion
(3d,4s) > e
repulsion
(4s,4s).
E
21
Anomalous Configurations 1
Pere e-e repulslon of -!,(&# elecLrons ls hlgher Lhan
placlng all Lhe elecLrons ls separaLe orblLals 5,.3
-!(!//&/ 2-,"2*
- As ls Lhe basls of Pund's rules, elecLrons wlLh parallel splns
naLurally keep furLher aparL from each oLher so elecLron
repulslon ls reduced. Pere all 6 valence elecLrons have
parallel splns.
- nb and Mo are oLher examples, buL slmply ln Lhe nexL
perlod (n=3).
22
Anomalous Configurations 2
Cu has Lhe conflguraLlon 4s
1
3d
10

1he energy gap beLween 3d and 4s ls large enough
Lo overcome Lhe lncrease ln energy due Lo e-e
repulslons ln 3d.

- 1he reason for anomalles for 8u, 8h, d and Ag
are Lhe same as well, excepL we are Lalklng abouL
Lhe 4d and 3s raLher Lhan Lhe 3d and 4s ACs.
23
The consistent changes in properties such as atomic size, Ionization
energies etc within a group or period are called periodic properties.
Periodic Properties of the Elements
An understanding of how Z
eff
and n vary in the periodic table as well
as the most stable electronic configurations, helps us to understand
the trends in the following properties:

Ionization Energy.
Electron Affinity.
Atomic Radius.
Electronegativity.
Oxidation states (which we will not discuss, but you may review
for your own interest in the movie (IVLE workbin-videos-
Oxidations states)
24
25
Moving across a period,

n is constant, and Z
eff
increases.

Moving down a group

Z
eff
increases somewhat, but n

increases by

one unit
Z
eff
and n
Atomic Radii
There are different types of atomic radii.

Covalent radii (also unfortunately
sometimes called Atomic radii)
! the distance between the nuclei of single bonded
atoms, e.g., Cl
2

Metallic radius is one-half the shortest
distance between nuclei of adjacent individual atoms in a
crystal of an element, e.g., Fe
(S)


Ionic radii
Obtained from solids that exhibit ionic bonding, e.g.,
NaCl.
van der Waals radii
The radius of the sphere surrounding the nucleus that
contains 98% of the electron density.
26
27
Periodicity in Atomic Radii
Varies in a systematic way along the group and the period.

Review the trend in the movie (IVLE-workbin-videos-atomic
radii)

From the radial distribution for a hydrogenic atom we have

r
nl
n
2
/Z
eff
,


where n and l refer to the highest occupied AO (HOAO).

Moving across a period, n is constant, but Z
eff
increases,
so the radii decrease.
Moving down a group Z
eff
increases somewhat, but n
2

increases more, so the radii increase.
28
Periodicity in Atomic Radii
Ionic Radii
lL ls a measure of slze of an lon and ls obLalned from
Lhe dlsLance beLween Lhe nuclel of ad[acenL lons ln a
crysLalllne lonlc compound.
CaLlons are smaller Lhan parenL aLoms and anlons
are larger Lhan Lhelr parenL aLoms.
CaLlon slze decrease wlLh Lhe charge
e.g: le
3+
ls smaller Lhan le
2+
uown Lhe group lonlc slze lncreases.
Across Lhe perlod Lhe paLLern ls complex.
29
Ionic Vs Atomic radii
30
Notice the trend in
the sizes for an
isoelectronic
series like N
3-
, O
2-
,
F
-
, Na
+
, Mg
2+
, Al
3+
.


Isoelectronic
the same
electronic
configuration
(s
2
p
6
).
Ionization Energy (IE)
The first IE is defined as the energy needed to remove the most weakly
bound electron i.e., the electron from the Highest Occupied Atomic Orbital
(HOAO).

This process requires energy to overcome their electrostatic attraction.
Hence IE is always positive.

The second, third and continuing IE correspond to removing the
easiest electron from A
+
, A
2+
, etc.


For a given element there is an increase in IE
1
, IE
2
,IE
3
..etc

This is because each electron is pulled away from a species with
a higher positive charge.
31
Review the trend seen in the 1st, 2nd, and 3rd IE via the movie
(IVLE workbin-videos-Ionization Energy)
Periodicity in the first IE
For a given period as we
move from left to right,
the IE increases.
This is because Z
eff

increases from left to
right.

The IE falls slowly down
a group.
n increases as we
move down a group,
Z
eff
also increases, but
slowly.
The increase in n
dominates over the
gradual increase in Z
eff
.
32
2
2
eff
n
Z
k E
n
=
Orbital energies very roughly follow
the Bohr formula:
33
Little glitches occur at Be-B and N-O.

For Be-B, With the c
2p
> c
2s
the
IE is therefore lower in B cf. Be.
For N-O, N has half filled p sub-shell, so the 4
th

electron to enter the p sub shell in O is forced to
pair with another electron and produces significant
e-e repulsion. This increases the orbital energy,
and hence reduces the IE.
34
Electron Affinity
Defined as the energy required to remove the least tightly
bound electron from an singly charged anion, A
-
.
Forming an A
-
depends on the stability and availability
of an AO to hold the extra electron.
EA are always smaller than IE because there is very
little attraction between an e and a neutral atom at long
distances compared with an e and a positively charged
atom.
35
Periodicity in the first EA
Those elements that require energy to add an electron are assigned an EA of zero.
1he Lrends are
noL regular.

1here ls an
overall lncrease
from lefL Lo rlghL
and decrease
down Lhe group.
Trends in metallic behavior.
1he Lyplcal behavlor of meLals ls Lo
lose elecLrons Lo non-meLals.
1he meLalllc behavlor decreases lefL-
Lo-rlghL across a perlod.
-Lhls ls because of a decrease
ln slze, an lncrease ln lL and a
more favourable LA
lL lncreases down Lhe group ln
Lhe perlodlc Lable
-Lhls ls conslsLenL wlLh an
lncrease ln slze and a decrease ln lL.
36
Redox and Acid base behavior
1he elemenLs wlLh low lL and small
LA (eg:gp1,2) are sLrong reduclng
agenLs.
1he elemenLs wlLh hlgh lL and large
LA (eg: gp 16 and 17) are sLrong
oxldlzlng agenLs.
As Lhe elemenLs become more
meLalllc down Lhe group, Lhelr
oxldes become more baslc.
As Lhe elemenLs become less
meLalllc across a perlod, Lhelr oxldes
become more acldlc.
37
Electronegativity (_)
Several definitions exist, but all give very similar results.
_ is proportional to the average of the ionization energy and electron affinity.
_ has no units (review its overall trend in the movie (IVLE workbin-videos-
electronegativity).
If an element can readily give up an electron (low IE), and is not interested in
accepting an electron (small EA), then it will have a low _, e.g., Na.
If an element does not easily ionize (high IE), and is quite interested in accepting
an electron (large EA), then it will have a high _, e.g., F.
Small values of _ favor electron donation, whereas large values favor accepting
electrons.
Metals have small values of _, whereas nonmetals have large values.
Chemical bonds between atoms with large differences in _ have strong ionic
character.
Chemical bonds between atoms with similar _ values are largely covalent.
38
39
IE (eV), EA (eV) and EN(Pauling scale) of elements
Summary
Anomalous electronic configurations can be understood by considering the
overall stability of a particular electronic configuration.
An understanding of how Z
eff
and n vary in the periodic table as well as the most
stable electronic configurations is enough to understand the trends in the
following properties.
Ionization Energy
Roughly follows Z
eff
2
/n
2
, with some differences seen in the transition metals.
Electron Affinity
Depends on the stability and availability of an AO in a neutral atom to hold
the extra electron.
Atomic Radius
Roughly follows n
2
/Z
eff
.
Electronegativity.
Proportional to the average of IE and AE.
Provides much insight into the nature of chemical bonds (covalent, ionic, and
can even be related to the energy change that occurs in a redox reaction!)
40