Principles of Chemistry

CHEM 101
Lecture 9

https://www.youtube.com/watch?v=vpph2cHx6gk
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Multi-electron atoms
1H = 1s1
Electron-electron repulsion Repulsion
2He 1s2 Electron
Electron
Attraction
Attraction
Li 1s 2 2s1
3
2 2
4Be 1s 2s Nucleus
2 2 1
5B 1s 2s 2p
each electron experiences the nuclear
10Ne 1s2 2s2 2p6 charge and an average repulsion from all
of the other electrons in the atom.

Energies of these orbitals in multi-electron atoms are different from those in hydrogen.

Energy of an orbital in a multi-electron atom is influenced by all the other electrons as a result of the
electron-electron repulsion.
Orbital energies in multi-electron systems 2
Orbital energies 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, ……………

The energy of a set of orbitals with the same n and l Once a shell is full its
falls steadily as the nuclear charge increases. energy falls rather rapidly.
Orbital energies
Z 2 RH RH = Rydberg Constant
En = − 2 (2.178  10-18 J or 13.61 eV) 1H 1s1 = –13.6eV
n
1s2 (2 2 )(13 .6eV )
2He E1s ( He) = − 2
= −54 .4eV Calculated
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Experimental
Orbital energy of 1s in He = –25 eV

Electron-electron repulsion 29.4 eV Difference

3Li 1s2 2s1

If 2s electron experiences full nuclear charge (Z = +3)

(32 )(13 .6eV )

− = −30 .6eV Calculated
n=2
2 2
En = – 5.34 eV Zeff = 1.25
If 2s electron experiences reduced nuclear charge (Z = +1) RH = 13.6 eV
(12 )(13 .6eV )
− 2
= −3.4eV Calculated
2

E2s (Li) = – 5.34 eV Experimental Effective charge is in between:

Neither 3 nor 1
 Z 2 RH 3Li 1s2 2s1
En = − 2s electron will experience full nuclear charge (Z=+3)
n2 Zeff = 1.25
(32 )(13 .6eV )
2He 1s2 − 2
= −30 .6eV Calculated
2 Effective charge is
2
(2 )(13 .6eV ) 2s electron will experience reduced nuclear charge (Z=+1)
in between: Neither
E1s ( He) = − 2
= −54 .4eV
1 (12 )(13 .6eV ) +3 nor +1
Calculated − 2
= −3.4eV Calculated
Orbital energy of 1s in He = –25 eV 2
Experimental E2s (Li) = – 5.34 eV
Zeff = 1.34 Why the ground state
Experimental
configuration of Li is 1s2 2s1
and not 1s2 2p1?
Higher the penetration of electron
closer to the nucleus, lower its
energy will be.
1s P(r)
2s electrons will be lower in
P(r) P(r) 1s energy than 2p electrons.
2s

Z =+2 r Z = +3 r
r, aₒ
Moving across the second period

3Li 1s2 2s1 Z=3

E2s = – 5.34
Zeff = 1.25
Li
1s2 2s2 Be
4Be Z=4 B
E2s = – 8.41
Zeff = 2.47

5B 1s2 2s2 2p1 Z=5

E2s = – 13.5
Zeff = 3.97

E2p = – 8.43
Zeff = 2.48

Z 2 RH
En = −
n2 7
 Boron orbitals are contracted but
similar to the orbitals of Hydrogen.
P(r)
 Orbital energies of excited states

One electron systems

1H = 1s1 Ground state

2s or 2p Excited state

Energy is defined by the n of the occupied orbital

6C = 1s2 2s2 2p2 Ground state

Energies of empty orbitals

Ground state Excited states
We can only talk about the energy of an occupied orbital.
Ionization energies (IE) and orbital energies
IE of a particular electron in an atom is defined as the energy change for the following process:

A (g) A+(g) + e −

IEn = energy of A+(g) – energy of A (g)

One-electron atom with nuclear charge Z

Z 2 RH
IEn = 0 − (− ) Z 2 RH
n 2 En = −
n2
Z 2 RH
IEn =
n2 For multi-electron atom

IEn = −( En ) IEn  −( En )

ionization energy = – orbital energy

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 Ionization Energies of multi-electron Atoms
First ionization energy and minus the energy of the highest energy AO

Experimental Ionization energy is lower Differences are associated with the way in which the electrons
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than the prediction from orbital energy fill the p orbital – changes in the exchange energy.
 Exchange energy px py pz Electrons are arranged in such a way as to
maximize the number of parallel spins.
5B 1s2 2s2 2p1
The result of the exchange interaction is that each
6C 1s2 2s2 2p2 pair of electrons with parallel spins (both up, or
1s2 2s2 2p3 both down) leads to a lowering of the electronic
7N
energy of the atom.
8O 1s2 2s2 2p4

1s2 2s2 2p5 n p3

9F

2 2 6
Three pairs of electrons with parallel spin
10Ne 1s 2s 2p

One pair of electrons with parallel spin

Effect on the ionization energies One pair of electrons with parallel spin

each pair of electrons with parallel One pair of electrons with parallel spin
spins contributes –K to the electronic
energy of the atom, where K is a
constant
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 Exchange energy # of pairs Exchange Eexch (ion) – Eexch (atom)
# of pairs
with contribution
with Exchange
same to Energy
Atoms Ions same contribution to the
spin (ECE)
spin ECE ionization energy

5B: 1s22s2 2p1 0 0 B1+: 1s22s2 2p0 0 0 0

6C: 1s22s2 2p2 1 -K C1+: 1s22s2 2p1 0 0 K

7N: 1s22s2 2p3 3 -3K N1+: 1s22s2 2p2 1 -1K 2K

2 2 4 -3K O1+: 1s22s2 2p3 -3K 0

8O: 1s 2s 2p 3 3

9F: 1s22s2 2p5 4 -4K F1+: 1s22s2 2p4 3 -3K K

2 2 6 6 -6K Ne1+: 1s22s2 2p5 4 -4K 2K
10Ne: 1s 2s 2p