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Lecture 9 CHEM 101 Fall 2023
Lecture 9 CHEM 101 Fall 2023
Lecture 9 CHEM 101 Fall 2023
CHEM 101
Lecture 9
https://www.youtube.com/watch?v=vpph2cHx6gk
1
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
1
Experimental
Orbital energy of 1s in He = –25 eV
Z =+2 r Z = +3 r
r, aₒ
Moving across the second period
E2s = – 5.34
Zeff = 1.25
Li
1s2 2s2 Be
4Be Z=4 B
E2s = – 8.41
Zeff = 2.47
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
2s or 2p Excited state
A (g) A+(g) + e −
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 )
Experimental Ionization energy is lower Differences are associated with the way in which the electrons
11
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
2 2 6
Three pairs of electrons with parallel spin
10Ne 1s 2s 2p
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
12
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