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Lecture 03

This document discusses the electron configurations of multi-electron atoms. It explains that while hydrogen has a simple electron configuration, larger atoms require approximations due to the Schrodinger equation being impossible to solve exactly. The key principles discussed include: 1. Pauli exclusion principle and Hund's rule govern how electrons fill atomic orbitals. 2. Electrons experience an effective nuclear charge that is reduced by shielding from inner electrons. 3. Orbital energies are influenced by the effective nuclear charge, with penetration ability affecting their relative energies. 4. Electron-electron repulsion and spin-pairing energy determine the lowest energy and most stable electron configurations. Exceptions to the aufbau

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46 views

Lecture 03

This document discusses the electron configurations of multi-electron atoms. It explains that while hydrogen has a simple electron configuration, larger atoms require approximations due to the Schrodinger equation being impossible to solve exactly. The key principles discussed include: 1. Pauli exclusion principle and Hund's rule govern how electrons fill atomic orbitals. 2. Electrons experience an effective nuclear charge that is reduced by shielding from inner electrons. 3. Orbital energies are influenced by the effective nuclear charge, with penetration ability affecting their relative energies. 4. Electron-electron repulsion and spin-pairing energy determine the lowest energy and most stable electron configurations. Exceptions to the aufbau

Uploaded by

yinglv
Copyright
© Attribution Non-Commercial (BY-NC)
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Discussion Session

Monday, 5-7 pm

9 LEWIS


Textbook

Chapter 2 (MT), Chapter 1 (DG)
20 copies on Reserve
Chemistry Library
Contour diagram
Orbital depiction is based on
With the sign of indicted (very important for
bonding considerations)
2

3pz
Orbital Radial
Function
R(r)
Angular
Function
Y(x,y,z)
Angular
Function
Y(u,|)
pp36, DG
pp26, MT
z
p 2
2 /
6 2
1
r
re

t 2
) / ( 3 r x
t
u
2
cos 3
Orbital Radial
Function
R(r)
Angular
Function
Y(x,y,z)
Angular
Function
Y(u,|)
pp36, DG
pp26, MT
t 2
) / ( 3 r x
t
u
2
cos 3
z
p 3
3 / 2
) 6 (
6 81
4
r
e r r


Orbital Radial
Function
R(r)
Angular
Function
Y(x,y,z)
Angular
Function
Y(u,|)
pp36, DG
pp26, MT
2
3
z
d
3 / 2
30 81
4
r
e r

t 4
/ ) 3 ( 5
2 2 2
r r z
t
u
4
) 1 cos 3 ( 5
2

All atomic orbitals (on same atom) are mutually orthogonal.


0
2 1
=
}
dV
Ungerade
x
y
z
1 electron system: Hydrogen

How about many-electron system?
Z+
1 electron with nuclear charge Z
Increasing electrostatic interaction
Orbital contract
Orbital energy drops
r
Ze
r V
2
) ( =
2
2
6 . 13
n
eV Z
E
n

=
Example: For He+, Z=2, E1=-54.4 eV
For multi-electron atoms, Schrodinger equation can be
set up, but can not be solved exactly.
Use approximation.
Build many-electron electron system:
1. Pauli exclusion principle:
No two electrons in an atom can have the same set of
four quantum numbers (n, l, ml, ms)

ms: spin quantum number
Quantized, +1/2 or 1/2
Each atomic orbital can contain at
most two electrons.
Aufbau principle: electron fill the atomic
orbitals from the lowest energy up.
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d..
Example:

He: 1,0,0, & 1,0,0, -1/2

Li: 1,0,0, ; 1,0,0,-1/2; 2,0,0,

Al: 13 electrons
2
1s
1 2
2 1 s s
1 2 1 2 6 2 2
3 3 ] [ 3 3 2 2 1 p s Ne p s p s s =
Core
electron
Valence
electron
Recall in Hydrogen:
2 2 2
4 2 2
2
2 n
k
h n
e m
r
e
E
e
n
n
= = =
t
Why are they different in multi electron system?
E(2s)=E(2p)
Electron-electron repulsion
2+
He = He + 1 e
+
First electron:
2
2
6 . 13
n
eV Z
E
n

=
Second electron??
Ionization Energy (IE): energy required to
remove an electron from the gaseous atom.
IE(He) =24.6 eV
eV He E 4 . 54 ) (
1
=
+
Each electron feels +2 nucleus and 1 electron.
In a many-electron atom, each electron is simultaneously:
attracted to the protons in the nucleus
repelled by other electrons (like-charge repulsion)

The net positive charge attracting the electron is called the effective
nuclear charge

For He:

34 . 1 =
eff
Z
eV
n
Z
E
eff
6 . 13
2
2
=
=-24.4 eV
IE(He) =24.6 eV
Now, Li?
1 2
2 1 s s
2s orbital penetrates the inner 1s electron shell better than 2p.

2s electron feel a greater effective nuclear charge lower E for 2s
) 2 ( ) 2 (
1 1
p Z s Z
eff eff
> E(2s) <E(2p)
Ground State: 1 2
2 1 s s
For Z >1:

E(ns) < E(np) < E(nd) < E (nf) for given n

Z(eff):

Penetrating ability:
low
poor
o = Z Z
eff
Shielding constant
Example:

O:
4 2 2
2 2 1 p s s
45 . 3 55 . 4 8
55 . 4 ) 35 . 0 ( 5 ) 85 . 0 ( 2
2
= = =
= =
o
o
Z Z
eff
p
Be:

B:

C:

2 2
2 1 s s
1 2 2
2 2 1 p s s
2 2 2
2 2 1 p s s
Hunds rule: For any set of orbitals of equal energy
(degenerate orbitals), the electron configuration with
the maximum number of parallel spins is the ground
state.
Now 4s, 3d orbitals:

K:

Ca:
1
4 ] [ s Ar
2
4 ] [ s Ar
For neutral, many-electron atoms, the 4s orbital is filled
before the 3d orbital.
How to write the electron configuration?
In the sequence of ionization energy from left to right, those first
Be removed , in the right.

Example: Fe (Z=26):

Note the aufbau process gives you:
2 6
4 3 ] [ s d Ar
6 2
3 4 ] [ d s Ar
Fe:

3p

3d

4s
2 6 6 2 6 2 2
4 3 3 3 2 2 1 s d p s p s s
25 . 11 ) 00 . 1 ( 2 ) 85 . 0 ( 8 ) 35 . 0 ( 7
3
= + + =
p
o
75 . 19 ) 00 . 1 ( 18 ) 35 . 0 ( 5
3
= + =
d
o
25 . 22 ) 00 . 1 ( 10 ) 85 . 0 ( 14 ) 35 . 0 ( 1
4
= + + =
s
o
75 . 3 ) 4 (
25 . 6 ) 3 (
75 . 14 ) 3 (
=
=
=
s Z
d Z
p Z
eff
eff
eff
E(3p)<E(3d)<E(4s)
4s electrons will be first removed!
Question:

Since E(3d) <E(4s), why not ??
8
3 ] [ d Ar
1. Electron-electron repulsion
2. Spin-pairing energy

Compare the total energy
n m
b a
) , (
2
) 1 (
) ( ) ( ) ( a a J
m m
b nW a mW A E

+ =
) , (
2
) 1 (
) , ( b b J
n n
b a nJ m

+ +
Binding energy
e-e repulsion
Example: Sc Z=21
2 1
4 3 ] [ s d Ar
3
3 ] [ d Ar
E=-W(d)-2W(s)+2J(ds)+J(ss)
E=-3W(d)+3J(dd)
W(d)=24.75eV
W(s)=21.60eV
J(ds)=8.38eV
J(dd)=11.78eV
J(ss)=6.6eV
eV
ss J ds J s W dd J d W
s d E d E
68 . 5
) ( ) ( 2 ) ( 2 ) ( 3 ) ( 2
) 4 3 ( ) 3 (
2 1 3
=
+ + =

Ground state:
2 1
4 3 ] [ s d Ar
e-e repulsion in d orbital: ground state


Stronger shielding for 4s, smaller effective Z:
4s electron will be first removed.

Ground state for
2 1
4 3 ] [ s d Ar
1 1
4 3 ] [ : s d Ar Sc
+
Exceptions:

Special stability of half-filled and filled shell:


s d f Xe Au
s d Kr Ag
s d Kr Mo
s d Ar Cu
s d Ar Cr
6 5 4 ] [ :
5 4 ] [ :
5 4 ] [ :
4 3 ] [ :
4 3 ] [ :
10 14
10
5
10
5
Next Lecture:



Atomic Energy States

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