Chapter 7:

The Quantum
Mechanical Atom
 Orbitals Characterized by Three
Quantum Numbers:
Quantum Numbers:
 Shorthand
 Describes characteristics of electron’s position
 Predicts its behavior
n = principal quantum number
 All orbitals with same n are in same shell
ℓ = secondary quantum number
 Divides shells into smaller groups called subshells
mℓ = magnetic quantum number
 Divides subshells into individual orbitals
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2
 n = Principal Quantum Number
 Allowed values: positive integers from 1 to 
 n = 1, 2, 3, 4, 5, … 
 Determines:
 Size of orbital
 Total energy of orbital
 For given atom,
 Lower n = Lower (more negative) E
= More stable

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 3

ℓ = Orbital Angular Momentum QN
 Allowed values: 0, 1, 2, 3, 4, 5…(n – 1)
 Letters: s, p, d, f, g, h
Orbital designation
 number nℓ letter
 Possible values of ℓ depend on n
 n different values of ℓ for given n
 Specifies orbital angular momentum of e
 Determines :
 Shape of orbital

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 4

 mℓ = Magnetic Quantum Number
 Allowed values:
 mℓ = ℓ, ℓ+1, ℓ+2, …, 0 , …, ℓ2, ℓ1, ℓ
 Possible values of mℓ depend on ℓ
 There are 2ℓ +1 different values of mℓ for given ℓ
 z axis component of orbital angular momentum
 Determines orientation of orbital in space
 To designate specific orbital, you need three
quantum numbers
 (n, ℓ, mℓ)
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 5
 Table 8.1 Summary of Relationships
Among the Quantum Numbers n, ℓ, and m

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 6

 4. Spin Quantum Number, ms
 Arises out of behavior of
e in magnetic field
 e acts like a top
 Spinning charge is like a
magnet
 e behave like tiny
magnets
 Leads to 2 possible
directions of e spin Possible Values:
 up and down
+½ ½
 north and south
 
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 7
 Pauli Exclusion Principle
 No two e in same atom can have same set of all
four quantum numbers (n, , m, ms)
 Can only have 2 e per orbital
 2 e s in same orbital must have opposite spin
 e s are paired
 Odd number of es
 Not all spins paired
 Have unpaired es
 Even number of es
 Depends on number of orbitals
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 8
 Know from Magnetic Properties
 Two e s in same orbital with different spin
 Spins paired—diamagnetic
 Sample not attracted to magnetic field
 Magnetic effects tend to cancel each other
 Two e s in different orbital with same spin
 Spins unpaired—paramagnetic
 Sample pulled into magnetic field
 Magnetic effects add
 Measure extent of attraction
 Gives number of unpaired spins
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 9
 Your Turn!
Which of the following is a valid set of four quantum
numbers (n, ℓ, mℓ, ms)?
A. 3, 2, 3, +½
B. 3, 2, 1, 0
C. 3, 0, 0, -½ true anwer
D. 3, 3, 0, +½
E. 0, -1, 0, -½

C
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 10
 Your Turn!
What is the maximum number of electrons allowed
in a set of 4p orbitals?- - -
A.14
B.6
C.0
D.2
E.10

B
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 11
 Energy Level Diagram for Multi e
Atom/Ion

4f
6s
5p
4d
5s
4p
4s 3d
3p
3s
Energy

2p  How to put e– into a diagram?

2s
 Need some rules

1s

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 12

 ss ps ps dps dps fdps fdps

 1s2s 2p3s 3p4s 3d4p5s 4d5p6s 4f5d6p7s

5f6d7p8s

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 13

 Hund’s Rule
 If you have more than 1 orbital all at the same
energy
 Put 1e into each orbital with spins parallel (all
up) until all are half filled
 Before pair up es in same orbital
Why?
 Repulsion of e in same region of space
 Empirical observation based on magnetic
properties

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 14

 Learning Check
Give electron configurations and orbital diagrams
for Na and As
6s
5p
4d
5s
4p
4s 3d
3p
3s
Energy

2p
2s

As Z = 33

1s
1s22s22p63s23p64s23d104p3
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 15
 Your Turn!
The ground state electron configuration for Ca is:
A.[Ar] 3s1
B.1s2 2s2 2p6 3s2 3p64s2
C.[Ar] 4s2
D.[Kr] 4s1
E.[Kr] 4s2

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 16

 Sublevels and the Periodic Table
 Each row (period) represents different energy level
 Each region of chart represents different type of
sublevel

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 17

 Noble Gas Core Notation for Mn
 Find last noble gas that is filled before Mn
 Next fill sublevels that follow [Ar] 4s 2 3d 5
n= 1 1 2
“ns” orbital being filled
H He
n= 2 3 4 “np” orbital being filled 5 6 7 8 9 10
Li Be “(n – 1)d” orbital being filled B C N O F Ne
n= 3 11 12 13 14 15 16 17 18
“( n – 2)f” orbital being filled
Na Mg Al Si P S Cl Ar
n= 4 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
n= 5 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
n= 6 55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
n= 7 87 88 89 104 105 106 107 108 109 110 111
Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 18
 Electronic Configurations:
 A few exceptions to rules

Element Expected Experimental

Cr [Ar] 3d4 4s2 [Ar] 3d5 4s1
Cu [Ar] 3d9 4s2 [Ar] 3d10 4s1
Ag [Kr] 4d9 5s2 [Kr] 4d10 5s1
Au [Xe] 5d9 6s2 [Xe] 5d10 6s1

 Exactly filled and exactly half-filled subshells have

extra stability
 Means that you can promote 1 electron into next
higher energy orbital to gain this extra stability
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 19
 Your Turn!
Which of the following choices is the correct
electron configuration for a cobalt atom?
4s 3d
A.[Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑
B.[Ar] ↑ ↑↓ ↑↓ ↑↓ ↑↓
C.[Ar] ↑ ↑↓ ↑↓ ↑↓ ↑ ↑
D.[Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑
E.[Ar] ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

E
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 20
 Atomic Size
 Theory suggests sizes of atoms and ions indistinct
 Experiment shows atoms/ions behave as if they
have definite size
 C and H have ~ same distance between nuclei in
large number of compounds
Atomic Radius (r)
 Half of distance between two like atoms
 H—H C—C etc.
 Usually use units of picometer
 1 pm = 1 x 1012 m
 Range 37 – 270 pm for atoms
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 21
 Trends in Atomic Radius (r)
 Down Column (group)
 Zeff essentially constant
 n, outer e s farther away from nucleus and radius

 Across row (period)
 n constant
 Zeff, outer e s feel larger Zeff and radius 
Transition Metals and Inner Transition Metals
 Size variations less pronounced as filling core
 n same (outer e s) across row
  Zeff and r more gradually
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 22
Atomic and Ionic Radii (in pm)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 23

 Ionic Radii
  down column (group)
  across row (period)
Cations smaller than parent
atom
 Same Zeff, less e s,
 Radius contracts
Anions larger than parent
atom
 Same Zeff, more e s
 Radius expands
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 24
 Your Turn!
Which of the following has the smallest radius
(size)?
A.Ar
B.K+ 
C.Cl–
D.Ca2+
E.S2–

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 25

 Ionization Energy
 Energy required to remove e from gas phase
atom
 Corresponds to taking e from n to n = 
 1st IE M (g)  M+ (g) + e

 IE = E

Trends: IE  down column (group) as n

IE  across row (period) as Zeff 

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 26

 Comparing 1st IE’s
 Largest 1st IEs are
in upper right
 Smallest 1st IEs
are in lower left

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 27

Successive Ionization Energies
  slowly as
remove each
successive e
 See big  in IE
 When break into
exactly filled or
half filled
subshell

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 28

Table 8.2: Successive Ionization Energies in
kJ/mol for H through Mg

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 29

 Your Turn!
Place the elements C, N, and O in order of
increasing ionization energy.
A.C, N, O
B.O, N, C
C.C, O, N
D.N, O, C
E.N, C, O

C
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 30