MSE 280: Introduction to Engineering Materials

Atomic structure and Bonding

Reading: Chapter 2 g p

Overview
Electrons, protons and neutrons in atoms (Bohr and QM models). IP, EA, , and periodic trends. Bonding between atoms. Intermolecular forces. Relation to macroscopic properties.
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Electrons in atoms
orbital electrons: n = principal quantum number
n=3 2

1
Adapted from Fig. 2.1, Callister 6e.

Nucleus: Z = # protons N = # neutrons

Atomic mass A Z + N

Electrons in discrete orbitals. Bohr atom: 1) electrons are particles that revolve around the nucleus. 2) quantized angular momentum. Quantum Mechanics: Wave or matrix mechanics Probability. 2
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Comparison of Bohr and QM models

Figs. 2.2 and 2.3 from Callister 6 ed.

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Atomic orbitals

dxy

dyz

px

py

pz

Electrons... have discrete energy states (Quantized). tend to occupy lowest available energy state.
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dxz

dx2 y2
-

dz2

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Quantum numbers
Principal: n = 1, 2, 3, 4 Angular momentum: l = 0, 1, 2, 3, n 1 = s, p, d, f s = sharp, p = principal, d = diffuse, f = fundamental Magnetic: ml = 0, 1, 2, 3 , l Determines the number of states in a given l subshell (2l +1 total) Spin: ms = 1/2
e.g. eg 2s 1s n = 2, l = 0, ml = 0, ms = 1/2 n = 1, l = 0, ml = 0, ms = 1/2 Which atom is this? Be
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n = 2, l = 0, ml = 0, ms = -1/2 n = 1, l = 0, ml = 0, ms = -1/2

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Electron Configuration
- Shorthand notation to represent which states electrons occupy in an atom (without specifying electron spin).
e.g. Carbon 2p 2s

1s

Electron configuration: 1s22s22p2

Note - each energy level can only hold two electrons of opposite spin (Pauli exclusion principle). - for degenerate levels (e.g. 2p-orbitals), each orbital is filled with one electron before electrons are paired up.
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Electron configuration
1 electron in the s-orbital: Alkali metals Li, Na, K, Rb 2 electrons in the s-orbital: Alkaline earths Be, Mg, Ca Filled s-orbital and 4 electrons in p-orbital: Chalcogens O, S, Se Filled s-orbital and 5 electrons in p-orbital: Halogens F, Cl Br F Cl, Br Partially filled d-orbital: Transition metals e.g. Mn, Fe, Co Valence electrons determine which group atoms belong to.
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Stable configuration
Stable electron configurations...
have complete s and p subshells t d t be i t tend to b inert.

Z Element 2 He 10 Ne 18 Ar 36 Kr
Noble gases

Configuration 1s 2 Adapted from Table 2.2, Callister 6e. 2 2s 2 2p 6 1s 1s 2 2s 2 2p 6 3 s 2 3p 6 1s 2 2s 2 2p 6 3 s 2 3p 6 3d 10 4 s 2 4p 6

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Valence electrons
3s 2p p 2s 1s Na

Valence electron

3s 2p 2s 1s Na+

} Filled shell
leads to stability.

Lose an electron

Valence electrons
3p 3s 3 2p 2s 1s Cl Gain an electron

3p 3s 2p 2s 1s Cl-

} Filled shell
leads to stability.

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How much energy does it require to take an electron out of an atom?

Energy of an electron in vacuum Energy

IP

Valence electron Ionization potential (IP): Energy required to pull out a valence electron (in vacuum). By convention, IP is positive (i.e. need to put in energy to pull out the electron).
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How much energy does it require to place an electron in an atom?

Energy of electron in vacuum

Energy

EA Lowest available state Valence electrons

Electron Affinity (EA): Energy gained by putting an electron in (from vacuum). By convention, EA is negative (i.e. electron goes from higher energy state in vacuum to lower energy state in atom).
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How do we determine when an atom will accept an electron or give one up?
Vacuum level Energy y EA IP Lowest available state Valence electrons

Electronegativity (): a measure of how likely an atom will take up or give up an electron A simple (and intuitive) definition:

x~

-When two atoms are brought together, the atom with larger will have higher electron density around its nucleus. -Larger more ionic bond.
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IP + EA 2

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Bonding
Primary
Ionic Covalent Metallic
E

Secondary
Dipole-dipole H-bonds H bonds Dipole-induced-dipole Fluctuating dipoles
Equilibrium bond length

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Ionic Bonding
Occurs between + and - ions. Requires electron transfer. Large difference in electronegativity required. Example: NaCl
3p 3s

Na (metal) unstable electron Na (cation) stable

Cl (nonmetal) unstable

+
Coulombic Attraction

Cl (anion) stable

3p 3s Na ( = 0.9) Cl ( = 3.0)

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Ionic Bonding
Na (metal) unstable electron Na (cation) stable Cl (nonmetal) unstable

+
Coulombic Attraction

Cl (anion) stable

z1 z 2 e 2 EA = 4 o r

Since z1 = +1 for Na+ and z2 = -1 for Cl2 Negative energy means attraction only. A Will the atoms collapse on themselves? o

E =

4 r
B rn

A r

No, there is also repulsive energy (e.g. e-e repulsion)

ER =

B and n depend on atoms involved. In many cases n ~ 8.

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Ionic Bonding
E

ER =

B rn
r

Bond energy gy

EA =
Equilibrium bond length

A r

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Ionic Bonding: examples

Predominant bonding in Ceramics
H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7

Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 Ba 0.9 Ra 0.9 Ti 1.5 Cr 1.6 Fe 1.8

NaCl MgO M O CaF 2 Cs Cl

Ni 1.8 Zn 1.8 As 2.0

O 3.5

F 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2

He Ne Ar Kr Xe Rn -

Give up electrons

Acquire electrons
From Callister 6e resource CD.

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

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Covalent Bonding
Sharing of electrons Why do some atoms want to share electrons?
H

Molecular orbitals

H
1s

Example1: H2
Atomic orbitals

1s

H H H

Example2: CH4
C: has 4 valence e, needs 4 more H: has 1 valence e, needs 1 more

CH 4
H

shared electrons from carbon atom

H shared electrons from hydrogen atoms

Adapted from Fig. 2.10, Callister 6e.

Electronegativities are same or comparable.

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atomic orbitals for carbon: 2p

2s 1s

Atomic Orbitals
an s-orbital
z y x

4 valence electrons but two different types orbitals. Hs on CH4 should be equivalent.

px

three p orbitals

py

pz

Hybridization y
1s + 1p = sp-orbitals 1s + 2p = sp2-orbitals

sp3 hybridization for C in CH4

1s + 3p = sp3-orbitals

z y x x

60
y

60
x

y
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EXAMPLES: COVALENT BONDING

H2
H 2.1 21 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7

c column IVA

H2 O

C(diamond)
Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 Ba 0.9 Ra 0.9

F2
He O 2.0 F 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2 Ne Ar Kr Xe Rn -

Si C
Ti 1.5 Fe 1.8 Ga 1.6

Cr 1.6

Ni 1.8

Zn 1.8

C 2.5 Si 1.8 Ge 1.8 Sn 1.8 Pb 1.8

Cl 2

As 2.0

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is p g , ( g adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

GaAs

Molecules with nonmetals Molecules with metals and nonmetals Elemental solids (RHS of Periodic Table) Compound solids (about column IVA)

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% ionic character
Most bonds between two different types of atoms are somewhere in between ionic and covalent.

% ionic character = {1 exp[0.25( A

B ) 2 ]}

j = electronegativity of atom j
KEY POINT: Larger electronegativity difference
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more ionic
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Example problem
Order the following semiconductors from most covalent to most ionic. t l tt ti i
1) ZnS, GaP, CuCl 2) ZnS, ZnSe, ZnO

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Whats so important about ionicity of bonds?

Chemical properties
NaCl (highly ionic solid) dissolves readily in water but Si (covalent solid) does not.

Electronic properties
Ionicity of the bonds will have a strong influence on the band gap and other electronic properties.

All properties of materials are largely determined by the types and strength of bonds between the constituent atoms.
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Metallic Bonding
Arises from a sea of donated valence electrons

+ + +

+ + +

+ + +

Fixed ion cores (nuclei and inner electrons) sea of electrons

Adapted from Fig. 2.11, Callister 6e.

Primary bond for metals and their alloys. Large atomic radius and small IP will more likely lead to metallic bonding.
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Secondary Bonds: Intermolecular Forces

Van der Waals
Dipole-dipole interaction: secondary bond between molecules with permanent dipole moments

-general case: -ex: liquid HCl -ex: polymer

secondary bonding secondary bonding

Adapted from Fig. 2.14, Callister 6e. Adapted from Fig. 2.14, Callister 6e.

H Cl
second a

H Cl

ry bon ding

From Callister 6e resource CD.

Hydrogen bonding

H O H

O H H O H H
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 Dipole-induced-dipole interaction: secondary bond between molecules with permanent dipole moments
+ + +

polar

Nonpolar (e.g. atom)

secondary bonding

Fluctuating dipoles
asymmetric electron clouds

ex: liquid H 2 H2 H2

- secondary
bonding

H H

H H
secondary bonding
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Adapted from Fig. 2.13, Callister 6e.

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SUMMARY: BONDING
Type
Ionic Covalent

Bond Energy
Large! Variable large-Diamond small-Bismuth Variable large-Tungsten small-Mercury smallest

Comments
Nondirectional (ceramics) Directional (semiconductors, ceramics polymer chains) Nondirectional (metals) Directional inter-chain (polymer) inter-molecular
From Callister 6e resource CD.

Metallic Secondary

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PROPERTIES FROM BONDING: TM

Bond length, r
F

Melting Temperature, Tm
F

Energy (r)

r
Bond energy, Eo

ro r smaller T m

Energy (r) ro
u st etc ed e gt unstretched length

r Eo = bond energy

larger T m
Tm is larger if Eo is larger.
From Callister 6e resource CD.

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Elastic modulus, E
length, Lo

PROPERTIES FROM BONDING: E

cross sectional area A o

Elastic modulus
F L =E Ao Lo

undeformed deformed

E ~ curvature at ro Energy
unstretched length

ro r

E is larger if curvature at ro is larger.

From Callister 6e resource CD.

smaller Elastic Modulus larger Elastic Modulus

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SUMMARY: BONDING and Materials properties

Ceramics
(Ionic & covalent bonding):

Large bond energy

large Tm large E small

Metals
(Metallic bonding):

Variable bond energy

moderate Tm moderate E moderate

Polymers
(Covalent & Secondary):
second ary bo nding

Directional Properties
Secondary bonding dominates small T small E large
From Callister 6e resource CD.

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