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Chapter 3
Chapter 3
Chapter 3
Crystal Binding
The internal energy of a crystal
Ionic crystals
The Born theory of ionic crystals
Van Der Waals crystals
Dipoles
Inert cases
Induced dipoles
The lattice energy of an inert-gas solid
The Debye frequency
The zero-point energy
Dipole-quadrupole and quadrupole-quadrupole terms
Molecular crystals
Refinements to the Born theory of ionic crystals
Covalent and metallic bonding
1
物理冶金 Crystal Binding 魏茂國
Introduction
- Crystalline solids are empirically grouped into 4 classifications: (1) ionic,
(2) van der Waals, (c) covalent, and (d) metallic.
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物理冶金 Internal Energy of a Crystal 魏茂國
3
物理冶金 Ionic Crystals 魏茂國
4
Fig. 3.1 The sodium chloride lattice
物理冶金 Ionic Crystals 魏茂國
5
Fig. 3.3 The zincblende lattice, ZnS.
物理冶金 Born Theory of Ionic Crystals 魏茂國
where e1 and e2 are the charges on the ions, r12 is the center-to-center distance
between the ions, and k is a constant.
If cgs units are used, k = 1 dyne (cm2)/(statcoulombs)2, and if mks units are
employed, k = 9109 Nm2/C2.
e1 r12 e2 6
物理冶金 Born Theory of Ionic Crystals 魏茂國
where is the total potential energy of the ion, M is its energy due to coulomb
interactions with all the other ions, and R is the repulsive energy.
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物理冶金 Born Theory of Ionic Crystals 魏茂國
If one uses the cgs system of units where, in Eqs. 3.1 and 3.2, k = 1 this expression
may be written
Az 2 e 2 Be 2
n (3.4)
r r
where e is the electron charge, z is the number of electronic charges on the ions, r is
the distance between centers of an adjacent pair of negative and positive ions (Fig. 3.4),
n is a large exponent, usually of the order of 9, and A and B are constants.
8
Fig. 3.4 Interionic distances in the sodium chloride lattice.
物理冶金 Born Theory of Ionic Crystals 魏茂國
If we now think in terms of the potential energy of a crystal containing one mole of
NaCl, the preceding equation becomes,
ANz 2 e 2 NBe 2
U n (3.5)
r r
where N is Avogadro’s number (6.0221023) and U is the total lattice potential
energy. The first term on the right-hand side of this equation represents the
electrostatic energy due to simple coulomb forces between ions, whereas the second
term is that due to the repulsive interactions that arise when ions closely approach
each other.
It is a basic assumption of the Born theory that the repulsive energy can be expressed
as a simple inverse power of the interionic distance.
9
物理冶金 Born Theory of Ionic Crystals 魏茂國
- Let us consider the coulomb energy term of the Born equation, which for a single ion
is z 2e 2 A
M (3.6)
r
Assumed that we are specially interested in a sodium chloride crystal where there is a
unit charge on each ion and z2 = 1.
e2 A
M (3.7)
r
Because the coulomb energy varies inversely as the first power of the distance
between charged ions, coulomb interactions act over large distances, and it is not
sufficient to consider only the coulomb energy between a given ion and its immediate
neighbors.
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物理冶金 Born Theory of Ionic Crystals 魏茂國
In Fig. 3.4, the coulomb energy of a single ion equals a series of terms of the form
6e 2 12e 2 8e 2 6e 2 24e 2
M ... (3.8)
1r 2r 3r 4r 5r
Ae2 e2
M 6 8.45 4.62 3.00 10.7... (3.9)
r r
For sodium chloride, the Madelung number (A) is
1.7476 and the coulomb, or Madelung energy, for
one ion in the crystal is, accordingly,
1.7476e 2
M (3.10)
r
12
Fig. 3.4
物理冶金 Born Theory of Ionic Crystals 魏茂國
14
物理冶金 Born Theory of Ionic Crystals 魏茂國
- The general equation for the force between electric charges is f ke1e2 / r122 , where k is
a constant with units force distance2 charge2. In the electrostatic or cgs system of
units, k = 1 dynecm2/(statcoulombs)2. Prove that k = 9109 Nm2/C2 in the
international (mks) system of units. (1 dyne = 10-5 N, 1 statcoulomb = 10-9 C/3)
1 10 N 10 m
5 2 2
1dyne cm 2
N m 2
k 9 10 9
15
物理冶金 Van der Waals Crystals 魏茂國
16
物理冶金 Dipoles 魏茂國
Dipole (偶極)
- An electrical dipole is formed by a pair of oppositely charged particles (+e1 and –e1)
separated by a small distance (a). Because the charges are not concentric, they
produce an electrostatic field that is capable of exerting a force on other electrical
charges.
- In Fig. 3.6, let l1 and l2 be the respective distances from the 2 charges of the dipole
to a point in space at a distance r from the midpoint of the dipole. If r is large
compared to a, then the potential at the point p, using cgs units, is given by
e1 e2 e1 e1
V (3.14)
l1 l2
a
a
r cos r cos
2 2
a a
1 cos 1 cos
e 2r 2r
V 1 2 (3.15)
r a
1 cos
2 r
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Fig. 3.6 An electrical dipole.
物理冶金 Dipoles 魏茂國
a
cos
e1 r
V 2 (3.16)
r a
1 cos
2 r
Since (a/2r) <1, Eq. 3.16 simplifies to
e1 a cos e1a cos
V (3.17)
r r r2
The components of the electric field intensity in the radial and transverse directions are
then given by
V 2e1a cos
Er
r r3
(3.18)
1 V e1a sin
E
r r3
where r is the distance from the dipole to the point p, and is the angle between the
axis of the dipole and the direction r. It is customary to call the quantity e1a, the
product of one of the dipole charges and the distance between the dipole charges, the
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dipole moment () (偶極矩).
物理冶金 Dipoles 魏茂國
2ke cos
Fr
r3
(3.20)
ke sin
F
r3
Note that the electric field intensity due to a dipole varies as the inverse cube of the
distance from the dipole, whereas the field of a single charge varies as the inverse
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square of the distance.
物理冶金 Inert Cases 魏茂國
Inert cases
- It is interesting that the inert-gas atoms crystallize (at low temperature) in the face-
centered cubic system.
- Because of their closed-shell structures, we can consider that over a period of time
the negative charges of the electrons are distributed about the nucleus with complete
spherical symmetry. The center of the negative charge on a time-average basis
therefore coincides with the center of the positive charge on the nucleus, which
means that the inert gas atoms have no average dipole moment.
- They do, however, have an instantaneous dipole moment because their electrons, in
moving around the nuclei, do not have centers of gravity that instantaneous coincide
with the nuclei.
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物理冶金 Induced Dipoles 魏茂國
21
物理冶金 Induced Dipoles 魏茂國
- In Fig. 3.7, consider the force exerted by the left dipole on the right dipole. The
induced dipole in the right-hand atom is equivalent to the pair of charges –e’ and +e’
separated by the distance a’. According to this, the induced dipole moment is e’a’.
Let E be the field intensity due to the instantaneous dipole on the left atom at the
negative charge (-e’) of the induced dipole. The corresponding field at the position of
the positive charge (+e’) of the induced dipole is E+a’dE/dr. The total force on the
induced dipole to the field of the other dipole is
dE dE dE
f e' E e' E a' e ' a ' I (3.22)
dr dr dr
dE dE
I E f I E (3.23)
dr dr
In general the field of a dipole is proportional to the inverse cube of the distance
2e1a cos 2 cos
E (3.24) E r
3 3
r3 r r
dE d 3 3 2 2
f E 3 3 3 4 7 (3.25)
dr r dr r r r r 7
r
The energy of a pair of inert-gas atoms due to the dipole interactions can be evaluate
as follows
2 2 2
r
r 2 1 6
dr r 6 6 (3.26)
6
7
r 6r r
The van der Waals energy between a pair of inner-gas atoms due to dipole interactions
varies as the square of the dipole moment and the inverse sixth power of their distance
of separation.
Over a period of time the average dipole moment for an inert-gas atom must be zero.
The square of this quantity does not equal zero, and it is on this basis that inert-gas
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atoms can interact.
物理冶金 Lattice Energy of an Inert-Gas Solid 魏茂國
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物理冶金 Debye Frequency 魏茂國
Debye frequency
- In a crystalline solid, an atom is free to vibrate independently in 3 orthogonal
directions. A crystal of N atoms is considered as equivalent to 3N oscillators of
various frequencies v.
- Debye assumed that the forces of interaction between a neighboring pair of atoms
were roughly equivalent to a linear spring.
Pushing the atoms together would have the effect of compressing the spring, and in
so doing, a restoring force would be developed that would act to return the atoms to
their rest positions.
Pulling the atoms apart would produce an equivalent opposite result.
On this basis, Debye concluded that the entire lattice might be considered to be a
3-dimensional array of masses interconnected by spring.
In fact, assuming a simple cubic crystal, each atom would be held in space by a set
of 3 pairs of springs, as indicated in Fig. 3.8B. A one-dimensional crystal will be
considered, as indicated in Fig. 3.8B.
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物理冶金 Debye Frequency 魏茂國
(A) (B)
Fig. 3.8 (A) Debye model of a simple cubic crystal pictures an atom
as a mass joined to its neighbors by springs. (B) A one-dimensional
crystal model.
- The vibration modes of such an array are analogous to the standing waves that can be
set up in a string. According to Debye, as shown in Fig. 3.9, the minimum wavelength
or the mode of maximum frequency is obtained when neighboring atoms vibrate
against each other.
- The minimum wavelength corresponds to twice the spacing between the atoms, or
min = 2a, where a is the interatomic spacing.
The (maximum) vibrational frequency associated with this wavelength is
v
vm (3.28)
where v is the velocity of the shortest sound waves. This latter is normally of the
order of 5103 m/s.
At the same time, the interatomic spacing in metals is ~0.25 nm, so that
The value, vm = 1013 Hz, is often used in simple calculations to represent the vibration
frequency of an atom in a crystal.
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物理冶金 Zero-Point Energy 魏茂國
Zero-point energy
- The zero-point energy of a crystal is its thermal energy when the atoms are
vibrating in their lowest energy states.
- In a 3-dimensional crystal of N atoms, each atom inside the
crystal can undergo transverse vibrations in 3 independent
directions (Fig. 3.8A), it is possible to show that there are
3N independent transverse modes of vibrations.
- In a linear crystal (Fig. 3.8B), the density of vibrational Fig. 3.8(A)
modes is the same in any frequency interval dv.
However, in a 3-dimensional array or crystal the Fig. 3.8(B)
vibrational modes are 3-dimensional, and the multiplicity of the standing wave
patterns increases with increasing frequency. As a result, in the 3-dimensional case
the number of modes possessing frequencies in the range v to v+dv is given by
9N
f ( v )dv 3 v 2dv (3.30)
vm
where f(v) is a density function, N is the number of atoms in the crystal, v is the
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vibrational frequency of an oscilllator, and vm is maximum vibrational frequency.
物理冶金 Zero-Point Energy 魏茂國
- Fig. 3.10 is a schematic plot of the Debye density function f(v) as a function of v. The
area under this curve from v = 0 to v = vm equals 3N, the total number of oscillators.
According to the quantum theory, the zero-point energy of a simple oscillator is hv/2.
The total vibrational energy of the crystal at absolute zero is, accordingly,
vm
vm hv 9 N 2 hv
vm 9 Nhvvm 9 Nhv 4
3
9
EZ 0 f ( v ) dv 0 3 v dv 0 dv 8v 3 Nhvm (3.31)
2 vm 2 2vm3 m 0 8
- The correction due to the zero-point energy is ~31% or ~0.5 kJ/mol in the case of
neon, so that the lattice energy U0 should be ~2.47 kJ/mol rather than 1.88 kJ/mol, as
shown in Table 3.1.
31
Source: http://hyperphysics.phy-astr.gsu.edu/hbase/electric/elequad.html
物理冶金 Molecular Crystals 魏茂國
Molecular crystals
- Many molecules form crystals which are held together by van der Waals forces.
Among these are N2, H2, and CH4; these are typical covalent molecules in which the
atoms share valence electrons to effectively obtain closed shells for each atom in
the molecule. These molecules are nonpolar molecules; they do not have permanent
dipole moments.
- There are also polar molecules, such as water (H2O), which possess permanent
dipoles. The interaction between a pair of permanent dipoles is, in general, much
stronger than that between induced dipoles.
32
物理冶金 Refinements to the Born Theory of Ionic Crystals 魏茂國
33
物理冶金 Covalent and Metallic Bonding 魏茂國
Introduction
- In Fig. 3.11, the coordination number of the diamond structure is 4.
- Pauli exclusion principle: two electrons can occupy the same quantum state only if
the spins are oppositely directed.
- In general, covalent crystals follow what is known as the (8-N) rule, where N is the
number of valence electrons, and the factor (8-N) gives the number of nearest
neighbors in the structure.
A much more important type of electron interchange occurs when both electrons
simultaneously exchange nuclei. The resulting shifting of the electrons back and forth
between the nuclei, which occurs at a very rapid rate, is commonly known as a
resonance effect, and ~80% of the binding energy of the hydrogen molecule is
attributed to it.
In addition to the ionic and the exchange, or resonance energy, there are other more
complicated electrostatic interactions between the two electrons and the two protons.
These contribute the remaining 15% of the binding energy of the hydrogen molecule.
Quantum mechanics shows that, on the average, the electrons spend more of their time
in the region between the two protons than they do on the far sides of the protons.
From a very elementary point of view, we may consider that the binding of the
hydrogen molecule results from the attraction of the positively charged hydrogen
nuclei to the negative charge which exists between them.
36
物理冶金 Covalent and Metallic Bonding 魏茂國
Attention is called to the interrelation between space and time implied in this
discussion concerning the time-average position of the electrons.
This is a coordination system that includes both the positions of the particles and their
momenta (that is, velocities). Thus, for a single particle free to move along a single
direction (the x-axis), there will be 2 dimensions in phase space: its position along the
axis, and its momentum.
For n particles capable of moving in a single direction, there will be 2n linear
dimensions in the phase space associated with these particles. These are x1, x2, … xn,
the positions of the particles; and p1, p2, … pn, the momenta of the particles.
For particles capable of moving in 3 dimensions, there will be 6n degrees of freedom
and therefore a corresponding number of dimensions in phase space.
An important theorem in statistical mechanics that bears on the subject of phase space
states that the position and momentum average in phase space coincide with the same
average over an infinite time.
37
物理冶金 Covalent and Metallic Bonding 魏茂國
The lower curve is for opposed electron spins, and it can be observed that this curve
has a pronounced minimum, indicating that in this case a stable molecule can be
formed.
Fig. 3.12
39
物理冶金 Covalent and Metallic Bonding 魏茂國
40
物理冶金 Covalent and Metallic Bonding 魏茂國
The cooperative interaction between the electron gas and the positively charged nuclei
forms a structure that is stable.
The binding forces that hold a metallic crystal together can be assumed to come from
the attraction of the positively charged ions for the cloud of negative charge that lies
between them
As the distance between nuclei is made smaller (as the volume in metal is decreased),
the velocities of the free electrons increase with a corresponding rise in their kinetic
energy. This leads to a repulsive term which becomes large when a metal is
compressed.
41
物理冶金 Covalent and Metallic Bonding 魏茂國
Born-Haber cycle
- There are several important concept to understand before the Born-Haber Cycle can
be applied to determine the lattice energy of an ionic solid; ionization energy,
electron affinity, dissociation energy, sublimation energy, heat of formation, and
Hess's Law.
- Ionization energy is the energy required to remove an electron from a neutral atom
or an ion. This process always requires an input of energy, and thus will always
have a positive value. In general, ionization energy increases across the periodic
table from left to right, and decreases from top to bottom. There are some excepts,
usually due to the stability of half-filled and completely filled orbitals.
- Electron affinity is the energy released when an electron is added to a neutral atom
or an ion. Usually, energy released would have a negative value, but due to the
definition of electron affinity, it is written as a positive value in most tables.
Therefore, when used in calculating the lattice energy, we must remember to
subtract the electron affinity, not add it. In general, electron affinity increases from
42
left to right across the periodic table and decreases from top to bottom.
物理冶金 Covalent and Metallic Bonding 魏茂國
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Source: http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Crystal_Lattices/Thermodynamics_of_Lattices/Lattice_Energy%3A
_The_Born-Haber_cycle
物理冶金 Covalent and Metallic Bonding 魏茂國
H 0f step 1
NaCl(s)
44
Source: http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Crystal_Lattices/Thermodynamics_of_Lattices/Lattice_Energy%3A
_The_Born-Haber_cycle
物理冶金 Covalent and Metallic Bonding 魏茂國
- Step 1: Determine the energy of the metal and nonmetal in their elemental forms.
(Elements in their natural state have an energy level of zero.) Subtract from this the
heat of formation of the ionic solid that would be formed from combining these
elements in the appropriate ration. This is the energy of the ionic solid, and will be
used at the end of the process to determine the lattice energy.
- Step 2: The Born-Haber Cycle requires that the elements involved in the reaction are
in their gaseous forms. Add the changes in enthalpy to turn one of the elements into
its gaseous state, and then do the same for the other element.
- Step 3: Metals exist in nature as single atoms and thus no dissociation energy needs to
be added for this element. However, many nonmetals will exist as polyatomic species.
For example, Cl exists as Cl2 in its elemental state. The energy required to change Cl2
into 2Cl atoms must be added to the value obtained in Step 2.
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Source: http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Crystal_Lattices/Thermodynamics_of_Lattices/Lattice_Energy%3A
_The_Born-Haber_cycle
物理冶金 Covalent and Metallic Bonding 魏茂國
- Step 4: Both the metal and nonmetal now need to be changed into their ionic forms,
as they would exist in the ionic solid. To do this, the ionization energy of the metal
will be added to the value from Step 3. Next, the electron affinity of the nonmetal will
be subtracted from the previous value. It is subtracted because it is a release of energy
associated with the addition of an electron.
This is a common error due to confusion caused by the definition of electron affinity,
so be careful when doing this calculation.
- Step 5: Now the metal and nonmetal will be combined to form the ionic solid. This
will cause a release of energy, which is called the lattice energy. The value for the
lattice energy is the difference between the value from Step 1 and the value from
Step 4.
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Source: http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Crystal_Lattices/Thermodynamics_of_Lattices/Lattice_Energy%3A
_The_Born-Haber_cycle
物理冶金 Covalent and Metallic Bonding 魏茂國
H a0
Na(s) +1/2 Cl2(g) 1
Na(g) + Cl(g)
H d0
2
H 0f IE EA
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Source: http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Crystal_Lattices/Thermodynamics_of_Lattices/Lattice_Energy%3A
_The_Born-Haber_cycle