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Danglingbonds 2017

Dangling bonds are undercoordinated surface atoms with broken chemical bonds. For fcc crystals sliced along different planes, the (100) plane has 4 dangling bonds per atom, (110) has 5, and (111) has 3. The number of dangling bonds determines the surface energy, with (111) having the lowest energy followed by (110) then (100). Surface energy quantifies the excess energy of surface atoms from broken bonds and is important for understanding surface properties and reactions.

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37 views

Danglingbonds 2017

Dangling bonds are undercoordinated surface atoms with broken chemical bonds. For fcc crystals sliced along different planes, the (100) plane has 4 dangling bonds per atom, (110) has 5, and (111) has 3. The number of dangling bonds determines the surface energy, with (111) having the lowest energy followed by (110) then (100). Surface energy quantifies the excess energy of surface atoms from broken bonds and is important for understanding surface properties and reactions.

Uploaded by

Ps Shreyas
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Dangling bonds

Dangling bonds are the broken bonds yielding undercoordinated atoms. For
example, if we draw a simple fcc lattice and slice it along one of the facets, we'll
see directly how many bonds are broken.

When we slice along (100) , we are removing 4 nearest neighbors and each
atom will have 4 dangling bonds as shown below.

For (100) plane, there are 4 dangling bonds


When we slice along (110) , we are removing 5 nearest neighbors and each
atom will have 4 dangling bonds as shown below.
For (110) plane, there are 5 dangling bonds
When we slice along (111) , we are removing 5 nearest neighbors and each
atom will have 3 dangling bonds as shown below.

For (111) plane, there are 3 dangling bonds

The number of dangling bonds is a fundamental quantity that is important in


deducing surface energy. From the above drawings for metals of fcc structure:
{100} facets would have four broken chemical bonds, {110} surfaces has 5
broken chemical bonds and {111} has 3. Accordingly, in monometallic fcc crystal
the {111} family of surfaces have the lowest surface energy, followed by {110} and
{100} families of planes.

Surface Energy

The surface properties of a crystal are crucial to the understanding and


design of materials for many applications. For instance, technologies such as fuel
cells and industrial chemical manufacturing require the use of catalysts to
accelerate chemical reactions, which is fundamentally a surface-driven process.
Surface effects are especially important in nanomaterials, where relatively large
surface area to volume ratios lead to properties that differ significantly from the
bulk material. For example, the nanoscale stability of metastable polymorphs is
determined from the competition between surface and bulk energy of the
nanoparticle.
The stability of a surface is described by its surface energy γ, a measure of
the excess energy of surface atoms due to a variety of factors, such as the broken
bonds yielding undercoordinated atoms. This fundamental quantity is important in
understanding surface structure, reconstruction, roughening and the crystal’s
equilibrium shape.

Each facet has a characteristic surface energy, the value depending of how many
broken chemicals bonds you have in the surface.
Calculation of surface energy per unit area γ

The surface energy (ꙋ)per unit area of different crystal faces can be calculated
using the following relation:

Dangling bonds
ꙋ= ( )  U  ao
Bulk coordination number N A

where:
ꙋ = Energy per unit area of a particular crystal plane,

CN = 12
U = lattice energy
NA = Avogadro’s number
a₀ = Planar density in atoms/m2
For (100) of Ca metal possesses a fcc structure of unit cell constant a = 5.6 Å,
U = 180 kJ mol-1, dangling bonds = 4, CN in the bulk = 12, the surface density is 2/a2
atoms per unit area. i.e.

Planar density = 2
(5.6  10 10 m) 2

= 0.35571020 atom/m2
Then,
1
180000 (J mol )
ꙋ= 4  1
 0.3557  10 m
20 2

12 6.02  10 mol
23

= 0.63 J/m2
= 630 mJ/m2

One can proceed with calculations for fcc (111) faces in which: dangling bonds = 3,
CN in the bulk = 12, the surface density is 2 / 3 a2 atoms per unit area.
For fcc (110) faces, dangling bonds = 5, CN in the bulk = 12, the surface density is
2/ 2 a2 atoms per unit area.
It is clear that magnitude of lattice energy reflects the strength of chemical
bonding. The surface energy (ꙋ)per unit area of the (100) faces of different
materials is given as follows.

(100) faces ꙋ mJ/m2


Diamond 9800
MgO 1200
Ca 630
LiF 480

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