Descriptors

Descriptor: a conceptual scheme that provides quantitative

characterization of some part of structure.

Tools that can be used to build a descriptor are:

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 Generic descriptors

• Gases, liquids, and glasses are disordered and therefore

structurally similar
• We can use the same structural descriptors to define them and
distinguish them
• Because structure changes spatially and temporally, we will use
some kind of statistical averages:

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 Generic descriptor #1: free volume
• Free volume (VF): the difference between the total sample specific volume (volume per unit
mass) in the noncrystalline sate and the occupied specific volume V0:

• V0 can be approximated as the specific volume of all the structural units and spaces between
them on the crystalline state: V0(T)≈Vcryst(T)
• Therefore, the free volume is the difference of the specific volumes of the noncrystalline solid
and the crystalline material

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 Generic descriptor #2: Pair distribution function

dr

Pair distribution function:

dn: number of atoms in a spherical shell

dv: spherical shell volume
r: distance of the shell from an arbitrary atom selected as the origin
<ρ>: average particle density
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 Pair distribution function

1 dn(r,r + dr)
g(r) =
ρ dv(r,r + dr)

• Proportional to the volume-normalized average relative number of units in

each successive spherical shell
• In other words,
€ g(r) provides the local density in the structure surrounding a
typical atom

• Units?
• Does it depend on dr?

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 Pair distribution function

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From The Structure of Materials, Allen and Thomas,copyright 1999 John Wiley and Sons, Inc
Reproduced with permission of John Wiley and Sons, Inc.
 Pair distribution function for crystals

• g(r) exhibits an infinite series of discrete peaks at precise values of

interatomic separation
• depends on the particular crystal structure

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 Pair distribution function for liquid/glass

• There is a short-range order

• g(r) shows several broad peaks and valleys, and then reaches a
constant value at large distances r

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 Pair distribution function for gas

• Atoms (or molecules) are uncorrelated

• Below the hard-sphere diameter the probability of finding another atom is zero
• Beyond the hard sphere diameter, probability of finding another atom is simply
equal to the average gas density (both numbers are small), and g(r)=1

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 Pair distribution function

There are several important features of the pair distribution function

Why valley?

Second…
Average distance to the first shell
of the nearest neighbors

• Correlation distance ξ [Xi]: distance at which g(r) reaches its asymptotic

value of 1
• All correlation information is lost beyond that point 35

Image from The Structure of Materials, Allen and Thomas,copyright 1999 John Wiley and
Sons, Inc Reproduced with permission of John Wiley and Sons, Inc.
 Pair distribution function: reality check

The pair distribution function provides a

measure of the order/disorder in the system.

•  label all of the relevant points and axes in the following pair distribution function
•  units?
•  on the same graph draw the evolution of a liquid toward a crystalline solid assuming
that the density of the solid is higher than that of the liquid

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 Pair distribution function: reality check

The pair distribution function provides a

measure of the order/disorder in the system.

•  label all of the relevant points and axes in the following pair distribution function
•  on the same graph draw the evolution of a liquid toward a crystalline solid assuming
that the density of the solid is higher than that of the liquid