Bulk Modulus

From the curve for the Energy

versus distance between the
atoms (for the example of a cubic
material), the Bulk Modulus can
be obtained as:
where K is the compressibility and
V is the volume per atom, here V=a
3
The bulk modulus measures a materials
resistance to uniform compression
Bulk modulus, ideal strength, hardness
Bulk modulus
(Gpa)
Ideal strength,
(Gpa)
[100] [110] [111]
Hardness (Gpa)
VN 303 29 44 84 15
BN 380 185 92 113 63
Diamond C 421 215 119 134 96
Ideal strength is maximum of stress-strain curve:
Stress-strain curves
Squares = [100] direction;
Circles = [110] ; Triangles = [111]
-rs
rocksalt
zincblende/diamond
[100] [110] [111]
Evolution of Quantum Theory
1900 1950 2000
E. Schrdinger P. A. M. Dirac D. Hartree M. Planck W. Kohn J. Pople Louis de Broglie
More recent
developments
Recall: Ground state [Born-Oppenheimer
energy surface, or potential energy
surface (PES)]
Electronic Hamiltonian
v
e
v v
e
E H u = u

= = =

+ + V =
N N
k k k k
k' k
N
k
k
r
N
k
e
e
m
H
k
,
' , ' ,
2
0
1
2
1
2
r r 4
1
2
1
) v(r
2 tc

Recall
Potential of the lattice components (ion or nuclei)
of the solid - External potential
V
e-e
Electronic
Hamiltonian
) r R ( v ) v(r
1
ion
k I
M
I
k
=

=
Hartree Theory - Concept
Hartree simplified the problem by making an assumption
about the form of the many-electron wavefunction, namely that
it was just the product of a set of single-electron
wavefunctions.
Based on idea: the effect of the electron-electron interaction
on a certain electron at position r should approximately be
given by the electrostatic potential, which is generated by all
other electrons on average at position r.
Fig. 3.2
Schematic of the self-consistent
field method for solution of the
Hartree Eq. Here v
SIC
has been
neglected Analogous diagrams
exist for Hartee-Fock and
Density-Functional Theory
SCF cycle
Hartree Theory cont.
Reason - the initial assumption of a product
wavefunction. This product wavefunction does not obey
the Pauli exclusion principle.
The Pauli exclusion principle states that it is not
possible for two fermions to exist at the same point in
space with the same set of quantum numbers. This
principle manifests as an effective repulsion between
any pair of identical fermions possessing the same set of
quantum numbers.
Does yield several quantities that agree with experimental
data, e.g. the (negative)
i
approximately agree with
measured ionization energies.
Unfortunately, the Hartree approximation does not yield
particularly good results for other important properties, for
example, it predicts that in a neutral uniform system there
will be no binding energy holding the electrons in the
solid.
Hartree Theory cont.
The Pauli exclusion principle can be accounted for by
ensuring that the wavefunction is antisymmetric under
exchange of any pair of particles.
That is, swapping any one of the fermions for any other
of the fermions, should leave the wavefunction unaltered
except for a change of sign. Any wavefunction
possessing that property will tend to zero (indicating zero
probability) as any pair of fermions with the same
quantum numbers approach each other.
The Hartree product wavefunction is symmetric (i.e. stays
precisely the same after interchange of two fermions), so the
Hartree approach effectively ignores the Pauli exclusion
principle!
Hartree-Fock Theory
Hartree-Fock Approach
The many-electron wavefunction is constructed out of single-electron
wavefunctions in such a way as to be antisymmetric. It is written as a
Slater determinant .
Simple equation for each single-electron wavefunction. In addition to the
Hartree potential there is now an exchange potential.
For an electron with spin-up, the Pauli exclusion principle means that
other nearby spin-up electrons will be repelled.
Spin-down electrons will not be affected since
they have a different spin quantum number.
Thus the spin-up electron is surrounded by a
region depleted of other spin-up electrons. The
edge of the electron depleted region is called
the exchange hole.
The exchange potential contributes a binding energy for electrons, so
correcting one of the failings of Hartree theory.
+
Hartree-Fock Approach cont.
The Hartree-Fock approach gives quite creditable results for small
molecules.
Does not provide a good description for solids - does not describe the
electrostatic correlation of electrons.
- each electron surrounded by an electron-
depleted region known as the Coulomb
hole or the correlation hole
Implications - (i) negatively charged electron and its positively charged hole
experience a binding force due to electrostatics.
(ii) entities which interact with the electron over a length scale larger than
the size of the correlation hole will interact with the electron+correlation
hole. Thus any other interaction effects, will tend to be reduced i.e.
screened by the correlation hole.
More advanced wavefunction methods,
Density-functional Theory
e
e
e
e
e
e
e
e
e
e
e
-
+