From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary

Microscopic-Macroscopic connection
relating experiment and theory
Silvana Botti
European Theoretical Spectroscopy Facility (ETSF)
CNRS - Laboratoire des Solides Irradies
Ecole Polytechnique, Palaiseau - France
Temporary Address:
Centre for Computational Physics
University of Coimbra - Portugal
June 27, 2007 Queens University, Belfast
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
How to relate macroscopic
and microscopic world?
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Outline
1
Starting point: Maxwells equations
2
Averaging procedure
3
Macroscopic dielectric function in cubic crystals
4
Dielectric tensor for non-cubic symmetries
5
Summary
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Outline
1
Starting point: Maxwells equations
2
Averaging procedure
3
Macroscopic dielectric function in cubic crystals
4
Dielectric tensor for non-cubic symmetries
5
Summary
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
How to study optical processes?
The propagation of electromagnetic waves in materials is described by the
Maxwells equations, supplemented by appropriate constitutive equations.
The optical phenomena (reection, propagation, transmission) can be
quantied by a number of parameters that determine the properties of the
medium at the macroscopic level.
Microscopic (semiclassical) models and averaging procedures yield these
macroscopic parameters.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
The response of a dielectric material to an external electric eld
is characterized by three macroscopic vectors:
the electric eld strength E,
the polarization P,
the electric displacement D.
The response of a dielectric material to an external magnetic eld
is characterized by three macroscopic vectors:
the electric eld strength H,
the magnetization M,
the magnetic ux density B.
The macroscopic vectors have microscopic counterparts.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Maxwells equations in presence of a medium
E(r, t) = 4
ind
(r, t) + 4
ext
(r, t)
B(r, t) = 0
E(r, t) =
1
c
B(r, t)
t
B(r, t) =
4
c
(j
ind
(r, t) + j
ext
(r, t)) +
1
c
E(r, t)
t

ext
, j
ext
= external (or free) charges and currents

ind
, j
ind
= induced (or bound) charges and currents
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Maxwells equations in presence of a medium
D(r, t) = 4
ext
(r, t)
B(r, t) = 0
E(r, t) =
1
c
B(r, t)
t
H(r, t) =
4
c
j
ext
(r, t) +
1
c
D(r, t)
t

ext
, j
ext
= external charges and currents
Continuity equation: j
ext
+

ext
t
= 0
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
In the linear response regime, for an isotropic medium:
P =
e
E
D = E + 4P = E
M =
m
H
B = H + 4M = H
electric permittivity
e
dielectric function
magnetic susceptibility
m
magnetic permeability
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Linear response
Perturbation theory
For a suciently small perturbation, the response of the system can be
expanded into a Taylor series, with respect to the perturbation.
We will consider only the rst order (linear) response, proportional to the
perturbation.
= strong eld interaction (intense lasers for instance).
The linear coecient linking the response to the perturbation is called a
response function. It is independent of the perturbation and depends only
on the system.
We will consider non-magnetic materials.
Example
Density-density response function: (r, t) =
_
dt

_
dr

(r, t, r

, t

)v
ext
(r

, t

)
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Which quantities are measured?
Absorption coecient
The general solution of Maxwells eqs in vacuum is E(r, t) = E
0
e
i (krt)
.
Dening the complex refractive index as N =

= + i , the electric eld

inside a medium is the damped wave:
E(x, t) = E
0
e
i
c
xN
e
i t
= E
0
e
i
c
x
e

c
x
e
i t
and are the refraction index and the extinction coecient and they are
related to the dielectric constant as

1
=
2

2
= 2
The absorption coecient is the inverse distance where the intensity of the
eld is reduced by 1/e:
=

2
c
(related to the optical skin depth ).
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Which quantities are measured?
Schematic diagram
x
z
Incident beam
Reflected beam
Transmitted beam
Reectivity
Normal incidence reectivity:
R = |
E
T
E
i
|
2
< 1
R = |
(1 )
2
+
2
(1 +)
2
+
2
|
The knowledge of the optical constant
implies the knowledge of the
reectivity, which can be compared
with the experiment.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Which quantities are measured?
Example: Photoabsorption cross section
Rem: (r, ) =
_
dr

(r, r

, )v
ext
(r

, )

ph
() =
4
c
Im
_
dr
_
dr

z (r, r

, ) z

with v
ext
(r

, ) =
0
z

ph
() =
4
c
0
Im
_
dr z (r, )
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Which quantities are measured?
Example: Energy loss by a fast charged particle
Given an external charge density
ext
, one can obtained the external potential v
ext
k
2
v
ext,ind
(k, ) = 4
ext,ind
(k, ) (Poisson equation)
The response of the system is an induced density, dened by the response
function

ind
(k, ) = (k, )v
ext
(k, )
and the total (induced + external) potential acting on the system is
v
tot
(k, ) =
_
1 +
4
k
2
(k, )
_
v
ext
(k, ) =
1
(k, )v
ext
(k, )
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Which quantities are measured?
Energy loss by a fast charged particle: classical electron
Particle (e

) with velocity v:
ext
(r, t) = e(r vt);
ext
(k, ) =
e
(2)
3
(k v)
The total electric eld is E
tot
(r, t) =
r
V
tot
(r, t) and the energy lost by the
electron in unit time is
dW
dt
=
_
dr j . E
tot
with the current density j = ev(r vt). We get
dW
dt
=
e
2

2
_
dr
k
2
Im
_

(k, )
_
Im
_
1
(k,)
_
is called the loss function.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Outline
1
Starting point: Maxwells equations
2
Averaging procedure
3
Macroscopic dielectric function in cubic crystals
4
Dielectric tensor for non-cubic symmetries
5
Summary
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Macroscopic average
Macroscopic quantities
At long wavelength, external elds
are slowly varying over the unit
cells.
=
2
q
>> V
1/3
where V is the volume per unit cell
of the cystal.
Example
E
ext
(r, t), A
ext
(r, t), V
ext
(r, t),
Microscopic quantities
Total and induced elds are rapidly
varying: they include the
contribution from electrons in all
regions of the cell.
Large and irregular uctuations
over the atomic scale.
Example
E
tot
(r, t), j
ind
(r, t),
ind
(r, t),...
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Macroscopic average
Measurable quantities
One usually measures quantities that vary on a macroscopic scale.
We have to average over distances
large compared to the cell diameter,
small compared to the wavelength of the external perturbation.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Macroscopic average
Procedure
Average over a unit cell whose origin is at point R;
Regard R as the continuous coordinate appearing in the Maxwells
equations.
The dierences between the microscopic elds and the averaged
(macroscopic) elds are called the crystal local elds.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Macroscopic average
Procedure
In presence of a periodic medium, every function can be represented by the
Fourier series
V(r, ) =

qG
V(q + G, )e
i (q+G)r
where R is any vector of the Bravais lattice, q is in the rst Brillouin zone and G
is a reciprocal lattice vector.
It is equivalent to write
V(r, ) =

q
V(r; q, )e
i qr
where V(r; q, ) =

G
V(q + G, )e
i Gr
is a periodic function, with respect to
the Bravais lattice.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Macroscopic average
For a monocromatic eld with wavevector q
Spatial average over a unit cell:
V(R, ) = < V(r; q, ) >
R
e
i qR
= e
i qR
1

_
dr

G
V(q + G, )e
i Gr
= e
i qR
V(q + 0, )
The macroscopic average corresponds to the G = 0 component.
Macroscopic quantities have all their G components equal to 0, except the
G = 0 component.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Macroscopic average
A simple example
v
ext
(q + G, ) =

GG
(q, )v
tot
(q + G

, )
v
ext
is a macroscopic quantity : v
ext
(q + G, ) = v
ext
(q, )
G0
This not the case for v
tot
(q + G, )
Macroscopic average of v
ext
v
ext
(q, ) =

0G
(q, )v
tot
(q + G

, )
=
00
(q, )v
tot
(q, )
The average of the product is not the product of the averages
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Macroscopic average
A simple example
We have also the relation
v
tot
(q + G, ) =

1
GG

(q, )v
ext
(q + G

, )
where

GG
(q, )
1
G

(q, ) =
GG

Macroscopic average of v
tot
v
ext
is macroscopic v
tot
(q + G, ) =
1
G0
(q, )v
ext
(q, )
v
tot
(q, ) =
1
00
(q, )v
ext
(q, )
v
ext
(q, ) =
M
(q, )v
tot
(q, )
M
(q, ) =
1

1
00
(q, )
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Macroscopic average
Summary
We have dened microscopic and macroscopic elds
Microscopic quantities have to be averaged to be compared to
experiments
The dielectric function also has a microscopic expression and its
macroscopic counterpart

M
(q) =
1

1
00
(q)
Absorption Im{
M
} and EELS Im
_
1

M
_
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Macroscopic dielectric function
Question

00
is not the macroscopic dielectric function
What is it then ?
Answer

00
is the macroscopic dielectric function without crystal local elds.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Microscopic dielectric Function
Question
How can we calculate the microscopic dielectric functions?
Answer
They are determined by the elementary excitations of the medium:
interband and intraband transitions, as well as collective excitations.
This issue will be addressed in the next lectures!!!
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Outline
1
Starting point: Maxwells equations
2
Averaging procedure
3
Macroscopic dielectric function in cubic crystals
4
Dielectric tensor for non-cubic symmetries
5
Summary
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Dielectric tensor for cubic symmetries
Macroscopic elds
q denes the direction for the propagation: we assume q x
Longitudinal elds
E q
Coulomb gauge: A = 0
Poisson equation:
2
v
ext
= 4
ext
EELS
Electrostatic interaction
Transverse elds
E q
Optical spectroscopy
Photons
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Dielectric tensor for cubic symmetries
Properties - Macroscopic quantities
Electric displacement D(q, ) =

M
(q, )E
tot
(q, )
No symmetry

M
(q, ) =
_
_
_

LL

xy

xz

yx

yy

yz

zx

zy

zz
_
_
_
Cubic symmetry

M
(q, ) =
_
_
_
_

LL
M
0
0
TT
M
_
_
_
_
Macroscopic quantities only:
A longitudinal pertubation induces a longitudinal response
A transverse pertubation induces a transverse response
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Dielectric tensor for cubic symmetries
Longitudinal and transverse components

LL
M
=
1
1 +
4
q
2

(q, )

TT
M
= ... more complicated

...
* H. Ehrenreich, Electromagnetic Transport in Solids, in The Optical Properties
of Solids, Varenna Course XXXIV, edited by J. Tauc (Academic Press, New York,
1966) p 106.
R. Del Sole and E. Fiorino, Phys. Rev. B 29, 4631 (1984).
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Dielectric tensor for cubic symmetries
In the limit q 0
lim
q0

TT
M
=
LL
M
=
1
1 +
4
q
2

(q, )
We nally reach a familiar result!
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Outline
1
Starting point: Maxwells equations
2
Averaging procedure
3
Macroscopic dielectric function in cubic crystals
4
Dielectric tensor for non-cubic symmetries
5
Summary
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Non-Cubic symmetries
Properties - Macroscopic quantities
D(q, ) =

M
(q, )E
tot
(q, )

M
(q, ) =
_
_
_
_
_

LL
M

LT
M

TL
M

TT
M
_
_
_
_
_
Microscopic and macroscopic quantities
A longitudinal pertubation induces a longitudinal and a transverse response
A transverse pertubation induces a longitudinal and a transverse response
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Non-Cubic symmetries
Dielectric tensor - General case

M
(q, ) = 1 + 4

(q, q, )
_
_
1 + 4
q
q
q
q
.

(q, q, )
1 4
LL
(q, q, )
_
_
COMPLICATED! But one can show that the relation

LL
M
=
1
1 +
4
q
2

(q, )
holds also for the non-cubic symmetries.
R. Del Sole and E. Fiorino, Phys. Rev. B 29 4631 (1984).
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Non-cubic symmetries - Principal axis
Principal axis
In the limit q 0, one can nd 3 axis n
1
,n
2
,n
3
, dening a frame in which

M
is diagonal.
Applying a longitudinal eld E
tot
(q, ), parallel to one of these axis
(q n
i
) leads to

M
(n
i
, ) : E
tot
(n
i
, ) =
LL
M
(n
i
, )E
tot
(n
i
, )
Along these directions, a longitudinal perturbation induces a longitudinal
response through the usual relation
lim
q0

LL
M
(q, ) = lim
q0
1
1 +
4
q
2

(q, )
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Non-cubic symmetries - Principal axis
Longitudinal and transverse dielectric functions
For q 0, we have dened three quantities:

LL
M
(n
1
, ),
LL
M
(n
2
, ) and
LL
M
(n
3
, )
Using the crystal symmetries, they can be used to dene also the
transverse dielectric functions (depending on the symmetry)
The full dielectric tensor for q = 0 will not be adressed here!
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Dielectric tensor for non-cubic symmetries
In conclusion, in the limit q 0
lim
q0

TT
M
=
LL
M
=
1
1 +
4
q
2

(q, )
can also be true for non-cubic symmetries, provided that the correct
reference frame is chosen and symmetries are used.
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Outline
1
Starting point: Maxwells equations
2
Averaging procedure
3
Macroscopic dielectric function in cubic crystals
4
Dielectric tensor for non-cubic symmetries
5
Summary
Microscopic-Macroscopic connection Silvana Botti
From Maxwells equations Averages Cubic symmetry Non-cubic symmetries Summary
Summary
The key quantity is the (microscopic and macroscopic) dielectric
tensor.
Relation between microscopic and macroscopic elds through
averages.
For cubic crystals, the longitudinal dielectric function denes entirely
the optical response in the long wavelength limit.
The situation is not so simple for non-cubic crystals.
Microscopic-Macroscopic connection Silvana Botti