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L. Paolasini - X-rays and their interaction with matter
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X-rays and their interaction with matter
Luigi Paolasini
European Synchrotron Radition Facility
paolasini@esrf.eu
OUTLINES
L. Paolasini - X-rays and their interaction with matter
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“X-rays and their interaction with matter”
Ø Waves and photons
Ø Elastic and inelastic scattering
Ø Absorption spectroscopies
Ø Optical properties
X-RAY DISCOVERY: W.C. RÖNTGEN, 1895
L. Paolasini - X-rays and their interaction with matter
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Röntgen discovered a penetrating form of electromagnetic radiation able to pass
through the human body: the X-rays.
X-rays are produced by collision of electrons with a metal target (kinetic energy
loss, “bremstralung”)
Röntgenogram
CRYSTAL DIFFRACTION: MAX VON LAUE, 1912
L. Paolasini - X-rays and their interaction with matter
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X-rays are electromagnetic waves:
- The x-ray wavelengths are comparable with the interatomic distances and
molecular bonds.
- Typical interference x-ray patterns when pass through a periodic arrangement
of atoms, like in a crystal, and reveal their crystallographic symmetries.
k
i
kf
THEORY OF X-RAYS DIFFRACTION: BRAGG LAW, 1913
L. Paolasini - X-rays and their interaction with matter
Bragg Law: 2d sinq = nl
l : wavelength
q : diffraction angle
d : interatomic distance
n : integer number
The interference X-ray pattern contains the signature of the periodic
arrangement of atoms in a crystals.
The Bragg’s law define the relation between interatomic distances d and
scattering angle q
Crystal
Photographic film
l q
d = l/2 sinq
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FROM COOLIDGE TUBE TO ROTATING ANODE.
L. Paolasini - X-rays and their interaction with matter
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W.D. Coolidge’s tube from General Electric developed in 1912 served as
the standard X-ray tube for many decades until the advent of rotating
anode generators.
The X-ray spectrum has two distinct components:
- Bremsstrahlung radiation : a continuous component
- Sharp radiations with a characteristic energy emission Ka and Kb of
the metal target.
- Only 1% of the incident energy is emitted in the form of x-rays
X-RAY TUBES: ROTATING ANODE
L. Paolasini - X-rays and their interaction with matter
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Today powerful x-rays sources can be obtained by rotating
anode x-ray tubes.
X-ray tubes are also used in CAT scanners, airport luggage
scanners, X-ray crystallography, and for industrial
inspection.
DISCOVERY OF SYNCROTRON RADIATION : GENERAL ELECTRIC 1947
L. Paolasini - X-rays and their interaction with matter
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Visible light emission discovered in a 70-MeV
betatron at General Electric in 1947.
First observation of synchrotron radiation
Electromagnetic radiation emitted when charge particles moving at ultra-relativistic energies are forced to
change direction under the action of a magnetic field.
Synchrotron emission
1/g
E >> mec2 ~ 0.511 MeV
g = E/mec2 >> 1
g ~ 1957 E[GeV]
Gas emission (red) and synchrotron light (blu) produced
by high energy electrons in the magnetic field of a neutron
star (Crab nebula)
Crab nebula
L. Paolasini - Introduction to X-ray sources and their applications: from synchrotrons to free electron lasers
Most of the radiation of our galaxy is composed by synchrotron radiation.
Synchrotron light was first detected in a jet emitted by
M87 in 1956 by Geoffrey R. Burbidge.
SYNCHROTRON RADIATION IN ASTRONOMY
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THE SYNCHROTRON RADIATION FACILITY
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L. Paolasini - Introduction to X-ray sources and their applications: from synchrotrons to free electron lasers
The Synchrotron is a “storage ring” where the electrons are first accelerated by a booster at high
energies and then constrained on a circular orbit.
X-rays are produced by the insertion devices (bending magnets or undulators) and then used in the
different beamlines located in the tangent of electron trajectory
LINAC
Booster
Synchrotron
Storage ring
Beamlines
electrons
X-rays
X-RAYS LARGE SCALE FACILITIES
L. Paolasini - X-rays and their interaction with matter
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European Synchrotron Radiation Facility
SYNCHROTRONS :
the electrons circulate in a close orbit
FREE ELECTRON LASERs:
the electrons travel in linear accelerators
X-Fel Ambourg
X-RAYS ARE ELECTROMAGNETIC WAVES
L. Paolasini - X-rays and their interaction with matter
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Microscopes
Radar Synchrotrons
Radio waves Large accellerators
Small wavelengths
Large wavelengths
Buildings Human body Insects Needle Cells Molecules Atoms Nuclei/quark
radio
103
microwaves
10-2
visible
0.510-6
infrared
10-5
ultraviolet
10-8
X-rays
10-10
ultraviolet
10-8
Gamma rays
10-12
m
Wavelenght : l = 2p/k = c/ n Energy : hn = E Planck’s constant : h
X-RAYS LENGTH SCALES
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Hard X-rays
1.2 MeV - 2.5 keV ~ 0.001÷ 0.5 [nm]
Soft X-rays
2.5 keV - 100 eV ~0.5 ÷ 12 [nm]
ULTRA SMALL
Planck’s constant h = 4.135 x 1015 eV s
ex. 1 Å = 0.1 nm @ 12.398 keV
X-RAYS TIMESCALES
Page 14 L. Paolasini - X-rays and their interaction with matter
10keV X-rays
2.4 x 1018 Hz = 2.4 exa Hz
T = 41 x 10-3 fs = 41 attosecond
l = 12.5 nm = 1.25 Å
ULTRA FAST
Pulse duration ESRF
20 ps
Pulse duration X-FEL (theory)
4.5 fs
ELECTROMAGNETIC WAVES AND MAXWELL EQUATIONS
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The electromagnetic field generated by the electrons is described by the electric E and
magnetic B in term of scalar F and vector A potential:
Time periodicity
T=1/n
Space periodicity
l=2p/k
Vector potential
Transverse EM waves
X-RAYS POLARISATIONS
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- The X-rays delivered by the insertion devices (bending magnets or undulators) are transverse polarized
electromagnetic waves
- The polarization vector e is parallel to the electric field E.
- Some particular insertion devices can also deliver circular polarization (ex. helical undulators, phase
plates)
e
Linear transverse EM wave Circular transverse EM wave
WAVE - PARTICLE DUALITY
Page 17 L. Paolasini - X-rays and their interaction with matter
Oscillations ® wave
Envelope ® particle localization
Heisenberg uncertainly principle:
Cannot define both D and l to an arbitrary accuracy
Energy: E = hν = ħω
Momentum: p=h/λ = ħk
Decreasing D to define better the position, but we lose information on l
Wave: D>>l particle: D<<l
Description of the behaviour of a quantum-scale objects.
where
h= Planck’s constant
ν=frequency
k=wavevector
WAVES AND PHOTONS : QUANTUM MECHANICS ASSUMPTIONS
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(i) Particles are represented mathematically by a wavefunction, ψ(r)
(ii) Probability of finding a particle in a (infinitesimal) volume dV is |ψ(r)|2dV
Infinite plane wave (spatial part):
ψ(z) = eikz = cos(kz) + i sin(kz)
|ψ|2 = ψψ* = eikze-ikz =1
1 particle per unit volume everywhere!
Spherical wave:
ψ(r) = b/r eikr
|ψ(r)|2 = ψψ*= b2/r2
Density of particles falls as 1/r2
Flux of particles
I = No. of particles incident normally on unit area per second =
= particle density x velocity
= |ψ|2 x v = |ψ|2 ħk/m (m-2 s-1)
r
TOTAL SCATTERING CROSS SECTION
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Total cross section: Effective area viewed by scattering particles!
σ = 4πb2
Quantum case:
no. particles scattered per second = fsc x 4πr2
Incident wave ψ0 = eikz
Incident flux f0=|ψ0|2 v = v
Scattered wave ψsc = b/r eikr
Scattered flux fsc=|ψsc|2 v = b2v/r2
b= scattering length
Classical case:
no. particles scattered per second = f0 x πa2
n. Particles x unit area x sec.
σ = πa2
Cross-sectional area of
sphere
Incident flux f0
Incident flux
f0=|ψ0|2 v
L. Paolasini - X-rays and their interaction with matter
DIFFERENTIAL SCATTERING CROSS SECTION
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Definition:
Solid angle subtended by the detector:
DW = A/L2
No. particles detected per sec.:
ds/dW =( |ψsc|2 v x A) / (|ψ0|2 v dW)
(barns/steradian) 1 barn=10-28 m2
Notice that ysc is a spherical wave |ysc|2 = b2/L2
Detector area
|ysc|2 = b2/L2
L. Paolasini - X-rays and their interaction with matter
SCATTERING PROBES AND INTERACTION POTENTIALS
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The scattering length b depends from the type of interaction potential with the scattering probes
Neutrons:
Nuclear and magnetic interaction
X-rays:
Electromagnetic and core-hole interactions
Electrons:
Electrostatic interaction
X-RAY MATTER INTERACTION
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sample
Photon absorption/emission : Excitation with or without emission of electrons
Photon scattering : Elastic coherent => Thomson
Inelastic incoherent => Compton
Resonant => elastic or inelastic
Photons are totally absorbed by the
material
Photons are deviated by their
straight direction
X-RAY ELASTIC SCATTERING BY A FREE ELECTRON
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w The incident electric field Ein forces the motion of the electron : Lorentz’s Force F=qE
w Re-radiation of a spherical wave Erad
Radiated spherical field Erad at observer position R:
- proportional to the electron acceleration
- anti-phase with respect Ein
- decreases with cos(y)
Thomson scattering length:
(Classical electron radius)
POLARIZATION DEPENDENCE OF THOMSON SCATTERING
Page 24 L. Paolasini - X-rays and their interaction with matter
The differential cross section for the Thomson scattering depends from the incident and
scattered photon polarizations
Dipole radiation
a) b)
MAGNETIC SCATTERING BY A FREE ELECTRON
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The magnetic scattering amplitudes are very weak because proportional to the relativistic factor E/mc2
Both the H magnetic and the electric E
field interact with the charge and
magnetic moments of the electron
from: de Bergevin and Brunel (Acta Cryst, 1981)
THOMSON SCATTERING BY TWO FREE ELECTRONS
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Differential scattering cross section
Q = wavevector transfer or scattering vector
- Interference between scattered X-rays observed in the direction k’ and at large distances (far field limit),
with |k|= |k’|= 2p/l.
- The phase difference between the two scattered X-rays is Df=(k-k’) . r = Q . r
RANDOM DISTRIBUTION OF TWO FREE ELECTRONS
Page 27 L. Paolasini - X-rays and their interaction with matter
Scattering cross section (two electrons):
orientational average
Scattering cross section (two electrons):
The scattering intensity depends from the relative orientation of scattering vector Q and the
vector rn. (with neglet the polarization)
THOMSON SCATTERING BY MANY FREE ELECTRONS
Page 28 L. Paolasini - X-rays and their interaction with matter
In general if we have a random distribution of electrons, the scattering function is obtained sum
“coherently” all the individual terms
Thomson differential scattering cross
section for a electron charge distribution
THOMSON SCATTERING BY ONE ATOM
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The form factor is related to the Fourier transform of charge density distribution:
a0=Bohr radius
Z=1
Z=3
Z=1
Z=3
The Q dependence is due to the fact that the Thomson scattering is produced by all atomic electrons,
which have a spatial extent of the same order of magnitude as the X-ray wavelength.
Z=1 H
Z=3 Li
SCATTERING BY TWO ATOMS
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The scattering of two atoms which have a spatial extent of electron distribution of the same order of magnitude
as the X-ray wavelength.
Zr0
Q
Atomic form factor
f(Q)
Electron distribution
SCATTERING FROM A MOLECULE
Page 31 L. Paolasini - X-rays and their interaction with matter
Molecular structure factors
Q // C-F bond
Orientational average
Mo Form factor
(Mo=42 electrons)
|Fmol
±|2
|Fmol|2
F
F
F
F
CF4 molecule
C
F=fluorine= 9e-
C=carbon= 6e-
COMPTON SCATTERING (BY A FREE ELECTRON)
Page 32 L. Paolasini - X-rays and their interaction with matter
Inelastic collision between a photon and an electron at the rest in which part of the the photon energy is
transferred to the electron (photon “red shift”)
Compton scattering wavelength
Fine structure constant
Maximum “red-shift” when y=180 deg.
No variation when y=00
~
This scattering is incoherent and contribute only to the background.
Energy shift
INCOHERENT INELASTIC COMPTON SCATTERING
Page 33 L. Paolasini - X-rays and their interaction with matter
The inelastic scattering dominates at high Q vectors and for low Z elements
Thomson scattering intensity approach Z2 when Q®0
Compton scattering approaches Z when Q®∞
Compton scattering
elastic scattering
Elastic and inelastic scattering in noble gas
COHERENT ELASTIC SCATTERING(THOMSON)
Page 34 L. Paolasini - X-rays and their interaction with matter
one atom
Scattering processes conserve the number of photons
If the photon energy is conserved, the scattering is elastic. If not. It is inelastic
a molecule
a crystal
Atomic form factor
Molecule structure factors
Crystal structure factors
CRYSTAL STRUCTURE FACTOR
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The Fourier transform of the crystal (the crystal structure factor) is equal to the product of the FT of
lattice and the basis
The lattice sum is non vanishing only when:
FT Lattice FT Basis
Rn
Laue conditions
EXAMPLE OF RECIPROCAL SPACES
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EQUIVALENCE BRAGG-LAUE
Page 37 L. Paolasini - X-rays and their interaction with matter
Bragg’s law:
Laue’s condition
Differential cross section for the
Bragg diffraction in crystals
EWALD SPHERE
Page 38 L. Paolasini - X-rays and their interaction with matter
Geometric construction that allows one to visualize the Bragg' law during the elastic diffraction experiment
Only all the reciprocal lattice points Ghkl intercepting the
Ewald sphere fulfill the Bragg conditions
All the Ghkl contained in limiting sphere could be reached
by rotating the sample about the goniometer axis
POWDER DIFFRACTION
Page 39 L. Paolasini - X-rays and their interaction with matter
Size and symmetry of the unit cell
Debye-Scherrer cone
Lorentz factor
Detector aperture d
Multiplicity mhkl Polarization factor
At RT-RP, Orthorhombic Fddd
based on S8 rings (molecular units)
EXAMPLE : HIGH PRESSURE SYNTESIS OF SULFUR
L. Paolasini - X-rays and their interaction with matter
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• Pressure up to 17 GPa on 2 mm3 sample volume
• Resistive heating up to 2000 K
P=3GPa T=600K
Hexagonal P3221
WHITE BEAM LAUE PATTERN
Page 41 L. Paolasini - X-rays and their interaction with matter
Polychromatic beam technique used in protein crystallography or in more complex structures.
Data collection of a large number of reflections
All the lattice points contained in the grey area
contribute to the Bragg diffraction
Structure of MbCO at different time delays after
photolysis. The bound CO dissociates, eventually
becoming trapped in sites 4 and 5, where it remains
out to the microsecond time scale.
F. Schotte et al., (2003), Science, 300, 1944-1947.
Time-resolved MX using the Laue technique (White/Pink beam)
TIME RESOLVED PROTEIN CRYSTALLOGRAPHY
L. Paolasini - X-rays and their interaction with matter
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X-RAY DIFFRACTION WITH 2D DETECTORS
• Multi-length scale problems
L. Paolasini - X-rays and their interaction with matter
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(b) Powder
diffraction at large
working distances
(a) Powder diffraction at
short working distances
(d) Liquid and amorphous materials
scattering at short working distances
(e) Specialized single crystal
diffraction.
(c) Single crystal diffuse scattering
- Large input surface (>150 mm diameter)
- High spatial resolution (50 to 100 mm)
- High dynamic range (14 bits or more)
- High sensitivity (quantum efficiency)
- Fast read-out (a few seconds or less)
L. Paolasini - X-rays and their interaction with matter
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State-of-the-art methods for diffuse scattering/diffraction
studies of crystalline materials
- Direct space real structure of systems with correlated disorder
- Time-resolved diffuse scattering studies of phase transitions
- Electron-phonon coupling in strongly correlated electron system
- Shape determination of Fermi surface in metallic systems
- Vibrational properties of nano-modulated and low-dimensional systems
Multiple phase crystal Static disorder
Structured diffuse
scattering Thermal diffuse
Ø Absorption
L. Paolasini - X-rays and their interaction with matter
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Inelastic X-ray
scattering
LATTICE VIBRATIONS
Page 46 L. Paolasini - X-rays and their interaction with matter
Vibrations around equilibrium position Origin: - Thermal vibration
- Zero point fluctuations
Temporal (thermal) average
Istantaneous displacement
Around the equilibrium position
Istantaneous structure factor:
Scattering intensity proportional to the thermal average
INELASTIC X-RAY SCATTERING
Page 47 L. Paolasini - X-rays and their interaction with matter
- High energy resolution studies of collective motion in solids and liquid phases
- Simultaneous information on energy E and momentum Q transferred between the photons and the electonic
systems of interest
• Energy transfer: Ei - Ef = DE = 1 meV – 200 meV
• Momentum transfer: Dk= 1 – 180 nm-1
Thermal Conductivity
Sound velocities and
elasticity
Superconductors
- Phonon dispersion in single crystals with small sample volume
- Collective dynamics in disordered systems
- Phonon dispersion in geophysical relevant materials
- Lattice dynamics in thin films and interfaces
Phase stability
Q = ki-kf
ki
kf
S. Galombosi, PhD thesis, Helsinki 2007
Schematic inelastic X-ray spectrum
phonons +
magnons
L. Paolasini - X-rays and their interaction with matter
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L. Paolasini - X-rays and their interaction with matter
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Scattering in
non-crystalline materials
NON CRYSTALLINE MATERIALS
Page 50 L. Paolasini - X-rays and their interaction with matter
The radial distribution function g(r) is the FT of the scattered intensity I(Q).
Radial distribution function:
g(r)®1 r(r)®rat
Radial electronic density:
Averaged areal el. density
rat
SCATTERING INTENSITIES : FROM GAS TO SOLIDS
Page 51 L. Paolasini - X-rays and their interaction with matter
SCATTERING OF GLASSES AND LIQUIDS
Page 52 L. Paolasini - X-rays and their interaction with matter
Deviation of the electron density between two different scattering centers with respect to the averaged
electron density
Short range order ISRO
Small angle scattering ISAXS
electron density at rnm=(rn-rm) with
respect at rn
we add and subtract this term at the scattering intensity
Scattering intensity
ISRO : Structural information on interatomic distances
ISAXS : Information on shape. Morphology and size of molecular aggregate
EX.: LIQUID METALS
Page 53 L. Paolasini - X-rays and their interaction with matter
Radia
Liquid/glass “structure factor”
Radial distribution function of Liquid/glass
The integral of the first peak gives the number of the
atoms in the first coordination shell
L
Ti39Zr39.5Ni21
Electrostatic levitation
Laser heating
2mm
N~12 nearest neighbours
Icosahedral coordination
The peak position indicate the first neighbour distance
r=2.5 Å
SMALL ANGLE X-RAYS SCATTERING (SAXS)
Page 54 L. Paolasini - X-rays and their interaction with matter
Scattering at small Q vectors is sensitive to the uniform electron distribution in molecules of shaped large
object (polymers, biological macro-molecules ...)
Scattering length density: Fourier transform of charge density
Solvent scattering
length density
Particle scattering
length density
Particle “form factor”
Vp particle volume
For diluted molecules in solutions:
EX.: SAXS ON RIGID SPHERES
Page 55 L. Paolasini - X-rays and their interaction with matter
Form of the a sphere of radius R
Small angle scattering experiment on a rigid sphere of radius R
Dr= excess of number of electrons with respect to the solvent
F(Q) form factor of the sphere
Vp=volume of the sphere
Long wavelength limit
PARTICLE DIMENSIONALITY
Page 56 L. Paolasini - X-rays and their interaction with matter
Sphere
Radius of giration
Uniform sphere
SMALL ANGLE X-RAY SCATTERING (SAXS) IN STRUCTURAL BIOLOGY
molecular shape, molecular interactions, kinetics, etc…
Small Angle X-ray Scattering (SAXS) is a technique for studying structure at low resolution in
solution & under normal biophysical/biochemical conditions
Information from SAXS: - model independent parameters (Rg, I(0))
- ab initio shape determination
- rigid body modelling
L. Paolasini - X-rays and their interaction with matter
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L. Paolasini - X-rays and their interaction with matter
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X-rays absorption
PHOTON ABSORPTION/EMISSION
Page 59 L. Paolasini - X-rays and their interaction with matter
The absorption of electromagnetic radiation change with the wavelength and depends from the
characteristic properties of photon/matter interaction.
8-9 µm
(IR)
3.3 mm
(microwaves)
0.35-0.38 µm
(UV)
25 pm ~ 10-10mm
(X-rays)
0.74-0.38 µm
(visible)
> 10-11mm
(g-rays)
ABSORPTION AND EMISSION PROCESSES
Page 60 L. Paolasini - X-rays and their interaction with matter
Photo-electric absorption
Photon absorbed and electron emitted in the
continuum
Fluorescent emission
An electron from the outer shell fill the
hole and emit a photon
Auger electron emission
The atom relax into the ground state by emitting an
electron
Absorption and emission processes are tools for basic analysis of the electronic structure of atom,
molecules and solids over different energy scales.
INTERACTION HAMILTONIAN
L. Paolasini - X-rays and their interaction with matter
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The interaction Hamiltonian is the weak relativistic limit of Dirac’s equation (terms v/c < 1)
Absorption and emission processes
Scattering processes
PHOTO-ELECTRON ABSORPTION AND EMISSION PROCESSES
L. Paolasini - X-rays and their interaction with matter
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Absorption and emission processes of photo-electrons probe the atomic level and valence orbital
symmetries of the material under investigation.
ABSORPTION OF AN ISOLATED ATOM
Page 63 L. Paolasini - X-rays and their interaction with matter
X-RAY ABSORPTION EDGES
Page 64 L. Paolasini - X-rays and their interaction with matter
100
101
102
103
104
1 10 100
µ/ρ
(cm
2
/g)
65-Tb,
hω (keV)
LIII 2p3/2
LII 2p1/2
LI 2s
K 1s
MV 3d5/2
MIV 3d3/2
MIII 3p3/2
MII 3p1/2
MI 3s
(nlj)2j+1
j=l±½
X-rays energies are able to extract atomic electrons from the atomic core.
The element-specific energies of the discontinuous jumps in the x-rays absorption spectra are called
absorption edges.
ABSORPTION EDGES SCALE FACTORS : EXPERIMENT
Page 65 L. Paolasini - X-rays and their interaction with matter
K-edges
L-edges
~0.02 barn
ABSORPTION IN GAS AND CRYSTALLINE MATERIALS
Page 66 L. Paolasini - X-rays and their interaction with matter
Graphite surface
EXAFS
NEXAFS
XANES (near edge structure)
Page 67 L. Paolasini - X-rays and their interaction with matter
R
2R= double distance (neighbour)-(absorbing atom)
t(q) = scattering amplitude of neighbour atom
d = phase shift
EXAMPLE: CdTe NANO-CRYSTALS - I
Page 68 L. Paolasini - X-rays and their interaction with matter
Te K-edge
Nano-crystals:
N=3.55
Only first neighbours
(reduced clusters)
Bulk
N=4
Complex EXAFS structure
1/E3
SCATTERING AND ABSORPTION CROSS SECTIONS
Page 69 L. Paolasini - X-rays and their interaction with matter
10-15
10-10
10-5
10-2
100
102
104
106
Cross
section
(Å
2
)
E (keV)
Photoelectric
absorption
Coherent sc.
Incoherent sc.
Pair prod.
nucl. field
elec. field
32 - Ge hv=2mc2 ~ 2x511 keV
POLARIZATION DEPENDENT ABSORPTION
Page 70 L. Paolasini - X-rays and their interaction with matter
Linear dichroism
Produced by the preferential absorption of one of the two orthogonal photon polarization
Circular dichroism
Produced by the preferential absorption of one of the two circular photon polarization
Linearly oriented polimers
When the electric field is parallel to the
preferential molecular axis, it is absorbed
Combination of l/4 and linear polarized filters
have the different effect on circular polarization.
Circular dichroism is found also in chiral
molecules which select only one circular
polarization (ex. sugar)
X-RAYS MAGNETIC CIRCULAR DICHROISM
Page 71 L. Paolasini - X-rays and their interaction with matter
Quantum description of a a circular polarised
photon beam:
RCP and LCP eigenstates of Jz
Ex.: Dipole electric transitions in Oxigen
(E1)
selection rule: Dl±1
(odd function for coordinate exch.)
Transition allowed:
Dm=+1 for RCP
Dm=-1 for LCP
= +ħ = -ħ
Eigenvalues of
angular momentum
operator Jz
z
+ħ -ħ
Dm=+1 Dm=-1
Zeeman
splitting
H
The sum rule for the conservation of angular momentum in electronic transition produces a difference in the
absorption of RCP and LCP photons.
X-RAY MAGNETIC CIRCULAR DICROISM
Page 72 L. Paolasini - X-rays and their interaction with matter
Orbital occupation
(linear dichroism)
Spin moment Orbital moment
X-ray magnetic dichroism is the difference in the absorption coefficients µ± of left (-) and right (+) circularly
polarized x-rays.
SINGLE MOLECULE MAGNETS ON FERROMAGNETIC METALS
Page 73 L. Paolasini - X-rays and their interaction with matter
A. Lodi Rizzini et al., Phys. Rev. Lett. 107, 177205 (2011)
Element-resolved magnetization
measurements using X-ray magnetic
circular dichroism (soft x-rays)
Tb-complex on Ni metal film
a) Cu(110) substrate -> out-of-plane magnetization
b) Ag(100) substrate -> in-plane magnetization
a) Ni AF to Tb at H=0
H-dependent F or AF coupling
finite remanent magn. up to 100K
square hysteresis loop
b) Frustrated Tb magnetization
zero remanence at H=0
Single molecule magnets are ideal candidates for magnetic data storage
and quantum computing applications.
L. Paolasini - X-rays and their interaction with matter
Page 74
X-rays optical
properties
SCATTERING FROM BOUND ELECTRONS
Page 75 L. Paolasini - X-rays and their interaction with matter
We suppose the electron be subject to the electric field Ein of an incident X-ray beam and to a damping
term G proportional to the electron velocity ẋ which represents dissipation of energy.
G= damping factor
ws= resonant frequency
1/G= core-hole lifetime
ħws= resonant energy
THE CLASSICAL FORCED OSCILLATOR
Page 76 L. Paolasini - X-rays and their interaction with matter
The amplitude of the forced oscillations:
The radiated field Erad is proportional to the acceleration of the electron ẍ(t-R/c) at the detector position R
and at retarded time t’=t-R/c:
Total scattering length
G= damping factor
ws= resonant frequency
Thomson term
(Q dependence)
Absorption correction
(dissipation term)
Frequency-dependent refraction
index n(w)
X-RAY ABSORPTION AND DISPERSION CORRECTIONS
Page 77 L. Paolasini - X-rays and their interaction with matter
Because the electrons are bound in atoms with discrete energies, a more elaborate model than that of a cloud
of free electrons must be invoked.
The scattering amplitude includes two energy dependent term f’(w) and f”(w) which are called
“dispersion corrections”.
The absorption cross section sa is a
superposition of oscillators with relative weights,
so-called oscillator strengths, g(ωs), proportional
to σa(ω= ωs).
Thomson term
(Q dependence)
Absorption correction
(dissipation term)
Frequency-dependent refraction
index n(w)
SCATTERING AND REFRACTIVE INDEX
Page 78 L. Paolasini - X-rays and their interaction with matter
The existence of resonant scattering terms
arising from the dispersion corrections can therefore be
expected to lead to a frequency dependence of the refractive
index n.
For w<<ws => n>1 visible light
For w>>ws => n<1 x-rays
n>1 n<1
Notice that if w>>ws >>G
Real part of
refractive index
SCATTERING AND REFRACTION INDEX
Page 79 L. Paolasini - X-rays and their interaction with matter
Scattering and refraction are alternative ways to view the same physical phenomenon.
atomic number
density
n= 1- d + ib
REFRACTIVE INDEX AND ABSORPTION COEFFICIENT µ
Page 80 L. Paolasini - X-rays and their interaction with matter
X-rays propagating from vacuum to a absorbing medium of thickness Z
The waves amplitude in attenuated (b) and phase shifted (d)
I(z) attenuated transmitted wave
µ= absorption coefficient (m-1)
The attenuation length µ-1 is the distance where the intensity of the transmitted beam has dropped to
1/e
Relation between the absorption and the
refraction index
OPTICAL THEOREM
Page 81 L. Paolasini - X-rays and their interaction with matter
Taking into account the Thomson dispersion
corrections
Relation between the imaginary part of anomalous dispersion and the absorption coefficient
And because
Forward direction Q=0
REFRACTION: X-RAYS AND VISIBLE LIGHT
Page 82 L. Paolasini - X-rays and their interaction with matter
n=1-d+ib
d(air)~10-8
d(solids)~10-5
b~10-8<<d
Snell law: n1cosa=n2cosa’
Refraction index for X-rays:
Low focusing power compared
with the visible light
X-RAY FOCUSING MIRRORS
Page 83 L. Paolasini - X-rays and their interaction with matter
Ex: silicon mirror with toroidal shape
Distance from source p=76m,
Distance mirror object q=26m
q=2.7 mrad
rsagital=27 cm rtang=27 km
The critical angle for the total reflection
High quality mirrors are required for x-rays focusing and a large radius tangential focusing
ρtang.
ρsag.
ρsag.
ρtang.
X-RAYS MONOCHROMATORS
Page 84 L. Paolasini - X-rays and their interaction with matter
The Bragg diffraction from perfect crystals select a wavelength l from the synchrotron radiation
spectrum emitted by bending magnets or undulators
Reflection Transmission
X-RAY SCATTERING METHODS
Page 85 L. Paolasini - X-rays and their interaction with matter
Structural informations
Spatial informations
Absorption
contrast
Phase
contrast
L. Paolasini - X-rays and their interaction with matter
Page 86
Thank you for your attention!

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X-rays and their Interaction with Matter.pdf

  • 1. L. Paolasini - X-rays and their interaction with matter Page 1 X-rays and their interaction with matter Luigi Paolasini European Synchrotron Radition Facility paolasini@esrf.eu
  • 2. OUTLINES L. Paolasini - X-rays and their interaction with matter Page 2 “X-rays and their interaction with matter” Ø Waves and photons Ø Elastic and inelastic scattering Ø Absorption spectroscopies Ø Optical properties
  • 3. X-RAY DISCOVERY: W.C. RÖNTGEN, 1895 L. Paolasini - X-rays and their interaction with matter Page 3 Röntgen discovered a penetrating form of electromagnetic radiation able to pass through the human body: the X-rays. X-rays are produced by collision of electrons with a metal target (kinetic energy loss, “bremstralung”) Röntgenogram
  • 4. CRYSTAL DIFFRACTION: MAX VON LAUE, 1912 L. Paolasini - X-rays and their interaction with matter Page 4 X-rays are electromagnetic waves: - The x-ray wavelengths are comparable with the interatomic distances and molecular bonds. - Typical interference x-ray patterns when pass through a periodic arrangement of atoms, like in a crystal, and reveal their crystallographic symmetries. k i kf
  • 5. THEORY OF X-RAYS DIFFRACTION: BRAGG LAW, 1913 L. Paolasini - X-rays and their interaction with matter Bragg Law: 2d sinq = nl l : wavelength q : diffraction angle d : interatomic distance n : integer number The interference X-ray pattern contains the signature of the periodic arrangement of atoms in a crystals. The Bragg’s law define the relation between interatomic distances d and scattering angle q Crystal Photographic film l q d = l/2 sinq Page 5
  • 6. FROM COOLIDGE TUBE TO ROTATING ANODE. L. Paolasini - X-rays and their interaction with matter Page 6 W.D. Coolidge’s tube from General Electric developed in 1912 served as the standard X-ray tube for many decades until the advent of rotating anode generators. The X-ray spectrum has two distinct components: - Bremsstrahlung radiation : a continuous component - Sharp radiations with a characteristic energy emission Ka and Kb of the metal target. - Only 1% of the incident energy is emitted in the form of x-rays
  • 7. X-RAY TUBES: ROTATING ANODE L. Paolasini - X-rays and their interaction with matter Page 7 Today powerful x-rays sources can be obtained by rotating anode x-ray tubes. X-ray tubes are also used in CAT scanners, airport luggage scanners, X-ray crystallography, and for industrial inspection.
  • 8. DISCOVERY OF SYNCROTRON RADIATION : GENERAL ELECTRIC 1947 L. Paolasini - X-rays and their interaction with matter Page 8 Visible light emission discovered in a 70-MeV betatron at General Electric in 1947. First observation of synchrotron radiation Electromagnetic radiation emitted when charge particles moving at ultra-relativistic energies are forced to change direction under the action of a magnetic field. Synchrotron emission 1/g E >> mec2 ~ 0.511 MeV g = E/mec2 >> 1 g ~ 1957 E[GeV]
  • 9. Gas emission (red) and synchrotron light (blu) produced by high energy electrons in the magnetic field of a neutron star (Crab nebula) Crab nebula L. Paolasini - Introduction to X-ray sources and their applications: from synchrotrons to free electron lasers Most of the radiation of our galaxy is composed by synchrotron radiation. Synchrotron light was first detected in a jet emitted by M87 in 1956 by Geoffrey R. Burbidge. SYNCHROTRON RADIATION IN ASTRONOMY Page 9
  • 10. THE SYNCHROTRON RADIATION FACILITY Page 10 L. Paolasini - Introduction to X-ray sources and their applications: from synchrotrons to free electron lasers The Synchrotron is a “storage ring” where the electrons are first accelerated by a booster at high energies and then constrained on a circular orbit. X-rays are produced by the insertion devices (bending magnets or undulators) and then used in the different beamlines located in the tangent of electron trajectory LINAC Booster Synchrotron Storage ring Beamlines electrons X-rays
  • 11. X-RAYS LARGE SCALE FACILITIES L. Paolasini - X-rays and their interaction with matter Page 11 European Synchrotron Radiation Facility SYNCHROTRONS : the electrons circulate in a close orbit FREE ELECTRON LASERs: the electrons travel in linear accelerators X-Fel Ambourg
  • 12. X-RAYS ARE ELECTROMAGNETIC WAVES L. Paolasini - X-rays and their interaction with matter Page 12 Microscopes Radar Synchrotrons Radio waves Large accellerators Small wavelengths Large wavelengths Buildings Human body Insects Needle Cells Molecules Atoms Nuclei/quark radio 103 microwaves 10-2 visible 0.510-6 infrared 10-5 ultraviolet 10-8 X-rays 10-10 ultraviolet 10-8 Gamma rays 10-12 m Wavelenght : l = 2p/k = c/ n Energy : hn = E Planck’s constant : h
  • 13. X-RAYS LENGTH SCALES Page 13 L. Paolasini - X-rays and their interaction with matter Hard X-rays 1.2 MeV - 2.5 keV ~ 0.001÷ 0.5 [nm] Soft X-rays 2.5 keV - 100 eV ~0.5 ÷ 12 [nm] ULTRA SMALL Planck’s constant h = 4.135 x 1015 eV s ex. 1 Å = 0.1 nm @ 12.398 keV
  • 14. X-RAYS TIMESCALES Page 14 L. Paolasini - X-rays and their interaction with matter 10keV X-rays 2.4 x 1018 Hz = 2.4 exa Hz T = 41 x 10-3 fs = 41 attosecond l = 12.5 nm = 1.25 Å ULTRA FAST Pulse duration ESRF 20 ps Pulse duration X-FEL (theory) 4.5 fs
  • 15. ELECTROMAGNETIC WAVES AND MAXWELL EQUATIONS Page 15 L. Paolasini - X-rays and their interaction with matter The electromagnetic field generated by the electrons is described by the electric E and magnetic B in term of scalar F and vector A potential: Time periodicity T=1/n Space periodicity l=2p/k Vector potential Transverse EM waves
  • 16. X-RAYS POLARISATIONS Page 16 L. Paolasini - X-rays and their interaction with matter - The X-rays delivered by the insertion devices (bending magnets or undulators) are transverse polarized electromagnetic waves - The polarization vector e is parallel to the electric field E. - Some particular insertion devices can also deliver circular polarization (ex. helical undulators, phase plates) e Linear transverse EM wave Circular transverse EM wave
  • 17. WAVE - PARTICLE DUALITY Page 17 L. Paolasini - X-rays and their interaction with matter Oscillations ® wave Envelope ® particle localization Heisenberg uncertainly principle: Cannot define both D and l to an arbitrary accuracy Energy: E = hν = ħω Momentum: p=h/λ = ħk Decreasing D to define better the position, but we lose information on l Wave: D>>l particle: D<<l Description of the behaviour of a quantum-scale objects. where h= Planck’s constant ν=frequency k=wavevector
  • 18. WAVES AND PHOTONS : QUANTUM MECHANICS ASSUMPTIONS Page 18 L. Paolasini - X-rays and their interaction with matter (i) Particles are represented mathematically by a wavefunction, ψ(r) (ii) Probability of finding a particle in a (infinitesimal) volume dV is |ψ(r)|2dV Infinite plane wave (spatial part): ψ(z) = eikz = cos(kz) + i sin(kz) |ψ|2 = ψψ* = eikze-ikz =1 1 particle per unit volume everywhere! Spherical wave: ψ(r) = b/r eikr |ψ(r)|2 = ψψ*= b2/r2 Density of particles falls as 1/r2 Flux of particles I = No. of particles incident normally on unit area per second = = particle density x velocity = |ψ|2 x v = |ψ|2 ħk/m (m-2 s-1) r
  • 19. TOTAL SCATTERING CROSS SECTION Page 19 Total cross section: Effective area viewed by scattering particles! σ = 4πb2 Quantum case: no. particles scattered per second = fsc x 4πr2 Incident wave ψ0 = eikz Incident flux f0=|ψ0|2 v = v Scattered wave ψsc = b/r eikr Scattered flux fsc=|ψsc|2 v = b2v/r2 b= scattering length Classical case: no. particles scattered per second = f0 x πa2 n. Particles x unit area x sec. σ = πa2 Cross-sectional area of sphere Incident flux f0 Incident flux f0=|ψ0|2 v L. Paolasini - X-rays and their interaction with matter
  • 20. DIFFERENTIAL SCATTERING CROSS SECTION Page 20 L. Paolasini - X-rays and their interaction with matter Definition: Solid angle subtended by the detector: DW = A/L2 No. particles detected per sec.: ds/dW =( |ψsc|2 v x A) / (|ψ0|2 v dW) (barns/steradian) 1 barn=10-28 m2 Notice that ysc is a spherical wave |ysc|2 = b2/L2 Detector area |ysc|2 = b2/L2
  • 21. L. Paolasini - X-rays and their interaction with matter SCATTERING PROBES AND INTERACTION POTENTIALS Page 21 The scattering length b depends from the type of interaction potential with the scattering probes Neutrons: Nuclear and magnetic interaction X-rays: Electromagnetic and core-hole interactions Electrons: Electrostatic interaction
  • 22. X-RAY MATTER INTERACTION Page 22 L. Paolasini - X-rays and their interaction with matter sample Photon absorption/emission : Excitation with or without emission of electrons Photon scattering : Elastic coherent => Thomson Inelastic incoherent => Compton Resonant => elastic or inelastic Photons are totally absorbed by the material Photons are deviated by their straight direction
  • 23. X-RAY ELASTIC SCATTERING BY A FREE ELECTRON Page 23 L. Paolasini - X-rays and their interaction with matter w The incident electric field Ein forces the motion of the electron : Lorentz’s Force F=qE w Re-radiation of a spherical wave Erad Radiated spherical field Erad at observer position R: - proportional to the electron acceleration - anti-phase with respect Ein - decreases with cos(y) Thomson scattering length: (Classical electron radius)
  • 24. POLARIZATION DEPENDENCE OF THOMSON SCATTERING Page 24 L. Paolasini - X-rays and their interaction with matter The differential cross section for the Thomson scattering depends from the incident and scattered photon polarizations Dipole radiation a) b)
  • 25. MAGNETIC SCATTERING BY A FREE ELECTRON Page 25 L. Paolasini - X-rays and their interaction with matter The magnetic scattering amplitudes are very weak because proportional to the relativistic factor E/mc2 Both the H magnetic and the electric E field interact with the charge and magnetic moments of the electron from: de Bergevin and Brunel (Acta Cryst, 1981)
  • 26. THOMSON SCATTERING BY TWO FREE ELECTRONS Page 26 L. Paolasini - X-rays and their interaction with matter Differential scattering cross section Q = wavevector transfer or scattering vector - Interference between scattered X-rays observed in the direction k’ and at large distances (far field limit), with |k|= |k’|= 2p/l. - The phase difference between the two scattered X-rays is Df=(k-k’) . r = Q . r
  • 27. RANDOM DISTRIBUTION OF TWO FREE ELECTRONS Page 27 L. Paolasini - X-rays and their interaction with matter Scattering cross section (two electrons): orientational average Scattering cross section (two electrons): The scattering intensity depends from the relative orientation of scattering vector Q and the vector rn. (with neglet the polarization)
  • 28. THOMSON SCATTERING BY MANY FREE ELECTRONS Page 28 L. Paolasini - X-rays and their interaction with matter In general if we have a random distribution of electrons, the scattering function is obtained sum “coherently” all the individual terms Thomson differential scattering cross section for a electron charge distribution
  • 29. THOMSON SCATTERING BY ONE ATOM Page 29 L. Paolasini - X-rays and their interaction with matter The form factor is related to the Fourier transform of charge density distribution: a0=Bohr radius Z=1 Z=3 Z=1 Z=3 The Q dependence is due to the fact that the Thomson scattering is produced by all atomic electrons, which have a spatial extent of the same order of magnitude as the X-ray wavelength. Z=1 H Z=3 Li
  • 30. SCATTERING BY TWO ATOMS Page 30 L. Paolasini - X-rays and their interaction with matter The scattering of two atoms which have a spatial extent of electron distribution of the same order of magnitude as the X-ray wavelength. Zr0 Q Atomic form factor f(Q) Electron distribution
  • 31. SCATTERING FROM A MOLECULE Page 31 L. Paolasini - X-rays and their interaction with matter Molecular structure factors Q // C-F bond Orientational average Mo Form factor (Mo=42 electrons) |Fmol ±|2 |Fmol|2 F F F F CF4 molecule C F=fluorine= 9e- C=carbon= 6e-
  • 32. COMPTON SCATTERING (BY A FREE ELECTRON) Page 32 L. Paolasini - X-rays and their interaction with matter Inelastic collision between a photon and an electron at the rest in which part of the the photon energy is transferred to the electron (photon “red shift”) Compton scattering wavelength Fine structure constant Maximum “red-shift” when y=180 deg. No variation when y=00 ~ This scattering is incoherent and contribute only to the background. Energy shift
  • 33. INCOHERENT INELASTIC COMPTON SCATTERING Page 33 L. Paolasini - X-rays and their interaction with matter The inelastic scattering dominates at high Q vectors and for low Z elements Thomson scattering intensity approach Z2 when Q®0 Compton scattering approaches Z when Q®∞ Compton scattering elastic scattering Elastic and inelastic scattering in noble gas
  • 34. COHERENT ELASTIC SCATTERING(THOMSON) Page 34 L. Paolasini - X-rays and their interaction with matter one atom Scattering processes conserve the number of photons If the photon energy is conserved, the scattering is elastic. If not. It is inelastic a molecule a crystal Atomic form factor Molecule structure factors Crystal structure factors
  • 35. CRYSTAL STRUCTURE FACTOR Page 35 L. Paolasini - X-rays and their interaction with matter The Fourier transform of the crystal (the crystal structure factor) is equal to the product of the FT of lattice and the basis The lattice sum is non vanishing only when: FT Lattice FT Basis Rn Laue conditions
  • 36. EXAMPLE OF RECIPROCAL SPACES Page 36 L. Paolasini - X-rays and their interaction with matter
  • 37. EQUIVALENCE BRAGG-LAUE Page 37 L. Paolasini - X-rays and their interaction with matter Bragg’s law: Laue’s condition Differential cross section for the Bragg diffraction in crystals
  • 38. EWALD SPHERE Page 38 L. Paolasini - X-rays and their interaction with matter Geometric construction that allows one to visualize the Bragg' law during the elastic diffraction experiment Only all the reciprocal lattice points Ghkl intercepting the Ewald sphere fulfill the Bragg conditions All the Ghkl contained in limiting sphere could be reached by rotating the sample about the goniometer axis
  • 39. POWDER DIFFRACTION Page 39 L. Paolasini - X-rays and their interaction with matter Size and symmetry of the unit cell Debye-Scherrer cone Lorentz factor Detector aperture d Multiplicity mhkl Polarization factor
  • 40. At RT-RP, Orthorhombic Fddd based on S8 rings (molecular units) EXAMPLE : HIGH PRESSURE SYNTESIS OF SULFUR L. Paolasini - X-rays and their interaction with matter Page 40 • Pressure up to 17 GPa on 2 mm3 sample volume • Resistive heating up to 2000 K P=3GPa T=600K Hexagonal P3221
  • 41. WHITE BEAM LAUE PATTERN Page 41 L. Paolasini - X-rays and their interaction with matter Polychromatic beam technique used in protein crystallography or in more complex structures. Data collection of a large number of reflections All the lattice points contained in the grey area contribute to the Bragg diffraction
  • 42. Structure of MbCO at different time delays after photolysis. The bound CO dissociates, eventually becoming trapped in sites 4 and 5, where it remains out to the microsecond time scale. F. Schotte et al., (2003), Science, 300, 1944-1947. Time-resolved MX using the Laue technique (White/Pink beam) TIME RESOLVED PROTEIN CRYSTALLOGRAPHY L. Paolasini - X-rays and their interaction with matter Page 42
  • 43. X-RAY DIFFRACTION WITH 2D DETECTORS • Multi-length scale problems L. Paolasini - X-rays and their interaction with matter Page 43 (b) Powder diffraction at large working distances (a) Powder diffraction at short working distances (d) Liquid and amorphous materials scattering at short working distances (e) Specialized single crystal diffraction. (c) Single crystal diffuse scattering - Large input surface (>150 mm diameter) - High spatial resolution (50 to 100 mm) - High dynamic range (14 bits or more) - High sensitivity (quantum efficiency) - Fast read-out (a few seconds or less)
  • 44. L. Paolasini - X-rays and their interaction with matter Page 44 State-of-the-art methods for diffuse scattering/diffraction studies of crystalline materials - Direct space real structure of systems with correlated disorder - Time-resolved diffuse scattering studies of phase transitions - Electron-phonon coupling in strongly correlated electron system - Shape determination of Fermi surface in metallic systems - Vibrational properties of nano-modulated and low-dimensional systems Multiple phase crystal Static disorder Structured diffuse scattering Thermal diffuse Ø Absorption
  • 45. L. Paolasini - X-rays and their interaction with matter Page 45 Inelastic X-ray scattering
  • 46. LATTICE VIBRATIONS Page 46 L. Paolasini - X-rays and their interaction with matter Vibrations around equilibrium position Origin: - Thermal vibration - Zero point fluctuations Temporal (thermal) average Istantaneous displacement Around the equilibrium position Istantaneous structure factor: Scattering intensity proportional to the thermal average
  • 47. INELASTIC X-RAY SCATTERING Page 47 L. Paolasini - X-rays and their interaction with matter - High energy resolution studies of collective motion in solids and liquid phases - Simultaneous information on energy E and momentum Q transferred between the photons and the electonic systems of interest • Energy transfer: Ei - Ef = DE = 1 meV – 200 meV • Momentum transfer: Dk= 1 – 180 nm-1 Thermal Conductivity Sound velocities and elasticity Superconductors - Phonon dispersion in single crystals with small sample volume - Collective dynamics in disordered systems - Phonon dispersion in geophysical relevant materials - Lattice dynamics in thin films and interfaces Phase stability Q = ki-kf ki kf
  • 48. S. Galombosi, PhD thesis, Helsinki 2007 Schematic inelastic X-ray spectrum phonons + magnons L. Paolasini - X-rays and their interaction with matter Page 48
  • 49. L. Paolasini - X-rays and their interaction with matter Page 49 Scattering in non-crystalline materials
  • 50. NON CRYSTALLINE MATERIALS Page 50 L. Paolasini - X-rays and their interaction with matter The radial distribution function g(r) is the FT of the scattered intensity I(Q). Radial distribution function: g(r)®1 r(r)®rat Radial electronic density: Averaged areal el. density rat
  • 51. SCATTERING INTENSITIES : FROM GAS TO SOLIDS Page 51 L. Paolasini - X-rays and their interaction with matter
  • 52. SCATTERING OF GLASSES AND LIQUIDS Page 52 L. Paolasini - X-rays and their interaction with matter Deviation of the electron density between two different scattering centers with respect to the averaged electron density Short range order ISRO Small angle scattering ISAXS electron density at rnm=(rn-rm) with respect at rn we add and subtract this term at the scattering intensity Scattering intensity ISRO : Structural information on interatomic distances ISAXS : Information on shape. Morphology and size of molecular aggregate
  • 53. EX.: LIQUID METALS Page 53 L. Paolasini - X-rays and their interaction with matter Radia Liquid/glass “structure factor” Radial distribution function of Liquid/glass The integral of the first peak gives the number of the atoms in the first coordination shell L Ti39Zr39.5Ni21 Electrostatic levitation Laser heating 2mm N~12 nearest neighbours Icosahedral coordination The peak position indicate the first neighbour distance r=2.5 Å
  • 54. SMALL ANGLE X-RAYS SCATTERING (SAXS) Page 54 L. Paolasini - X-rays and their interaction with matter Scattering at small Q vectors is sensitive to the uniform electron distribution in molecules of shaped large object (polymers, biological macro-molecules ...) Scattering length density: Fourier transform of charge density Solvent scattering length density Particle scattering length density Particle “form factor” Vp particle volume For diluted molecules in solutions:
  • 55. EX.: SAXS ON RIGID SPHERES Page 55 L. Paolasini - X-rays and their interaction with matter Form of the a sphere of radius R Small angle scattering experiment on a rigid sphere of radius R Dr= excess of number of electrons with respect to the solvent F(Q) form factor of the sphere Vp=volume of the sphere Long wavelength limit
  • 56. PARTICLE DIMENSIONALITY Page 56 L. Paolasini - X-rays and their interaction with matter Sphere Radius of giration Uniform sphere
  • 57. SMALL ANGLE X-RAY SCATTERING (SAXS) IN STRUCTURAL BIOLOGY molecular shape, molecular interactions, kinetics, etc… Small Angle X-ray Scattering (SAXS) is a technique for studying structure at low resolution in solution & under normal biophysical/biochemical conditions Information from SAXS: - model independent parameters (Rg, I(0)) - ab initio shape determination - rigid body modelling L. Paolasini - X-rays and their interaction with matter Page 57
  • 58. L. Paolasini - X-rays and their interaction with matter Page 58 X-rays absorption
  • 59. PHOTON ABSORPTION/EMISSION Page 59 L. Paolasini - X-rays and their interaction with matter The absorption of electromagnetic radiation change with the wavelength and depends from the characteristic properties of photon/matter interaction. 8-9 µm (IR) 3.3 mm (microwaves) 0.35-0.38 µm (UV) 25 pm ~ 10-10mm (X-rays) 0.74-0.38 µm (visible) > 10-11mm (g-rays)
  • 60. ABSORPTION AND EMISSION PROCESSES Page 60 L. Paolasini - X-rays and their interaction with matter Photo-electric absorption Photon absorbed and electron emitted in the continuum Fluorescent emission An electron from the outer shell fill the hole and emit a photon Auger electron emission The atom relax into the ground state by emitting an electron Absorption and emission processes are tools for basic analysis of the electronic structure of atom, molecules and solids over different energy scales.
  • 61. INTERACTION HAMILTONIAN L. Paolasini - X-rays and their interaction with matter Page 61 The interaction Hamiltonian is the weak relativistic limit of Dirac’s equation (terms v/c < 1) Absorption and emission processes Scattering processes
  • 62. PHOTO-ELECTRON ABSORPTION AND EMISSION PROCESSES L. Paolasini - X-rays and their interaction with matter Page 62 Absorption and emission processes of photo-electrons probe the atomic level and valence orbital symmetries of the material under investigation.
  • 63. ABSORPTION OF AN ISOLATED ATOM Page 63 L. Paolasini - X-rays and their interaction with matter
  • 64. X-RAY ABSORPTION EDGES Page 64 L. Paolasini - X-rays and their interaction with matter 100 101 102 103 104 1 10 100 µ/ρ (cm 2 /g) 65-Tb, hω (keV) LIII 2p3/2 LII 2p1/2 LI 2s K 1s MV 3d5/2 MIV 3d3/2 MIII 3p3/2 MII 3p1/2 MI 3s (nlj)2j+1 j=l±½ X-rays energies are able to extract atomic electrons from the atomic core. The element-specific energies of the discontinuous jumps in the x-rays absorption spectra are called absorption edges.
  • 65. ABSORPTION EDGES SCALE FACTORS : EXPERIMENT Page 65 L. Paolasini - X-rays and their interaction with matter K-edges L-edges ~0.02 barn
  • 66. ABSORPTION IN GAS AND CRYSTALLINE MATERIALS Page 66 L. Paolasini - X-rays and their interaction with matter Graphite surface EXAFS NEXAFS XANES (near edge structure)
  • 67. Page 67 L. Paolasini - X-rays and their interaction with matter R 2R= double distance (neighbour)-(absorbing atom) t(q) = scattering amplitude of neighbour atom d = phase shift
  • 68. EXAMPLE: CdTe NANO-CRYSTALS - I Page 68 L. Paolasini - X-rays and their interaction with matter Te K-edge Nano-crystals: N=3.55 Only first neighbours (reduced clusters) Bulk N=4 Complex EXAFS structure 1/E3
  • 69. SCATTERING AND ABSORPTION CROSS SECTIONS Page 69 L. Paolasini - X-rays and their interaction with matter 10-15 10-10 10-5 10-2 100 102 104 106 Cross section (Å 2 ) E (keV) Photoelectric absorption Coherent sc. Incoherent sc. Pair prod. nucl. field elec. field 32 - Ge hv=2mc2 ~ 2x511 keV
  • 70. POLARIZATION DEPENDENT ABSORPTION Page 70 L. Paolasini - X-rays and their interaction with matter Linear dichroism Produced by the preferential absorption of one of the two orthogonal photon polarization Circular dichroism Produced by the preferential absorption of one of the two circular photon polarization Linearly oriented polimers When the electric field is parallel to the preferential molecular axis, it is absorbed Combination of l/4 and linear polarized filters have the different effect on circular polarization. Circular dichroism is found also in chiral molecules which select only one circular polarization (ex. sugar)
  • 71. X-RAYS MAGNETIC CIRCULAR DICHROISM Page 71 L. Paolasini - X-rays and their interaction with matter Quantum description of a a circular polarised photon beam: RCP and LCP eigenstates of Jz Ex.: Dipole electric transitions in Oxigen (E1) selection rule: Dl±1 (odd function for coordinate exch.) Transition allowed: Dm=+1 for RCP Dm=-1 for LCP = +ħ = -ħ Eigenvalues of angular momentum operator Jz z +ħ -ħ Dm=+1 Dm=-1 Zeeman splitting H The sum rule for the conservation of angular momentum in electronic transition produces a difference in the absorption of RCP and LCP photons.
  • 72. X-RAY MAGNETIC CIRCULAR DICROISM Page 72 L. Paolasini - X-rays and their interaction with matter Orbital occupation (linear dichroism) Spin moment Orbital moment X-ray magnetic dichroism is the difference in the absorption coefficients µ± of left (-) and right (+) circularly polarized x-rays.
  • 73. SINGLE MOLECULE MAGNETS ON FERROMAGNETIC METALS Page 73 L. Paolasini - X-rays and their interaction with matter A. Lodi Rizzini et al., Phys. Rev. Lett. 107, 177205 (2011) Element-resolved magnetization measurements using X-ray magnetic circular dichroism (soft x-rays) Tb-complex on Ni metal film a) Cu(110) substrate -> out-of-plane magnetization b) Ag(100) substrate -> in-plane magnetization a) Ni AF to Tb at H=0 H-dependent F or AF coupling finite remanent magn. up to 100K square hysteresis loop b) Frustrated Tb magnetization zero remanence at H=0 Single molecule magnets are ideal candidates for magnetic data storage and quantum computing applications.
  • 74. L. Paolasini - X-rays and their interaction with matter Page 74 X-rays optical properties
  • 75. SCATTERING FROM BOUND ELECTRONS Page 75 L. Paolasini - X-rays and their interaction with matter We suppose the electron be subject to the electric field Ein of an incident X-ray beam and to a damping term G proportional to the electron velocity ẋ which represents dissipation of energy. G= damping factor ws= resonant frequency 1/G= core-hole lifetime ħws= resonant energy
  • 76. THE CLASSICAL FORCED OSCILLATOR Page 76 L. Paolasini - X-rays and their interaction with matter The amplitude of the forced oscillations: The radiated field Erad is proportional to the acceleration of the electron ẍ(t-R/c) at the detector position R and at retarded time t’=t-R/c: Total scattering length G= damping factor ws= resonant frequency Thomson term (Q dependence) Absorption correction (dissipation term) Frequency-dependent refraction index n(w)
  • 77. X-RAY ABSORPTION AND DISPERSION CORRECTIONS Page 77 L. Paolasini - X-rays and their interaction with matter Because the electrons are bound in atoms with discrete energies, a more elaborate model than that of a cloud of free electrons must be invoked. The scattering amplitude includes two energy dependent term f’(w) and f”(w) which are called “dispersion corrections”. The absorption cross section sa is a superposition of oscillators with relative weights, so-called oscillator strengths, g(ωs), proportional to σa(ω= ωs). Thomson term (Q dependence) Absorption correction (dissipation term) Frequency-dependent refraction index n(w)
  • 78. SCATTERING AND REFRACTIVE INDEX Page 78 L. Paolasini - X-rays and their interaction with matter The existence of resonant scattering terms arising from the dispersion corrections can therefore be expected to lead to a frequency dependence of the refractive index n. For w<<ws => n>1 visible light For w>>ws => n<1 x-rays n>1 n<1 Notice that if w>>ws >>G Real part of refractive index
  • 79. SCATTERING AND REFRACTION INDEX Page 79 L. Paolasini - X-rays and their interaction with matter Scattering and refraction are alternative ways to view the same physical phenomenon. atomic number density n= 1- d + ib
  • 80. REFRACTIVE INDEX AND ABSORPTION COEFFICIENT µ Page 80 L. Paolasini - X-rays and their interaction with matter X-rays propagating from vacuum to a absorbing medium of thickness Z The waves amplitude in attenuated (b) and phase shifted (d) I(z) attenuated transmitted wave µ= absorption coefficient (m-1) The attenuation length µ-1 is the distance where the intensity of the transmitted beam has dropped to 1/e Relation between the absorption and the refraction index
  • 81. OPTICAL THEOREM Page 81 L. Paolasini - X-rays and their interaction with matter Taking into account the Thomson dispersion corrections Relation between the imaginary part of anomalous dispersion and the absorption coefficient And because Forward direction Q=0
  • 82. REFRACTION: X-RAYS AND VISIBLE LIGHT Page 82 L. Paolasini - X-rays and their interaction with matter n=1-d+ib d(air)~10-8 d(solids)~10-5 b~10-8<<d Snell law: n1cosa=n2cosa’ Refraction index for X-rays: Low focusing power compared with the visible light
  • 83. X-RAY FOCUSING MIRRORS Page 83 L. Paolasini - X-rays and their interaction with matter Ex: silicon mirror with toroidal shape Distance from source p=76m, Distance mirror object q=26m q=2.7 mrad rsagital=27 cm rtang=27 km The critical angle for the total reflection High quality mirrors are required for x-rays focusing and a large radius tangential focusing ρtang. ρsag. ρsag. ρtang.
  • 84. X-RAYS MONOCHROMATORS Page 84 L. Paolasini - X-rays and their interaction with matter The Bragg diffraction from perfect crystals select a wavelength l from the synchrotron radiation spectrum emitted by bending magnets or undulators Reflection Transmission
  • 85. X-RAY SCATTERING METHODS Page 85 L. Paolasini - X-rays and their interaction with matter Structural informations Spatial informations Absorption contrast Phase contrast
  • 86. L. Paolasini - X-rays and their interaction with matter Page 86 Thank you for your attention!