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Institute of Ion-Beam Physics and Materials Research � PD Dr. Sibylle Gemming � www.fzd.de � Member of the Leibniz Association
Structure of Matter
Density-Functional Theoryin Materials Science
S. GemmingInstitute of Ion Beam Physics and Materials Research
FZ Dresden-Rossendorf
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 2
Structure of Matter
Time and length scales in materials modelling
electronicstructure
atomisticmodelling
discrete particles, processesfinite-element
continuummodels
piko nano micro macro
Time/length scale of modelled phenomenon
Sys
tem
siz
elo
g N
(at)
0
3
6
20~~
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 3
Structure of Matter
(I) Electronic structure
calculations
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 4
Structure of Matter
I Electronic structure calculations –Quantum mechanics
• Explicit calculation of electron distribution and energies
• Separation of nucleus- and electron dynamics(= Born-Oppenheimer approximation)and stepwise optimisation of both systems
• Energy conservation in Hamilton formalism
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 5
Structure of Matter
I Electronic structure calculations –Quantum mechanics
• Explicit calculation of electron distribution and energies
• Separation of nucleus- and electron dynamics(= Born-Oppenheimer approximation)and stepwise optimisation of both systems
• Energy conservation in Hamilton formalism
i j
nucleus
electrons
E = Enn + Ene + Eee + Te
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 6
Structure of Matter
I Electronic structure calculations –Quantum mechanics
• Explicit calculation of electron distribution and energies
• Separation of nucleus- and electron dynamics(= Born-Oppenheimer approximation)and stepwise optimisation of both systems
• Energy conservation in Hamilton formalism
i j
Vijnn =
|Ri - Rj|ZiZje2
Vijee =
|ri - rj|e2
Vijne =
|Ri - rj|-Zie2
Te = 1/2 mv2E = Enn + Ene + Eee + Te
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 7
Structure of Matter
Standard Electronic Structure Methods
• Hartree-Fock (HF) formalism: wave function
scaling: N4
and spectroscopy with correlation correctionsscaling: N4 - N7
• Density Functional Theory (DFT): electron density
and atom arrangement via Car-Parrinello dynamicsscaling: N3
• Tight-Binding (TB) and semiempirical methodsscaling: N, NlogN, N2, N3
N = number of atoms
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 8
Structure of Matter
Hartree-Fock Method
• Idea: calculate everything, up to ∫∫∫∫∫∫∫ (7-fold integration !!) of interactions
• Virtue:inclusion of further interactions straightforward
strong electronic correlations = more than two electron cross-talkelectric and magnetic fields, relativistic corrections (spin-orbit)
• Limitation: system sizes up to 10-30 atoms
• Accuracy: spectroscopic accuracy (meV, pm)
• Acronyms: MPn = Møller-Plesset perturbation theory
CAS = Complete Active Space, CI = Configuration InteractionCC = Coupled Cluster
Very high predictive power, but computationally expensive
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 9
Structure of Matter
Density Functional Theory I
• Idea: Calculate up to 3-fold integrals, include others in "mean-field" potential
• Virtue:Inclusion of further interactions for larger systems
electric and magnetic fields, relativistic corrections (spin-orbit)
• Limitation: up to 103 atomsband gap too small, correction terms complicatedground state, no easy description of excited states
• Accuracy: atom distances ~ pm, lattice constants ± 3% occupied levels ~ meV
Very good predictive power for ground state (!) systems
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 10
Structure of Matter
Density Functional Theory II
• Basis: Hohenberg-Kohn Theorems (Hohenberg/Kohn/Sham, 1964/65)
Ø Theorem I:all observables = function(al)s of the ground state electron density n0.
Ø Theorem II:variational principle → ground state electron density n0
(total energy reaches is minimal, if n0 is inserted in the functional)
E[n0] = Enn[n0] + Ene[n0] + Eee [n0] + Exc[n0] + Te[n0]
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 11
Structure of Matter
Density Functional Theory II
• Basis: Hohenberg-Kohn Theorems (Hohenberg/Kohn/Sham, 1964/65)
Ø Theorem I:all observables = function(al)s of the ground state electron density n0.
Ø Theorem II:variational principle → ground state electron density n0
(total energy reaches is minimal, if n0 is inserted in the functional)
• Acronyms: LDA = Local Density ApproximationGGA = Generalized Gradient ApproximationVWN, PZ, PBE, BP, BLYP, B3LYP, … = different forms of Exc[n]
E[n0] = Enn[n0] + Ene[n0] + Eee [n0] + Exc[n0] + Te[n0]
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 12
Structure of Matter
Tight-Binding Method
• Idea: calculate only double integrals, parameters for other onesinner electrons + nucleus → effective core potential
separation into: on-site term (Coulomb)+ hopping term for electron interactions
between (directly) neighbouring atoms
• Easy incorporation of other interactions, including excitation
• Limitation: system sizes up to several 104 atoms
• Accuracy: mostly explanatory, limited predictive power
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 13
Structure of Matter
(II) Electronic structure
of the solid state
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 14
Structure of Matter
Modelling electronic structure of crystals
• Idea: exploit long-range periodicity
• Realisation:calculate smallest unit cell explicitlyapply Periodic Boundary Conditions
PBCa1a2
a3
basis vectors
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 15
Structure of Matter
Electrons in the lattice
• Basis set representation of electron distribution:ψk(r) = ΣG ck+G ei(k+G)r
• Typical basis sets:
plane waves
local orbitals
LAPW (linearised augmented plane waves =local orbitals for core, plane waves for rest)
s dp
FPLO (full potential local orbitals)LMTO (linearised muffin-tin orbitals)
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 16
Structure of Matter
The trick: reciprocal space
• not all plane waves eikr match latticeonly discrete subset G witheiG(r+R) = eiGr
= reciprocal lattice
• reciprocal space unit cell = Brillouin Zone
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 17
Structure of Matter
The trick: reciprocal space
• not all plane waves eikr match latticeonly discrete subset G witheiG(r+R) = eiGr
= reciprocal lattice
• reciprocal space unit cell = Brillouin Zone
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 18
Structure of Matter
Pseudopotentials
• Lattice periodic potential comprisesVnuc-nuc, Vnuc-el, Vel-el (Coulomb, XC)
• Problem:strong spatial modulation of core e-
requires many plane waves or local functions
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 19
Structure of Matter
Pseudopotentials
• Lattice periodic potential comprisesVnuc-nuc, Vnuc-el, Vel-el (Coulomb, XC)
• Problem:strong spatial modulation of core e-
requires many plane waves or local functions
• Solution: treat only valence e- explicitlyscreen Vnuc by potential of core e-
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 20
Structure of Matter
Pseudopotentials
• General form of ion-electron termVion-el = Vloc + Vnl
• Norm-conserving PP
∫ nPP dr = ∫ nAE dr in core region
• Ultrasoft PP
specially smooth nPP, few plane waves
long-rangelocal part
short-rangel-dependent part
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 21
Structure of Matter
Basic properties
• Total energy E and energy levels Enk
band structure (occupied) = levels vs. k,E
density of states (DOS) = levels vs. E
• Derivatives of E
Hellman-Feynman forces, geometry = ∂E / ∂Ri
stress tensor components = ∂2E / ∂Ri ∂Rj
phonons = ∂E / ∂Ri vs. k
external electric field (long-wave)
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 22
Structure of Matter
k0aπ
aπ-
Band structure
• Energy Enk depends on band index n (Pauli principle)wave vector k dispersion
• band structure – density of states (DOS)
k0aπ
2aπ
aπ
2aπ- -
E3
E2
E1
EFermi
DOS
occupied
virtual
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 23
Structure of Matter
Spectroscopy – ELNES, XANES
S. Köstlmeier, C. Elsässer, Phys. Rev. B 60 (1999) 14025.S. Köstlmeier, C.Elsässer, B. Meyer, Ultramicroscopy 80 (1999) 145.S. Köstlmeier, Ultramicroscopy 86 (2001) 319.
dens
ityof
sta
tes
DO
S
core statesEELS
valence statesVEELS
empty states Fermi'sGolden Rule:
ELNES ~ M(E) x DOS(E)
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 24
Structure of Matter
-10 0 10 20 -10 0 10 20 -10 0 10 20
exp.exp.
theo. theo.theo.
exp.
C
C
B
AA'
A
BA'
A'
A
B C
A' A
C
A'
A
B CA'
A
C
O-K Edges in Oxides - ELNES
MgO MgAl2O4 α-Al2O3
Energy [eV]
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 25
Structure of Matter
(III) Applications
2D structures – domain boundaries1D structures – wires
0D structures – clusters on surfaces
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 26
Structure of Matter
Time and length scales in materials modelling
electronicstructure
atomisticmodelling
discrete particles, processesfinite-element
continuummodels
piko nano micro macro
Time/length scale of modelled phenomenon
Sys
tem
siz
elo
g N
(at)
0
3
6
20~~
Page 27
Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 27
Structure of Matter
Piezo ||
109°
180°
conductivity
71°
109°
180° BiFeO
pseudo-cubicBi arrangement
tilted,distortedFeO6
Oktaeder
Seidel et al., Nature Mater. 8 (09) 229.
⟨111⟩ polarisation Tc = 650 Kantiferromagnet TN = 1103 K
Domains in BiFeO3
2D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 28
Structure of Matter
Piezo ||
109°
180°
conductivity
+
+
+
71°
109°
180°
P|| ⟨⟨⟨⟨1
11⟩⟩⟩⟩
71°
109°
180°
Domains in BiFeO3
2D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 29
Structure of Matter
Piezo ||
109°
180°
conductivity
+
+
+
71°
109°
180°
P|| ⟨⟨⟨⟨1
11⟩⟩⟩⟩
71°
109°
180°0.36 J/m2
0.21 J/m2
0.83 J/m2
0.02 eV
0.18 eV
0.15 eV
Domain boundaries in BiFeO3
2D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 30
Structure of Matter
MoS2 – based nanowires: S-deficient Mo6S6
(Nano Lett. 8 (2008) 3928-3931)
1D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 31
Structure of Matter
Ø maxima at SØ distances 4.4 Å, 10.2 ÅØ wire height 9.4(±0.1)Å
Connolly sphere onDFT density contour4 – 10 Å
experiment simulation
Mo6S6 nanowires: STM - structure
Electromechanics
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 32
Structure of Matter
Mo d+
S p
states
Mo dstates
=conductionband edge
Ø metallic conductance through Mo part, S insulates
Besenbacher(Aarhus)
energy [eV]
Mo6S6 nanowires: STS - conductivity
1D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 33
Structure of Matter
Mo6S6 : Electromechanic switch
(Nano Lett. 8 (2008) 4093-4097)
Mo S
tors
ion
[°/n
m]
energy [eV]
DFPT: Transmission
1D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 34
Structure of Matter
Mo6S6 : Electromechanic switch
(Nano Lett. 8 (2008) 4093-4097)
Mo S
tors
ion
[°/n
m]
energy [eV]
DFPT: Transmission
gap
1D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 35
Structure of Matter
ideal: C3v
alloweda1-a2-crossing
distorted: C3
forbiddena-a-crossing
Ene
rgie
[eV
]E
nerg
ie [e
V]
Γ k X
a1a2
e
aa
e
EF
EF
Mo6S6 : Structure-induced metal-insulator transition!
1D structures
Page 36
Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 36
Structure of Matter
Time and length scales in materials modelling
electronicstructure
atomisticmodelling
discrete particles, processesfinite-element
continuummodels
piko nano micro macro
Time/length scale of modelled phenomenon
Sys
tem
siz
elo
g N
(at)
0
3
6
20~~
Page 37
Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 37
Structure of Matter
Scale-bridging: Growth modes at vicinal surfaces
layer-by-layer
islandsroughening
phase-field (PF)
(kinetic) Monte-Carlo (KMC)
0D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 38
Structure of Matter
Motivation – Growth modes at vicinal surfaces
layer-by-layer
islandsroughening
phase-field (PF)
(kinetic) Monte-Carlo (KMC)
PF-KMC hybrid model
islands+step-flow
meandering
0D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 39
Structure of Matter
Particle-based Monte-Carlo approach
J12
J13
J12'
H
Lateral interactions:
Vertical interactions:
J13'
step
H-HsH+Hs
0D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 40
Structure of Matter
Particle-based Monte-Carlo approach
J12
J13
J12'
H
Total energy:
Etot
= Σij
J12
sis
j+ Σ
ijJ
13s
is
j+
+ Σij
J12‘
sis
j+ Σ
ijJ
13‘s
is
j
+ ΣiH s
i+
+ Σi' (H±Hs) si
NNNNN
adsorption strength
Schwöbel barrier
Monte-Carlo simulationMetropolis algorithm
si= 1: occupied; s
i= 0: empty
Lateral interactions:
Vertical interactions:
(Loppacher, Gemming, et al., Nanotechnology, 17 (06) 1568)(Kunze, Gemming, Numaza, Schreiber, CPC, accepted)
J13'
step
H-HsH+Hs
0D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 41
Structure of Matter
Burton-Cabrera-Frank model for surface growth
desorptionflux
F
diffusionD
τadatoms
adatom concentration c(r,t) surface topology= phase field
0D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 42
Structure of Matter
Continuum-theoretical phase-field description
Coupled differential equations
Evolution of the adatom concentration field c(r;t)
Evolution of the surface topology = phase field Ψ(r;t)
(I)
(II)
0D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 43
Structure of Matter
Continuum-theoretical phase-field description
Coupled differential equations
Evolution of the adatom concentration field c(r;t)
Evolution of the surface topology = phase field Ψ(r;t)
∂tc = D ∇2c – c/τ + F – ½ ∂tΨ
diffusion desorption flux coupling term
(I)
(II)
0D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 44
Structure of Matter
Continuum-theoretical phase-field description
Coupled differential equations
Evolution of the adatom concentration field c(r;t)
Evolution of the surface topology = phase field Ψ(r;t)
∂tc = D ∇2c – c/τ + F – ½ ∂tΨ
τΨ∂tΨ = W2 ∇2Ψ – sin(πΨ ) – λc[1+cos(πΨ )]
diffusion desorption flux coupling term
coupling termtopologysteps
interface motiondiffuse width W
(I)
(II)
0D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 45
Structure of Matter
Calculated properties
adatom density c(r,t), si
(T = 400 K, D = 3.2 x 105 a2/s, F = 3 ML/ms, τ = 104 s)
interface length Q(t)
nucleation rate τi(t)
topology Ψ(r,t), Hi
island density ni(r,t)
step density ns(r,t)
roughness R(t)
growth modes
(Radke, Kundin, Emmerich, Gemming, Physica B, 2009)
0D structures
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 46
Structure of Matter
Scale-CouplingScale-Hopping
MicromechanicsBCF-Phase-field with concentrations
Ising/HeisenbergMonte-Carlo (MC) with molecules/spins
(Semi-)Empirical Theorymolecular dynamics (MD) with atoms
First-principles Theoryquantum mechanics with electrons
Pa
ram
ete
r-T
ran
sfe
r
QM/MM
QM/QM‘TUD
PP/MCRWTHTUD
L [m] t [s]
10-9 10-9
10-6 10-6
10-3 10-3
100 100
10-12 10-12
Scale-bridging approaches
Goal – method cooperation
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 47
Structure of Matter
Thank you!
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Institute of Ion Beam Physics and Materials Research � FZ Dresden-Rossendorf � Sibylle Gemming � www.fzd.de � Slide 48
Structure of Matter