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Diss. ETH No.

17419

Ab initio simulations of Earth

forming

Minerals

A dissertation submitted to

ETH Zürich

For the

degree

of

Doctor of Sciences

Presented

by

Donat Jozsef Adams

Dipl. Phys.,

ETH Zürich

born March 19th, 1977

citizen of

Wangen b.

Olten

(SO)

accepted
Prof. Dr. Artem R.

on

the recommendation of

Oganov,

ETH Zürich & Moscow State

University,

examiner

Prof. Dr. Walter Steurer, ETH Zürich, examiner
Dr. Alberto Garcia, Institut de Ciencia de Materials de Barcelona,
co-examiner

Spain,

Prof. Dr. Walter Temmerman,

Daresbury Laboratory, U.K.,

co-examiner

2007

Contents

Abstract Abbreviations
1

iii
v

Computational methodology 1.1 Density functional theory (DFT) 1.2 The local density approximation 1.2.1 Inhomogeneous systems, spin polarization 1.3 Why does LDA work for inhomogeneous systems? 1.4 The generalized gradient approximation (GGA)
1.5 Self-Interaction corrected DFT 1.5.1
1.6
1.7

1
1 4

5
6
7

9
11

Exc, further developments
and the PAW method

Pseudopotentials
1.7.1

12

The linearized muffin tin orbitals method (LMTO)
1.7.2 1.7.3
1.7.4

15 15
17

potentials problem (single scatterer) The Multiple scattering problem
The atomic
Linearisation of the KKR-ASA

Muffin-tin

19
21 22

1.8

Molecular

dynamics
questions in geophysical studies of the Earth's

2

Methodology
interior
2.1

and open

25
25
27
transitions PREM

Chemical composition of the Earth
2.1.1 Seismic discontinuities and 2.2.1 2.2.2 2.2.3

2.2

phase Thermal and compositional Seismic tomography Earth's magnetic field

29 32 34

distribution

35

3

CaSi03 perovskite at P-T conditions of the Earth's lower mantle
3.1 3.2 Introduction

37
37 43 43

Methodology
3.2.1 3.2.2 3.2.3 3.2.4

Thermal equation of state

Classification of

perovskite

structures

45
46
autocor¬

Analysis

of quantities obtained in MD

Prediction of

phase

transitions

using the position

relation function

50
ionic diffusion

3.2.5
3.3

Conductivity through
Phase

51 52 54

Results 3.3.1 3.3.2

diagrams Hardening of the

unstable modes in CaSi03

60

l

2. (Mg.1.1 impurities in MgO Previous experimental and theoretical work on Mgx_xFexO 4.4 Discussion and conclusions 62 4 Effects of Fe 4.2.2.2.2.2.Fe)0.3.3 Low temperature.9 4. theoretical HS-LS transition Probable clustering of Fe-impurities Is there LS iron in the Earth's lower mantle? Densities of 93 95 96 4.5 (Mg.3.2 magnesiowustite 4. SIC-LSDA treatment of the Fe-3d electrons in 92 pressures .3.5 HS-LS spin transition in magnesiowustite 4.6 Further topics Data And Analysis 4. Mgi_xFexO 4.8 4.1 Fei_xO.5 4.2.2 4.4 Mg!_xFexO Experimental vs.1.4 67 67 67 69 in 72 on 4.5 Discussion 4.3 4. possible layering at the CMB 101 103 105 109 123 125 5 A B Conclusions and Outlook Elastic constants from the energy surface Possible configuration of Fe Bibliography Acknowledgements Curriculum Vitae . 4.2 4.Fe)Si03 perovskite and (Mg.2. defect ordering 4.1.1.1.1 GGA vs. jc=1 Two Fe impurities in the 8 atoms supercell. and high pressure phase transition Fei_xO 4.3. x =0.7 4.2 Elasticity of magnesiowustite. .Fe)Si03 97 post-perovskite.3 Equation of state 85 SIC-LSD calculations: Ionic relaxation Density of states 87 88 90 91 92 The endmember FeO in the SIC-LSD frame.3.4 PAW-GGA Theoretical work 75 76 77 78 78 79 82 84 methodology Clustering SIC-LSD methodology Transition pressures in the SIC-LSDA calculations 4.1 4.3.6 4.3 4.1.2.

comparison of the electronic density of states from these calculations with those of the more appropriate SIC-LSD results shows Fe A dard PAW-GGA method that PAW-GGA preserves the relevant features of the electronic configurations. These calculations reproduce the experimentally found linear dependence of the transition pressure upon Fe concentration well. The experimentally In a was found high Fe concentration hardening of the material across the transition was confirmed. These relaxations alter related to significantly the electronic large arrangement. The phase transition was found at a pressure range between 26 GPa to 63 GPa for low Fe < con¬ centrations [xFe 100 12. The projector augmented wave method (PAW) and the generalized gradient approximation (GGA) were applied in large scale ab initio molecular dynam¬ were tural parameter and the thermal phase boundaries of the high temperature cubic phase (s. Special attention was directed to the statistical analysis of the results obtained from MD simulations. In a follow up study the phase boundary between the ground state phase and the mechan¬ ically unstable intermediate phase was determined. The self-interaction corrected spin to density (SIC-LSD) formalism was applied collapse study magnetic moment of Fe impurities in MgO. They also show. which influence the transition pressure. A new phase for the intermediate ics (MD) simulations to determine the Grüneisen temperature region was proposed. 0-2500 K) investigated using ab initio molecular dynamics simulations and struc¬ optimization procedures.g. Pm3m) and low temperature tetragonal [14/mem) phase. which usually enhances ionic hop¬ ping. Thermal stabilization is observed at low temperatures already as it was expected from previous es¬ — structure. were In a first step the self-interaction corrections determined and added to the full are potential PAW total energy.5%). In order to determine the pressure and extract the geophysically important parameters a third order Birch-Murnaghan equation of state was applied to the volume-energy-data points. Ionic diffusion was studied by ab initio molecular dynamics simu¬ lations with the removal of oxygen atoms. A combination of the standard PAW-GGA method with the SIC-LSD formalism was used to dramatically study ionic relaxations of the structure. This method offers the advantage compared to the widely used DFT+U formalism the of the — — to be parameter free.Abstract / In the Zusammenfassung present thesis the phase diagram and the thermal properties of CaSi03 perovskite and the elastic and magnetic effects of Fe impurities in MgO magnesiowüstite under conditions of the Earth's interior (0-200 GPa.5 %) and 83 GPa to 296 GPa for (12. different series of calculation the stan¬ applied in a system with low concentrations of impurities (3-12.5< xFe < %). which can solve the long standing disagree¬ ment between experimental X-ray intensities and the theoretical ground state orthogonal Imma symmetry. The material does not have a high ionic conductivity and cannot be responsible for the observed modulation of the Earth's magnetic field. The static configuration of that phase shows the timations. and specific arguments are found to generally draw phase boundaries at a confidence level of a phase transition of 1/2. that the broad transition region can be explained with locally different Fe configura¬ tions. energy decrease although they do not .

wie sie im Einflüsse Erdinneren herrschen (0-200 GPa. Die statische Symmetrie dieser Phase ist Imma. ändern. Diese Berechnungen können die experimentell ge¬ fundene lineare Abhängigkeit des kritischen Druckes für den Phasenübergang gut reproduzieren. Experimente zeigten Dies wurde in den terials über die Phasengrenze hinweg. dass keine zusätzlichen unbekannten Parameter eingeführt werden. untersucht.5< xpe %). Ein einer weiteren Studie wurde die GGA-PAW Methode auf eine Versteifung des Ma¬ Rechnungen bestätigt. die fälschlicherweise durch die Einführung des 'local density approach' eingeführt wird. Die intermediäre Phase ist elastisch instabil. wie das magnetische Moment der Fe Einlagerungen in MgO unter Druck kollabiert. Diese Relaxationen sie die nicht ergeben signifikant eine starke Gesammt-Energie aus den PAW Energie-Erniedrigung. Sie zeigen auch. um den Druck und die Birch-Murnaghan Zustandsgieichung geophysikalischen relevanten Parameter zu bestim¬ in die Der Phasenübergang (xfé < findet zwischen bei 26 GPa und 63 GPa statt bei kleinen 12. für Elektronen in — peraturen stabilisiert was aus Der 'self-interaction corrected local stark lokalisierten atomaren Orbitalen subtrahiert.In der vorliegenden von Arbeit wurde das Phasendiagramm unter und die thermischen Eigen¬ von schaften Fe CaSiCh Perovskit und die elastischen und in Einlagerungen MgO Magnesiowüstit magnetischen Bedingungen. Der Kristall Leitfähigkeit Magnetfeldes der Erde Auswertung und kann deshalb nicht für die schwachen Modu¬ verantwortlich sein. 0-2500 K). lich die Wahrscheinlichkeit keine erhöhte ionische lationen des von gewöhn¬ zeigt ionischen Verschiebungen erhöht. . Dazu wurden die Methoden der ab in¬ Molekulardynamik und der Strukturoptimierung verwendet. Begründete Argumente wer¬ von dargelegt für die Wahl der Phasen-Grenze bei einer statistischen Sicherheit 1/2. Dieser Ansatz bietet den Vorteil. In ab initio MD Simulationen wurde die was zwischen bestimmten Intensitäten ionische Diffusion untersucht. Diese Konfiguratio¬ nen beeinflussen den kritischen Druck stark. aus wurde eine neue. Dazu wurden Sauerstoffatome entfernt. der Elektronen-Zustandsdichte mit den SIC-LSDA Resultaten dass PAW-GGA die relevanten Bestandteile Elektronen-Verteilung erhält. was ein wichti¬ ger Vorteil gegenüber dem verbreiteten DFT+U Ansatz darstellt. Energie) Datensätzen wurden eingesetzt men. wird aber durch thermische Fluktuationen schon bei niederen Tem¬ vorherigen Abschätzungen vermutet wurde. tetragonalen die die Phase (74/mcm) be¬ Es Die tetragonale Phase ist der Grundzustand bei tiefen Temperaturen. density approach' (SIC-LSDA) wurde benutzt um zu untersuchen. adäquateren der Vergleich zeigt. Die gewonnenen V. E (Volumen. dass die breite Phasengrenze erklärt werden kann durch lokale Unterschiede in der Konfiguration der Fe Atome.5 ^ Fe Konzentrationen Konzentrationen %) und zwischen 83 GPa und 296 GPa bei hohen Fe 100 (12. Die beiden Ansätze (PAW-GGA und um SIC-LSDA) wurden zusammengefügt Die die Relaxation der Atome zur zu untersuchen. langwährenden Nicht¬ übereinstimmungen experimentell RöntgenBeugungs-Experimenten und dem theoretischen tetragonalen Grundzustand löst. Beiträge wenn der Selbst-Wechselwirkung Elektronen-Besetzung wurden Rechnungen auch addiert. intermediäre Phase vorgeschlagen. In SIC-LSDA wird die Selbst-Wechselwirkung. In einer anschliessenden Untersuchung wurde die Phasengrenze zwischen dem Grundzustand und der intermediären Phase bestimmt. In Systeme mit kleinem Eisen¬ gehalt (3-12. Besondere der statistischen den der Resultate Beachtung wurde geschenkt.5%) angewandt. 'projector augmented wave method (PAW)' und die 'generalized gradient approxi¬ mation (GGA)' wurden in grossangelegten ab initio Molekulardynamik (MD) Simu¬ itio Die lationen verwendet und damit der Grüneisenparameter und die thermische Pha¬ sengrenze zwischen der kubischen [Pm3m) und stimmt.

g. for Fe2+) (Green Korringa-Kohn-Rostoker Method) Linearized Local LAPW LDA Augmented Plane Wave Density Approximation (method) e. e. 2001) VASP Vienna Ab Initio Simulation Package .) state Diamond Anvil Cell DOS EOS FCD-EMTO Density Functional Theory Density of states Equation of State Full Charge Density Exact - Muffin Tin Orbitals fee GEA GGA HS KKR face centered cubic Gradient expansion approximation Generalized Gradient Approximation Function High Spin (configuration..List of abbreviations (in alphabetical order): Abbreviation APW ASA Explanation Augmented Plane Wave Atomic sphere approximation bcc BM3 CMB DAC DFT body Core centered cubic 3rd order Birch-Murnaghan equation of Mantle Boundary (the Earth's . 1997a) Self Interaction SIC Corrected (density functional sgTPSS meta-GGA SPuDS theory) Space Group Tao-Perdew-Staroverov-Scuseria meta-GGA Structure Prediction and Diagnostic Software (Lufaso Woodward.. Spin Density (Approximation) Molecular Dynamics (Simulation) Local Methanol Ethanol Water MORB NRIXS OEP PAW POTATO (pressure medium in high pressure experiments) Mid-Ocean Ridge Basalt Nuclear Resonant inelastic X-ray scattering Optimized effective potential Projector Augmented Wave Program Originated to Analyze Tilted Octahedra (Woodward. for LMTO LS LSD MD MEW Linearized muffin tin orbitals Low Fe2+) Spin (configuration.g.

vi .

where z=z*.. Bloch states and the one-electron theories.1 Computational methodology Density functional theory (DFT) chapter as The aim of this tional is to review the fundamentals about density func¬ theory (DFT) it is implemented in many codes Stuttgart-LMTO). Most of the standard codes still introduce electronic orbitals because no functional could be found to reliably compute the kinetic energy from the density alone. the nucleus-nucleus re¬ pulsion Vnn — and the electron-electron interaction Vee. i y- = Z^rr^' i.g. Further reduction of dimensionality is introduced by the Hohenberg-Kohn theorems that state. Therefore in the Hamiltonian the terms that concern nuclei only [Tn.1 1. that for perfectly periodic systems instead of a macroscopic big sample only a limited cell in reciprocal Quantum-ESPRESSO. Expressed^in atomic Rydberg units {% = = = Hamiltonian is H = Te + Ven + Vee. a These codes broad range of (e. SIESTA. Bloch's theorem states. The exact Hamiltonian is the the nuclei Te + sum of the kinetic energy of the electrons and Tn. VASP. Wien2k. chemistry and based on the same few principles. the first Brillouin zone. This is the Born-Oppenheimer ap¬ e2/2 1) the full 2me proximation. the electron-nucleus attraction Ven. that the total density. These numbers have to be reduced further because the dimension of the exact problem for M electrons (which Fock-Space) grows exponentially with M. Pseudopotentials and especially the projector augmented wave method restrict the calculation to the treatment of the va¬ lence electrons while maintaining the high accuracy of the results. are applied to bio-chemistry and are — — space needs to be treated. Vnn) can be treated separately. problems in physics.i) ^-j \ri - rA 1 . is the fundamental variable.g. not the individual degrees of freedom of the electrons. - This reduces the number of electrons in the calculation from 1023 to 10 is formulated in the 103.i ' (l. Therefore approximations are introduced e. This in principle would reduce the di¬ mensionality to three. Although the Hamiltonian of solids which consists of electrons and nuclei is known exactly it is too difficult to be solved exactly. Because of their — mass which is 103 times the nuclei is slow bigger enough for than that of the electrons the electrons to the movement of almost in¬ adapt their positions stantaneously.

at T 0 K. charges of the nuclei. quantum objects still have kinetic energy. a (1. sitions rt the - The first = — — = Hohenberg-Kohn theorem states.1 Computational methodology and Z/ are the the electrons. The best known the local density approximation (LDA).3) much weaker correction to this term. that leads to the = The second electrons:2 y. more 2To be precise: All the interactions in the solids under discussion on due to the particles generate.1 This effective poten¬ tial isjsplitjnto two parts: the Hartree-part and the exchange-correlation part Vee Vhart + Vxc. (1.4) The exchange-correlation term is not (yet) known exactly. 2003) and the GW approximation (Shishkin and Kresse. 2000). effective potential. 2006.2) Hohenberg-Kohn theorem states. therefore both pictures should be applicable.. can be replaced by an outer. (Tao et al.The first term includes the electrostatic repulsion between the action. the Coulombic field the 2 . the generalized gradient approximation (GGA). Rr their position and The Schrödinger equation to be solved writes rt the positions of Hx¥ = ey¥. At first the electrostatic repulsion between particles is separated (Vhan) which would also be found in a system of charged macroscopic objects.(5(r r}).„ = J[?^W. 2007. the ground state. One of the first treatments of the by Hartree who simply neglected is the exchange-correlation potential was done exchange-correlation term whereas in the (which is formulated for the electronic appropriate orbitals <pt) this term term): more 1 Hartree-Fock method approximated by the Fock-term (also called exchange- In the DFT calculations of solids this potential Vhart + Vxc is added to the potential are generated by the nuclei Ven. On the other hand in a gas-like picture the kinetic energy of the particles one would expect the electrons to occupy In the whole space equally. that instead of the individual po¬ problem can be expressed in terms of the total density n(r) 2. whereas the second termincludes We are left with the full DFT Hamiltonian: H=Te+ Ven + Vhart +Vxc • (1. Better and better ones are approximations meta-GGA appear in the literature.e. They form standing waves. Here the different possible interac¬ charges tions should be classified.. Steinbeck et al. that the particle-particle inter¬ spatial density fluctuation in a homogeneous electron gas. In a particle picture one would expect that the electrons in a box in the lowest energy state would take a perfect order minimizing the mutual which accounts for repulsive forces. i. The electrons have a behavior which is in-between the two extrema: They occupy the full space but the particle density fluctuates.

and 101. (1980) developed a very accurate expression for the spin polar¬ ized correlation energy ec(n.1231 and for the ferromagnetic x2 + -0..cr2) (p2(r2. <rN) <Pn(Jn.6) constructed of the orbitals is introduced the basic wave function.<Ti) <pN(ri.7) To show that the two formulations equivalent wave I consider a wave function of two electrons t/Kri. r) i.1 Density functional theory (DFT) Vy -£wJJ*^wv. r„ .They use a Padé approximation technique in order to interpolate the Quantum Monte Carlo results of Ceperley and Alder (1980).409286.#_. 13.. . The final expression is Vosko et al.0621814.5) This term results when Pauli's Instead of single orbitals <pt their Slater determinant 4>i(ri.0.10) (an alternative way to express densities) and x -\jrs.) are (1.8) collapses. The resulting wave function thus is forced to fulfill Pauli's principle. X and Q abbreviate X(x) xb + c and Q V4c - b2.cr2) <pi(r2. if/ = -if/ *A = 0 (1.(Ti) 1 <p\(r2. and 20.1.1231. r) the wave = -if/(r.) = -if/{. This principle has two equivalent formulations: 1. If the two particles at the same position if/(r.. ^ ec(rs) = A „fi < In x 2b - + — \ tan Q 2x + bx0 b In (x-xo)2 —rr—— + 2(b + 2x0)t tan _j Q 2x + X(x) Q X(x0) X(x) Q b (1. c for the paramagnetic = case were case found to be -0. b... function . = 20. 3 . r„ rp . x0..e..(Ti) «Ahf = Im (1.cr2) 4>i(rN.. (1.) two electrons with the same spin cannot occupy the same orbital 2.0720.743294. <tn) as <p2(ri.) the wave function has to be antisymmetric: <A(.r2) and assume that the are function is antisymmetric r <A(/i. The correlation energy is approximated for the the and ferromagnetic [F) case.9) with Ann (1.. ri).. principle is taken into account. The individual parameters paramagnetic (P) rs is one the radius of the sphere containing = electron are Ap = 2AF = 0.crN) <Pi(rN.578. r2) = -i//(r2.

1

Computational methodology
For intermediate

polarizations the expression

ec(rs,0

=

e^rs)

+

Aec(rs,0

(1.11)

is used with

Aec(rs,0 ß(rs)

=

a(rs) [/(£)//"(())]

x

[l ß(rs)?}
+

f"(Q)Aec(rs,l)
a(rs)

U.12)

f(£)

is defined in eqn.
=

(1.21) and a{rr)
=

is
=

a

function of the form (1.9) with
c
=

coefficients A
It turns
atomic

-1/6tt2,

x0

-0.00475840, b

1.13107 and
a

13.0045.

out that the

Hartree-Fock method is

good approximation

for

energies and total energies ing energies on the other hand it
often underestimated.
For additional literature
see

in molecules. For the

computation of bind¬
are

is not

reliable, because these energies

(Pisani, 1996).

1.2 The local

density approximation
density approximation (LDA)
as

The aim of the local

is to introduce

simple,
Ç of
is
a

expression for VXc- It is useful to define the spin
The
situation

degree
are

of spin of spin

good, yet polarization
a

collinear

follows: if n(+) and n(-)

the individual den¬

sities for the up and for the down

component, the

£

=

"(+)~"(~).

strongest

assumption of LDA

degree might be density
can

polarization

that the

exchange
can

correlation energy eXc is volume additive i.e.

that the whole

system

be

split
sum

up into small volume fractions wherein the correlation energy eXc of the whole

is constant and the

exchange

system

be

computed from the

of the contributions of each sub-cell:

Vxc

=

/J

n(r)

exc

(w(r), Q d'r

.

(1.13)

exchange correlation energy eXc can be found Feynman diagrams (e.g. Mattuck, 1976, p. 222). density fermion system it is:
of

The

from
For

an

partial summations unpolarized high-

exc

=

0 4582 —: +

0.03109lnr,

+

B

+

CrsInrs

+

Drs

+

...

.

(1.14)

rs

Although the coefficients B, C and D can be found from the partial summa¬ tion directly (which is done in quantum field theory), they can be determined For the high-density more exactly from quantum Monte Carlo simulations. (0 < rs < 1) fermion system they yield:

4

1.2 The local

density approximation

exc(n,0)

=

—:

0 4582
+

0.03109 In rs -0.0480

+

0.0020r, In

rs

-0.0116rs
0.0047r,

(1.15) (1.16)

rs

exc(n, 1)

0.5773
=

+

0.01555 \nrs

-

0.0269

+

0.007r, \nrs

-

rs

whereas for the

low-density [rs

>

1)

case

the expressions

are:

eXc(n,0) exc(n, 1)

0.4582
=

0.1423
1 +1.0529

rs

V^+0.3334r, V^
+

(1.17) (1.18)

0.5773
=
-

0.0843
1
+

1.3981

0.261

\rs'

The parametrization is done in

a
=

respect
lations
was

to

n are

continuous at rs

way that exc(n, O and its first derivative with 1. Historically the basic Monte Carlo simu¬

were

done

details

performed by Ceperley and Alder (1980) while the parametrization by (Perdew and Zunger, 1981) and (Perdew and Wang, 1992). For see also (Eschrig, 1996, p. 160).

1.2.1
In
a

Inhomogeneous systems, spin polarization
collinear situation the

n(r) and the

degree
n(r, +) n(r, -)

of spin

spin density can be expressed using the density polarization £(r):

n(x)

n(r)

(l

+

£(r))/2

(W(r))/2 (1972) introduced
=

(1.19)
an

Von Barth and Hedin

and correlation

interpolation of the exchange 0 and energy EXc for the region between the paramagnetic £
=

the saturated

ferromagnetic £

1

cases:

6Xc(n, 0
and

=

6Xc(n, 0)

+

[eXc(n, 1)

-

eXc(n, 0)] /(£)

(1.20)

f(0
The

Q
=

+

<r)4/3

+

(i-<r)4/3-2
-

24/3

2

(1.21)
von

exchange-correlation
are

function and the

Barth-Hedin

interpolation

function

symmetric

in

£

exc(n, -0
The

=

exc(n, Ç)

/(-£)

=

f(0

.

(1.22)
be

exchange-correlation energy

can

computed from

Exc[n]

-

É£\n\

-I d3rn(r)exc(n,0

(1.23)

5

1

Computational methodology
and the

exchange-correlation potential

from

Vxc±(«(rU(r)) eXc(n,<T(r)) n(r)—exc(«(rU(r))±(l *£(#)) |UXc(«(rU(r)).
:=

+

(1.24)

This follows from

vxc(r,±)
and

-

^^{n(r)eXc(n(rU(r))}
dndd(dd\
+
+

(1.25)

<5

dn(+)

dn(±)dn

\

=

±

(d

,,
.

„^

dn(±)dÇ

dn

n

(1.26)

1.3 Why does LDA work for
It is not clear from the

inhomogeneous systems?

tained from simulations

beginning that the exchange correlation term ob¬ of a homogeneous electron gas is also valid in strongly
in
a

anisotropic
narsson

situations i.e.

systems

like atoms, molecules and solids. Gun-

plausible argument for the power of LDA also in those cases. They state that the exchange correlation energy can be expressed exactly in terms of the Kohn-Sham exchange correlation hole hKS '
et al.

(1979) gave

Vxc

=

fn(r)exc(n(r),Od3rd3
2

(1.27) (1.28)
r

exc(r)=1- fr^-A'
J \r'

r\

This is the interaction energy of
lation hole h]ns(r,r'). The further

one

electron at

with the

analysis
an

is done for the
r

exchange corre¬ exchange correlation
a

hole, which

can

be

expressed

in

absolute vector

and

relative vector

y':

hKs

=

Hc^, r)
=

y

In order to

eqn.

exploit the spherical symmetry of the Coulomb interaction in (1.27) the exchange correlation hole is expanded in spherical harmonics:

hKs=

V4^ÄL(y,r)yL(y).
L

U-29)

The vector y is
stands for the

split into its angular part y and its spherical harmonics with index L {l, ni). Resubstitution of eqn. (1.29) in eqn. (1.27), yields
=

radial

part

y while

YL

a

factor of

y2

for the

change disappear

of coordinates. On the other hand also all the contribution with L ± 0

6

4 The generalized gradient approximation (GGA) Despite the large success of LDA in many fields further improvements were needed (see also Leung et al.b. sum can be long wavelength limit of the linear response function of the homogeneous electron gas and is known 1968). = 1 - ^Je' -^^FL(j)^ f°° Jo h0(y. 1981) to problems which are not homogeneous at all e.g. 1996).r) y „ /AS _.34) The lowest order contribution ^2 to the derived from the exchange-correlation energy exactly (Ma and Brueckner.31) of LDA is that Another very important its property that parametrization preserves the hole i..e. 1. However. 2 the For the derivation of higher order terms in sm..r).r) - h£om(y. (1. Perdew et al.32) rules are general these sum hxdr' hrdr' = -1 (1. molecules. 1991).r)y2dy case = -l. which include dimensionless reduced density gradients '\Vmn\' up to order m 1\Vmn\' m (2kF)mn 2m(37r2Ym/3)(nY1+m^ ' (1.30) This proves that the exchange correlation interaction is a contribution to the total energy with spherical symmetry. 1.r)ydy .33) = 0 . 1980. successful. The numerical treatment of the gra¬ dients makes the implementation of higher gradients extremely complex.r) -^L-L A 2 2 Any1 dy = 2n \ y Jo h0(y. atoms: fxc(r) - 4°cm(r) <* ho(y.1. One of the first attempts was the in¬ troduction of the gradient expansion approximations (GEA). 1996a.4 The generalized gradient approximation (GGA) Vxc(r) V4^r = y^ f ^—) 2 I hL{y. (1. high exchange-correlation led to the success (1. m > knowledge of the long wavelength expansion of the linear and higher order response function is required (Svendsen and von Barth. 4tt Jo In a h0(y. Therefore it is appropriate to trans¬ fer its properties obtained from calculations in a homogeneous environment (Ceperley and Alder. solids. this coefficient leads to the violation of the which made the LDA so rules (eqn. Perdew and Zunger. The 7 .33).

1991). In a (1. Wang and Perdew. the reduced density gradient).35) LDA is exact and therefore uniform system. 1996a) development of further GEA approximation was also avoided. s «: 1) = Fxc(rs. gradient corrected exchange-correlation functionals when the generalized gradient approximation (GGA) was introduced (Perdew et al.b. The radius of the exchange- correlation hole is r. because little hope existed that higher gradient contributions could fully cancel the insuffi¬ ciency of the lowest order expansion. because it is caused by the Pauli exclusion principle: fulfill the sum Most successful «x(r. Perdew and Wang. 1996a.36) The second-order little over the gradient expansion remains exact for densities that vary range of the exchange-correlation hole.'7 ^Z // // l l 1/2// 'S/ —--^ 0 i i i i i 05 1 15 2 25 3 5 = | V«|/'(2kpYl) = Figure (Perdew 1.---' 'X . Further exact conditions to be fulfilled are: The exchange hole has to be strictly negative. 1. 1992.. s = 0) + [ax + ac(rs)]s2 + (1.s) rules exchange-correlation enhancement factors by construction (eqn. al. The exchange energy is New attention was attracted to E%GA= fd3rn4omFx(n.r')<0. FXc(rs.1: et Exchange-correlation enhancement factors for the PBE96 GGA. s = 0) = eXc(n)/ex(n) .33).37) 8 . Ç 0..'S _ 2 ------ . (1. but retaining higher contributions for the determination of coefficients of each contribution (usually one abbreviates s2 as s. It can be viewed as a partial resummation of the GEA dropping terms higher than ^2 for the functional dependence.-'i^ 'jS^ r <•' *'* 'S s N13 ^ 4 ' . the FXc(rs.1 Computational methodology 1 6 1 1 1 1 1 "j> 1 5 «-**** '<2^ " - *&^ ' 10 1 4 - S_jT ^-' ' .

H-atom or a single. The most instructive is the case to show this single electron in are an s-orbital with spin fixed upward.g. How this problem can be solved is presented in section 1. -) = 0 While in the Hartree-Fock theory Vxc = VX = -- : dr - 2 J \r r'\ and therefore VXc mation sumarized = -U. GGA corrects for the total PW overbinding present versions of GGA are in LDA and energies. (1. (Wang and Perdew.4) follows that the Hartree and the of In exchange-correlation energy should cancel each other exactly in the case a one-electron system (e. in LDA (and GGA. Therefore Vxc + U = 0 . This relation in LDA is not fulfilled. 1968). that case we should recover the Schrödinger equation consisting of the terms Te + Vext • The terms from the interaction of several electrons (VXc and U) should vanish because the single electron we want to describe has no other electrons to interact with.5 Self-Interaction corrected DFT where ax and ac(rs) are the gradient coefficients derived e. n(r. 1.1 shows the 1.g.5.g. Popular PBE gives more accurate (Perdew et al. s) of PBE GGA. The densities for spin up and down n(r. Fig. 1991). local together with any other approxi¬ as spin density approximation LSD) V 1 2 J fhom(n = W)\2^=l)\(p(r)\2 \r-r'\ 9 .1... Although the results are encourag¬ ing some problems remain e. fully occupied spin-orbital). in (Ma and Brueckner. 1996a) and gradient dependence of the enhancement factor FXc(n.5 Self-Interaction corrected DFT From the construction of DFT given in eqn. 1991). +) = \<p(r)\2 . problems with transition metal oxides (Leung et al.

(1. respectively. a = = where accounts for the N In order to generalize an this concept from fully occupied orbitals to arbitrary density distributions auxiliary function is introduced: ASIC[n]=min Vk^I-aI^)} U[na] LSDr - V£u[n] (1. n (nT(r).40) The minimization is constrained to be one-electron n. and na are (|^a(r)|2.4) gives an error a contribution even in the case of a single elec¬ tron.41) used LSD+U method has the into the calculations.38) distorted DOS and if the self-interaction This leads to wrong causes a fore in crossing over the Fermi energy also the wrong occupancies. where no Bloch states exists and locality Is ensured. n nT(r) + nJ-(r) the elec¬ the and tron density. r)|2) spin densities of the state a for up and down spin. This contribution is the so called self-interaction energy and in the hy¬ drogen p. of the self interaction energy (Perdew and Zunger. The discovery is based of the LDA energy of about 5 % (Eschrig. There¬ eqn. 1981) has lead to the idea of correcting the or it in the self interaction corrected DFT (SIC/ DFT) which electrons on following considerations:3 delocalized.38) is subtracted for each occupied orbital. nJ-(r)) is the total spin density of the system. In solids the d and can be localized The treatment of delocalized elec¬ localized electrons are trons in DFT is correct while the energies of shifted by the self-interaction energy U[na] + V^D[n] hybridization. (1.4) the self-interaction energy (eqn. This method in comparison with the widely advantage that it does not insert any new parameters 3The original work of (Perdew and Zunger.39) = Yj&a\ A|«Aa) + U[n] + V^D[n] + Vext[n] - £{£/[«„] = + V^t««]} occupied orthonormal single electron orbitals. 0) (\iffa(Q.1 Computational methodology the exchange + correlation term is different from the Hartree energy and there¬ fore Vxc U in eqn. 1. (1. over those sets {if/a} of iV orthonormal wave In the next functions whose spin densities add up to the total density step a density functional for an arbitrary charge distribution follows: can be defined as 7SICr E^[n] = AML[n] + k SIC Vext[n] + LSDr V^u[n] + U[n] (1. 1996. 1981) considered only atoms and molecules. atom leads to 169). 10 . This peels off their self interaction energy ti - /2LSD Yv\na} ~ "*" XC 1/^«' ha\ (1.

(1. Therefore basis to another are repeated transformations from one needed.. are spurious self-interaction reappears in the total New methods of the self-interaction corrections proposed (Perdew an et al. while the SIC potential is only defined in the localized basis set. and does not appear in the actual calcu¬ lation. further developments intensely used for molecular spectra and configurations (Patchkovskii and Ziegler.1.)^ v (1.1 Exc.43) t is the Weizäcker kinetic energy density. 2004). Vydrov and Scuseria.42). 2003).. Although further improvements tion should be self-interaction corrections have many advantages (Kümmel. 1998. Transformation tJ and tœ under unitary transformations supersedes the localizing transformations defined in eqn. that the energy.4 rov - 0.5. Patchkovskii and on and Scuseria. 2002. Among them the weighting of the self-interaction energy with ronment depending scaling factor — k g- where To¬ r^ := |V>v|2/8 na (1. 2004).42) where T indexes Bravais lattice sites and try. Vyd¬ hand bears the problem. varying limit k > 3 is ergy is computed in slowly required when the underlying exchange-correlation en¬ the TPSS meta-GGA {k > 2 for PBE GGA and k > 1 for invariance of In order to preserve the LSD). are needed. 1973. These transformations are (between extended Bloch states and localized Wannier orbitals) defined through ^rv = JV^^Ä. 2003).7 (Csonka and Johnson. ll . envi¬ 2005). Filippetti and Spaldin. Although successful in chemical applications.5 Self-Interaction corrected DFT Therefore the calculations remain ab initio. 2002. It is found that the self-interaction correc¬ weighted (at least in chemical of 0. Both methods of are costly because projections onto atomic orbitals. The SIC is transferred to the construction of the potentials. this method is not well suited for ultra high pressure calculations because it involves pseudopotenSIC-DFT is tials. In the SIC-DFT the Hamiltonian is the orbitals and their symme¬ diagonalized in the Bloch basis. This the other applications) by a scaling factor Ziegler. The optimized effective potential (OEP) is the most popular version of the SIC for these calculations (Baerends et al. 1.

2005).44) fully non-empirical and involves T^(r) and Ti(r) for the computation of the exchange correlation energy. p.35)-(1. (1.33) and eqns. The self-interaction correction could be also useful in the future. an — under the assumption 12 .45) highest momentum used for the plane waves.. GGA. These that take up the ideas developed in pseudopotentials consider¬ ations.g. This lowers computational costs.6 Pseudopotentials and the PAW method pseudopotentials is well established within the computational physics community (see e. which is a precondition in order to perform calculations on systems with charge transfer. (2005) introduces a Jacob's ladder to visualize the of DFT in the past and in the future. 2003) £cMGGA[nT...2). which correct for minor errors and prove that the new method is not approximation anymore but the exact calculation that the defined core regions remain unchanged. 1990 and Oganov et al. 1982). SIC corrections can restore this property (Perdew et al. its gradient Vn.35). hyper-GGA and generalized RPA.. 1. The exchange-correlation energy of the meta-GGA (Tao et al. the Up to hyper-GGA all exchange-correlation functionals fail to describe fractional particle numbers in many-electron systems. the pa¬ rameters in TPSS meta-GGA derived from constraints which involve among In TPSS atomization others eqn. Core electrons can be neglected when considering chemical properties. The concept of solid state 2002. Although fully non-empirical the results can compete with those of semiempirical approaches (Perdew et al. which allows to decrease the cut-off energy for the calculations which is £cut = ^|Gmax|2 2m (1. 144). (1. Rappe et al.nJ is = f tfrn^^in^Vn^Vn^rU^r)) are (1. also the In the meantime more where Gmax is the powerful methods such as the PAW have been estab¬ lished. As the extremely successful PBE-GGA. meta-GGA. 1.. The five rungs con¬ sist of LSD. respectively. the Laplacian of the density V2n and/or the kinetic energy density r. In chemistry the similar concept is used when only valence electrons are assumed to participate in the chemical bonding. It connects the crudest mation with the chemical calculation of development Hartree approxi¬ perfect accuracy. molecules and surface energies for energies for solids are better reproduced than in PBE. the exchange energy ex and the unoccupied Or¬ bitals {<pt}.1 Computational methodology Perdew et al. They involve in addition the density n. It consists mainly of the definition of a core region (see Fig.

u. core region the pseudo-wavefunction is a placed by smooth function. They probe Examples of these projection operators given in Fig.6 Pseudopotentials and the PAW method Figure 1. the operator T should add the part of the wave function that is not smooth: if/ = <r$ = fi + ^ Cm [\lffm) |^m>} - = 1 + ^ [\lffm) |^m>} (p - <A (1. The eigenvalue iff using the The main idea is to map the true eigenfunctions i]/ of the problem H if/ eip into new smooth so called pseudo-wavefunctions = transformation operator T (1.2: The main concept of pseudopo¬ re¬ tentials: The wavefunction (full line) is a pseudo-wavefunction (dashed line) that is equal to the true wave func¬ Inside the tion outside the core region. Projector Augmented Wave Method (PAW) combines the accuracy of the Augmented Plane Wave Method (APW) and the efficiency of the pseudopotential calculations. 6 7 Radius. 1. 13 . of the Ni atom is shown ter (atomic units).48) where the new projector function pm gives the coefficients cm through a pro¬ jection in each sphere = {Pn\f) (1.46) The eigenvalue problem for the pseudo-wavefunction then is {f+HT -ent"f) <À„(r) If the = 0.49) a projection operators are localized within the augmentation region of particular atom and obey the orthogonality condition The (Pi\fij) = ÔK the local character of the are wave (1. Here the 4s wavefunction 0 12 3 4 5 a. 1997).50) function.1.3. Af¬ (Ewels. (1.47) should be as pseudo-wavefunction smooth as possible.

a) & b) pm for e) d-type.. 14 . 2003).3: s-type partial Visualization of the waves projection functions c) & d) for p-type partial waves pm of a CI atom.1 Computational methodology Figure 1. After (Blöchl et al.

is The expectation value density for example given by n(r) where = n(r) + n\r)-n\r) . 225 and 259). relaxation turn out to be small 1. 1994). ferability and is computationally efficient. (Blöchl.7 The linearized mufßn tin orbitals method (LMTO) Expectation for the values can be derived from eqn.7. i n\r) = (1.1 The of electronic band calculations. which have become popular in solid state physics recently. spherical approximation for the This method turns out to be inalienable for the computation of final core state core For all other calculations the corrections due to the charge although the computational costs are not large. Therefore it is computationally cheap. (1. et al.52) m. which has several reasons: electrons approximation.|&(r)|2 Yjfi J]<<ÀJ<Àm)C(r)(Am'(r)<<Àm#i). As a "sideproduct" the KKR-ASA equations are derived..m' f are the occupations. The basis is perfectly adjusted to so neatly constructed Muffin-tin potentials spherical inside so potential is assumed to be called muffin-tin spheres of radius sR centered at sites R and constant outside theses spheres: V(r) = V0 + J\R(rR) R • (1. p. (Kresse and Joubert. is self-consistently optimized level shifts. 1999) and (Blöchl 2003).51) w(r) = £/.53) 15 .1. The core This method is of are great success. 2006). (1. This way the validity to frozen core PAW method could be proven for most problems apart from the exception mentioned. 1. explicitly included in the frozen core for any type of element with an accuracy The method shows no problems for trans¬ For further details see also (Martin.7 The linearized muffin tin orbitals method The LMTO method is the that (LMTO) appealing because its formalism is problem only few basis functions are needed to form the final solution.m' n\r) and = YJfl 2<^l(À->(Àm(r)'Àm'(r)<<Àm#i) i m. 1980.48). This method works comparable with the APW methods. The core charge within a density core. The underlying formalism is presented in this section. One of the latest proximation in developments in this field is to relax the frozen core ap¬ the PAW method (Marsman and Kresse.

e.) Outside the augmentation region <f>i(r) denotes the radius of the augmentation region of an individual site R.. where rCyR <f>i(r) for \r <f>i and fa.) Outside the augmentation region the true wave function deviates from the local expansion in partial waves because the molecular bonding alters the atomic charge distribution.orbital of the Cl2 molecule.4: PAW the a.46. 2003). c. 1. d. The true wavefunction can be recovered wave from the smooth wavefunction through the transformation in eqn.1 Computational methodology Figure 1. After = - (Blöchl et al. b.) The are functions f and f of the isolated CI atoms represented by auxiliary partial waves RR\ > rCyR. 16 .) In the part of the true wavefunction if/ which is responsible for chemical bonding is a approximated with smooth wavefunction iff.) Wave-function of the bonding p-o.

In the case of many scatterers they are exploited to find the intruding contribution to the wavefunction from all the other spheres. e) = YL(r) <fRi(r. The idea now is to find solutions for each individual sphere.55) 17 . e) as a The symmetry allows to write the total solution a product of spher¬ ical harmonics YL(r) and radial function <{>Ri(r. The individual follows potentials vR and positions within them rR are defined as vR(rR) rR v(r) := rR rR < > sR sR [0 := r-R.4).54) ^R/(r. e). as a below. At position R a spherically symmetric potential is placed. an tool rather than ing boundary.1.2 The atomic problem (single scatterer) equation for an First I want to solve the Kohn-Sham isolated Hamiltonian defined in eqn.5: The muffin-tin potentials. The contributions sphere for the through the potentials operator to the (Ven + = VW + Vex) are condensed in the potential v(r). which has the radical dependence vR(rR). L := (I. e) ^R/(r.7. m) (1. the matching conditions act helpful aggravat¬ single scatterer problem they allow to continue the wavefunction for the inner region of the sphere. according spherical A LA /(/ ------ + 1} ßf-2 y ßf f-2 (1. (1. The kinetic energy (V2 /\) problem is transformed into to be solved: spherical coordinates. impose a match¬ ing conditions at the as a sphere boundaries and construct solution for the whole As shown problem superposition of all the solutions of individual spheres. and outside the muffin tin radius sR it vanishes.7 The linearized mufßn tin orbitals method (LMTO) position R Figure 1. In the 1.

only region the smooth sphere matching of the solution terms of logarithmic derivatives. This equation has two solutions.e)] r = -/-! D[Ki(r)] .56) regular one (^R/(r. while is the orbital energy. analysis is continued outside the muffin-tin sphere.e) a = 0. (1.1 Computational methodology L is the composite index of the angular e tum number m. continue smoothly the wavefunction outside the sphere. The Atomic Sphere Approximation (ASA) neglects the kinetic energy (e V0) of the elctrons in that region. e) oc r1) and an irregular one (^R/(r. dln(r) f(r) (1. As before for the space inside the muffin-tin linear combinations of the regular and spheres. The matching has D[<pRi(r. They can be superimposed to form the solution of the Kohn-Sham equation within the muffin-tin sphere ^R/(r. (1. + or1 r or rl (1. The two through a matching condition.57. e). here irregular solutions: the solutions are Jl(t) = h(r) YL(r) = 2(2/+ l)\w/ ] (-) YL(r) YL(r) rR < sR ^ 58j rR>sR.£_!£ «Lti2Wo. The logarithmic In the presence of is most single easily expressed derivative of an arbitrary a function is nvff vi dln/(r) = = D[f(r)] r dlnf/dr = r—— f(r) f(r) . e) oc r~l~l). 18 . For rR < sR The momentum / and the corresponding problem d2 or1 2d + r or 1(1+1) —r~ rl ~7T2--7r + VR(r) ^R/(r. are KL(r= w Kt(r)YL(r)= (^)+ where is a constant to make the functions dimensionless.61) to SR It permits. Under the assumption that the constant potential is the zero of energy the radial solution has to satisfy The - .59) The logarithmic = derivatives of JL(r) and KL(r) yield D[JL(r)] I 1. under the knowledge of the solution inside the sphere <pRi(r. rR < regions the inside the sphere are sR solutions at the end combined is magnetic quan¬ problem is split into two and outside the sphere rR > sR.60 -I-I D[KL(r]= which are — surprisingly to be fulfilled on independent of the radius the muffin-tin sphere and reads now — r. e). Both the solutions in the used atomic in they are regular.

/^)}^^^)-^^^). (1.62) matching of the at the function f(r) to r = a linear combination of the functions f\(r) and f2(r) point r0 imposes the following condition on f(r) (r If -» . e).f2(r)}r=ro Mr) - {f(r).63 point r = f(r) = ipw(r. e) = KfryNwie) - PRi(e)/NRl(e) Mr) . f2(r) is introduced orthogonal among each other. .e).66) Djuie) := Diifjuir.K. e) automatically fulfills the boundary condition on the a upon the This function has to match linear combination of the functions JL(r) and KL(r).67) 19 .61) is not sufficient.65) and the normalization function NRi(e) are potential function Pw(e) as follows PRi(e) := {<Pu(r.(r)/2(r)j rMr)f2(r)[D[f2(r)] D[/i(r)]j = - .Mr)}r=ro for) . are the As Ui(r)J2{r)} Smooth = ryx(r)£(r) -/.e).Ki(r)} (1. {f\(r)J2{r)}r=ro is evaluated for (1. knowledge of the atomic solution <pRi(r. e)]r=SR Instead of and fix keeping the boundary conditions it is preferable to guarantee it cpRl(r. 2(2/+l)(A| l+l ' .64) can be simplified to -w/2 was used. fir) -» {f(r).^^)}^/^)] w = . '„„ . compound angular momentum separately. that sR. (1.(r)} {tpm(r.):= . (1. f(r)} r=SR ' ^2/+1 2{2l+Jir££L±L±± DRl(e)-l \sr) = «. ^(r.e)^-^^^^).1.64) identity {Ji(r). r0) fl .7 The linearized mufßn tin orbitals method (LMTO) 1.3 The Multiple scattering problem are When several atoms into the atomic introduced the solution of one atom ^/(rR) extends of the sphere of the other atoms. fir) is = = at the sR the resulting expression (r^sR) where the eqn. Therefore the matching part and the part within the sphere as given in eqn.. It is desirable to derive a function (this will be A^u(e) <pw + PRi(e)JL(r) extended ) with it a special property: a = yields sphere r analysis a function.63) JL(r) and f2(r) KL(r) expression 1.7. (1. Because these functions can be done for every useful tool the Wronskian of two functions fir). The right hand side in Ki(r)/Nw(e) when the introduced ~ Pm(e)/NRl(e) f(r) (1. (1.

1 Computational methodology The algebraic solution of this equation for Kt(r) yields Ki(r) The the = NRl(e) m(r.) (1.LJL.68) righthand side is useful.ruh>(fr') rR.73) only the first expression <pRi(r.e) KL(r) inside one + PRt(e) Jt(r) rR < sR -Zl'Srl.R'îR SRL.69) rR > sR {KL(r) The solution within the the sphere now is called the head of the function. CWL. Therefore the last two terms have to cancel each other.(rR.R'. e) is defined x¥RL(r. Therefore the muffin-tin orbital ^RzXr.Ru are and the double factorial n\\ is n\\ = \ 1 n = 0Vn = 1 . What is the contribution of tail of specific atom to wavefunctions in the sion surrounding spheres? in terms of functions To find this term the expres¬ in the KL(rR) is expanded JL(r) located surrounding spheres: KL(rK) = - ^ ^RL. e) ^RL(r. e) + PRl(e) Jt(r) (1.the Gaunt coefficients SRL. e) solves the Kohn-Sham equation in that region (upon a scaling constant).e) = \ (1.e) + PRl(e)Jl(r)- ^ L'.r(2r-l)!!CW (2/'-l)!!(2/-l)!! W-nMf?/-1V!lL"(R TR' < SR' SrL. This is the tail cancellation condition. outside one sphere its tail. > sRI r G (1-72) I of the spheres leads to NRi(e)ipRl(r.R'Z/- ~R) (L7°) L". as it is expressed in the But KKR-ASA equation: 20 .l"=l+l' cWl»-= -I YLWvWL»mdn the canonical structure constants. muffin-tin sphere in terms as because it expresses the wave function inside of regular functions.71 n>2 The superposition of all wave functions expressed as fNRt(e) tpRt(r.R.R'L'^L'(rR') 2j (_1) 8. Wn-2)!! 1.

aRL[ÖRL.R'L ] = 0 (1.R'L'Ju(rR') wave rR.R>L>PRl(6) RL ~ Srl. < sR.] = 0 (1.1. contain the geometric and scattering properties of the system and need to be calculated only once at the beginning of the calculation. e) inside the atom appears again.78) rR G I original wave function <fRi(r. The final expression for the LMTO orbitals is The 21 . It is used twice in order to cancel the implicit energy dependence and to guarantee smoothness at the boundary. The KKR-ASA is a non-linear eigenvalue problem and therefore can not be diagonalized using standard diagonalization techniques. The structure constants 1.7 The linearized mufßn tin orbitals method (LMTO) Y. (1. (1. e) = <pw(r. SRL.R/) <Pm(r) (1.77) The LMTO function xrl is m(r. e) is e = explicit energy dependence of eqn. > sR.7. because the boundary condition is not yet used.R.69) the expansion of KL(rR) be used for in terms of J'L(r'R) and the structure can r^ < sR KL(rR) = \ {-IiL'Srl.4 Linearisation of the KKR-ASA In order to suppress the wave function <pRi(r.75).76) As in eqn.rl> Ju (rR' ) KL(rR) and (R' * R) ( 1. constants (1.75) eigenvalues et and eigenvectors aRL constitute the solution of the equation and correspond to eigenenergies and wavefunctions of the system.L. e) Xrl rR < sR rR.RL< and the potential functions PRt are energy independent.74) It has non-trivial solutions only when the KKR-ASA secular determinant vanishes det^Rz^PRKe) The set of - SRL. -Xl>S rl. ev. the radial approximated by its Taylor series in e around a char¬ acteristic energy eViR/ <Pw(r.Rz) + de = (e-ey.

R^] = 0 (1. Therefore computational efforts are — the velocities lack at any time step need not be stored. 1986)..i>(r)}Ki\r=SR- (1. < sR. is the velocity and the acceleration of ion: x(t + + + ôt) ôt) ôt) = x(t) v(t) v(t) + + + v(t)6t + 1/2 a(t)6t2 v(t a(t = a(t)6t +1/2 b{t)ö? = b(t)6t + . 2006). and rR G I (R' * R) (1. advantage - of the Verlet algorithm is that it uses only the positions at new time t and t at time t + ôt and the accelerations at time t to compute the minimized quantities a ôt. This algorithm algorithm can be derived from the time an applied for MD simula¬ expansion of the position.1 Computational methodology -{K.Rru[{J. 1.v stand for the ements. (Skriver.79) KL(rR) are The Wronskians evalutated at the sphere boundaries: {K.<^ W^rO {J..R^-HR/. 1984) and (Zenia.81) where 0RiRV and HmR.and Hamiltonian matrix el¬ (Lambrecht and Andersen.80) The superposition of LMTO orbitals leads to the linear equation det[eOR/. Xrl = ^}R/^R/(rR) + {K. On the other hand this leads to of precision which might affect the energy conservation. the sign of ôt can be changed x(t The - ôt) = x(t) - v(t)ôt + l/2a(0(5^ • sum of the two expressions for the positions yields x(t The + ôt) = 2x(t) - x(t - ôt) + a(t)ôt2 . The velocity Verlet algorithm 22 . For further details see overlap.<p}RT<pR'i'(rRr)] rR. <^ WR/(rR) - rR < sR | - Zl' SRL. In the expansion for the position.8 Molecular dynamics In VASP and most other codes the Verlet tions.$}1il = {Kl(r).

This will generate thermal fluctuations in the physical system while the average temperature is kept constant.86) l)kg Tea J-^l Z0mlSi2-yl 4In eqn.84) the ions.83) the acceleration at time acceleration if + (1. The param¬ to the where <p stands for the external eter Q has the dimensions mass as a • potential that on length2 and is often called "Nosé mass". velocity and the position need to be stored. Traditionally in a the numerical solution of the equations of motion the total energy E (not tem¬ perature) was kept constant.8 Molecular dynamics x(t vit + + öt) öt) = x(t) vit) + + v(t)öt + l/2a(t)ôt2 + = 1/2 [a(0 ait + (50] (5? (1. This can be shown in the following can be viewed heat bath that is coupled Portions of energy can diffuse from the way: The equations of motion for r. V. The thermostat tem.83) for every step. (1. and these variables) are s (until further notice A stands for any of derived from the Lagrangian equation d_(d£\_ d£ dt\dA)~ 3Ä ' (1.87) The and t + ôt is computed using the position x(t + of). V. One time an experiment. N) ensemble instead of the [E. But this does not normally correspond to the conditions of stant. computed from the force F on the particle of mass m is a(t + ôf) ^ \t+St therefore independent of the velocity v(t + ôf) = 23 . where for constant-r most often the was temperature is kept con¬ approach known: to scale the velocities at each step.4 To simulate constant temperature ensembles. N) ensemble. The extension of the ditional results in the system of / physical degrees of freedom with the s ad¬ and macroscopic variable and its "velocity" is not straightforward Lagrangian a2 - *=I mt „2-i. Nosé (1984) proposed to in¬ troduce macroscopic variable and its conjugate momentum to simulate a canonical [T. But this method eliminates all temperature fluctuations which as are essential for the simulation of thermal properties such equilibrium distri¬ butions etc.l jl/_\ - . physical sys¬ physical system to the oscillator and back.85) This results in the equations for the particles and the thermostat 1 ml s2 drt d(p-%t s (1. the has better energy conservation but has higher computational costs because.1. /o /o 2 sltf <pir) + Q/2 sl if + l)kB Teq Ms) acts (1.

89) also holds same for the correct Nosé gi.. where Zc and Z„ partition function of the extended system Z. Further details about the integration of the equation of motion can be found in (Allen and Tildesley. (1. It equal to Zc Zn. As it is true for any harmonic oscillator the of the Nosé thermostat is proportional to the square oscillation time average following relations root of its mass: y system. 1983) contains more examples for constant temperature calculations. the phonon oscillation time rph and the (meaning that it reproduce the correct phonon frequency rph): (1-90) fph=Vß^CThe same expression is true when the trial mass and oscillation time are inserted. In (Nosé. (1. This is suggested by the following relation:5 '^(Z+D^rJ-j.88) Is true. ZJ Kb 1 eq where C stands for a constant that comprises all other properties of the In order to enhance heat transfer between thermostat and sample this oscillation time should match the average phonon oscillation time fph of the simulated structure.o that constant C corresponds mass to the trial Nosé mass go- Eqn. inserting resulting expression for gi yields C into eqn. The time average of vanishes and therefore eqn.» of the kinetic energy coincides with energy equivalent of the initially fixed Teq temperature of the / + 1 particle system.1 Computational methodology At first for the sight mainly the scaling factors 1/s2 and y physical degrees of freedom look unfamiliar.91) which expresses the correct Nosé mass only as a function of the trial oscil¬ mass and the "desired" phonon oscillation time. which can be shown to be are the partition functions of the canonical ensemble and the thermostat. In a trial-run VASP calculates the average oscillation time Ts. 1984) the proof is given that simulations in the [T. N) are equivalent to calculations on the canonical ensemble. 5Eqn. in the equation of motion But the extended system has the nice property that the time average (abbreviated by <. Whenever the Nosé the mass are (1. V.. (1. 1984). the trial (1.90) and solving gi=(^)go lation time. respectively 24 .87) through averaging over time. the Solving this equation for C.88) is obtained from eqn. s (1. (1. 1987) whereas (Nosé and Klein.88) needs to be tuned to a given oscillation frequency useful. The the the rigorous proof that the extended system reproduces Is based on averaged quantities of the canonical ensemble Is given In (Nosé.

p. which has some volatile abundance in the atmosphere. 2. as However. spectral observations of solid materials. gravitational and seismic measurements of the 4 Earth. Comets. 1989. Only are the CI chondrites (and sometimes enstatite as chondrites. The driving force was the gravitational attraction between the dust particles. The method to study photosphere through the elemental spectra. have not the gravitational field to retain gas-forming and volatile molecules such as H20. also true for the planet Earth. The first two methods from a are based on the fact that the solar system accreted rotating disk of gas. the Earth and the chondrites is identical elements are as far as non-volatile concerned. Javoy. C02 or Ar. These objects further accelerated the process of agglomeration. resulting composition of the Earth is given in Tab. The spectral lines correspond to excitations of atoms and are unam¬ biguously related to the corresponding elements (like fingerprints that unam¬ biguously identify a person). The intensity of the absorption is proportional at although big distance from the Earth provides a the composition of its to the abundance of the element. Chondrites teorites that have not in the solar nebula has started — which are me¬ undergone melting or differentiation since the accretion are interesting for studies of the composition of the original material that formed the solar system.1. They. The assumption that Sun and the Earth accreted from the same solar nebular implies. meteorites objects condensed like water and asteroids may be witnesses of that process. This is. to some extent. that the same solar photosphere has the same abundance ratios of non-volatile elements do not claim the as the Earth. Therefore the composition — of the Sun. 1995) Sun — used models for the Earth's — composition.1 Chemical composition of the Earth mainly based photosphere. During the cooling process the gas cloud became unstable and small drops in a rain cloud. 11).2 Methodology and open questions in geophysical studies of the Earth's interior 2. 25 . of course. precision chemical analysis The Therefore the spectroscopic data are mainly used for the abundance of very abundant volatile elements (Anderson. Elements present on the Sun absorb spectral lines from the thermal radiation of the Sun. The information about the chemical composition of the Earth is on independent methods: Spectroscopic studies of the Sun's composition of chondrites.

028 0. Abbreviations: LID. (Dziewonski Upper mantle TZ Lower mantle D" layer Core 1 1 Pressure (GPa) —I 125 1 CMB 136 Ca-perovskite (Cubic C or Tetragonal) px+0 px Calr03-type phase Fe. Seismic are Lithosphère. whereas the makes 36. Data in weight% and ppm. SiC-2 48.2 MnO 0.100 89.1: PREM. 6371 km crust. 2005). 6291 km LVZ.1 %. 1981).1 Mantle & crust MgO 34. 5701 Data from km lower mantle.12 U Cr203 1.33 H20 0. p.and Al-beanng Mg-perovskite Liquid Fe - Ringwoodite Wadsleyite - Ferropenclase (High spm)i(Low 2000 spin) 2700 2900 Depth (km) Figure 2.2: Phase relations in the Earth's mantle.3 CaO 4. Velocity Zone. Man¬ core tle and crust make 63.1 (ppm) 0.1: Composition of the Earth according to cosmochemical considerations. After Anderson (1989.9 K A1203 5.2 5. After (Ono and Oganov.11 Core Fe (ppm) 262 Ni (ppm) S 5. 3480 km outer core.27 FeO 7.2 Th Na20 0. 18). LVZ.9 % of the whole Earth. The outer radii of the and Anderson.7 0 1000 2000 3000 4000 5000 6000 radius (km) Low Figure 2. 6346 km LID.0 TiC-2 0. 26 .2 Methodology and open questions in geophysical studies of the Earth's interior Table 2. specific layers 1222 km inner core.

(2. 3. Upper mantle considered locity zone discontinuity. 27 .1) The pressure on the other hand distribution through be directly calculated form the density ^ dr = -4nGp/r2 f p{r')r'2dr' an .g. p (density). The aim of this model is to give a spherically symmetric self-consistent first approximation of the density and pressure depending on the radius that could be used in many different fields of geodesy.. Lower mantle (lowest part is the D" 6. The speed differs by 2-4% (not shown in Fig.1. 2. normal modes and 500 travel time observation to obtain the Atmosphere and hydrosphere.g Fowler. Outer 7. the low ve¬ (LVZ) and the region between low velocity zone and 400 km zone spanning the region between the 400 and 670 km dis¬ continuities.. precession and eters as a nutation of the Earth). 4. 5. 2005): VP=J^I^ and V. 309). Last two also influence the velocity of wave propagation. Earth's crust.1 Chemical composition of the Earth 2.= J=.1) and is more pronounced below Moho under the oceanic crust than under waves with horizontal (SH) and vertical (SV) the continental crust. 2. can (2. Numerous studies find anisotropy of the Shear polarization travel with different speed in that region. The following regions have to be distinguished: function of radius: 1. 1981. Transition consisting of the region above the low velocity zone (LID.Reference Earth Model (PREM) intro¬ by Dziewonski and Anderson (1981). qM and qK (isotropic dissipation of shear and compressional energy). geophysics (Earth tides.2. Inner core. . free oscillations. p.1 PREM The most used model for the the Earth is duced probably the density Preliminary p and pressure P distribution within . see (Dziewonski and Anderson. It consists of the inversion of 1000 following param¬ Vp and Vs (pressure and shear wave velocities). to be the main part of the seismic lithosphère). The velocities Vp and Vs are determined by the following relations (e.) and astronomy (e. layer) core.2) outermost 220 km of the mantle.

. Pressure [GPa] Fig.. After 80 90 100 110 120 130 140 (Oganov and Ono.56 MPa/K. However. No high temperature structural phase transition to a higher-symmetry perovskite-modification has been observed for Mg-perovskite (Oganov and Ono.2.2. and ratio of 9:10:8. in this work the more equal terms to name minerals of popular Magnesiowustite will be 28 . The mineral stems from the perovskite has composition CaTi03.. MgO magnesiowustite1 (20 vol%). Accord¬ physics (computational ing to this picture the lower mantle consists of MgSi03 perovskite (75 vol%). an Ti occupies octahedral sites while Ca is 12-fold coordinated. CaSi03 perovskite (5 vol%). As it is considered as the major phase in the lower mantle much effort was done to characterize its proper¬ ties. 2004. Oganov and Price. 2. /a / m m / / Post-perovskite / / / phase diagram Figure MgSi03 and MgSi03 post-perovskite. 2. whereas Fe and Al are achievements in mineral assumed to be absorbed as impurities in the main minerals. 2004).2 Methodology and open questions in geophysical 3000 studies of the Earth's interior / 2500 f 2000 • * / / / Z3 aj Q.c22 and c33) are et al.3) and (Oganov and Ono. It has orthorhombic symmetry which — tilting of octahedra as it is described in section 3. 1989). thermal expansion such as in good agreement with ex¬ 2000). At pressures that exceed 100 GPa a phase transition to the newly discovered post-perovskite phase is found (Fig.7 GPa at 0 K and a Clapeyron slope of 9. It is generally accepted that pressure gradually increases the tilting angles of the octahedra. 1974. 1975. (2001b) computed the elastic constants.3: on The of | 1500 Perovskite 1000 DFT calculations which result in a 500 ee® m ®» / m transition pressure of 98. pressure corrected GGA calcu¬ lations). Oganov et al. Mg-perovskite and Mg-magnesiowustite are clearly the dominant minerals.. Murakami et al. Based on the original suggestion by Ringwood (1962) the perovskite structure is found to be the stable phase for MgSi03 at pressures of 24 GPa and above (Liu. The phase boundary (solid line) is based 2. are bulk and shear modulus. 2005). shear and bulk modulus and the Grüneisen and temperatures from 0 K parameter for pressures from 0 GPa to 150 GPa to 3500 K (Oganov et al.. While the ab to determine the elastic initio techniques are unique properties at elevated temperatures and pressures. The phase boundary can be described by the linear equation Magnesiowustite used. 2001a. Gillet et al. that it takes on the Pbnm symmetry similar to the original CaTi03 perovskite. at a In these (Oganov et al.2 shows the composition of the Earth's mantle according and to the latest experimental). 2004.6 Mg-ferropericlase could be used in composition Mgi_xFexO. (Fiquet perimental findings calculations the crystal turns out to be anisotropic as far as the compress¬ ibility is concerned: Diagonal terms of the elastic tensor (cn. 2001a). 2000. the data for the volume at ambient conditions. X-ray experiments show. 2004a).

2.2 Seismic discontinuities and

phase

transitions

P

=

130(+3)

+

0.0070(+0.0030) x(T- 2500)

(2.3)

given in GPa and the temperature T in K (Ono and Oganov, 2005). A separate discussion of the other main phases are given in sections 4.1 for (Mg,Fe)0 and 3.1 for CaSi03 perovskite, respectively.
Besides the well known discontinuities at 400 km and 670 km minor discon¬
tinuities exist. It is
causes a

where the pressure P is

minor
some

generally discontinuity
on

believed that the ß- to
at
a

y-olivine phase

transition not to be

depth

of 520 km. It is weak

enough

found in

seismic studies it

(Cummins

et al., 1992; Jones et al.,

1992) while 1998).
It is

other studies report
an

(Deuss

and Woodhouse, 2001; Gu et al.,

open

it

can

be found

question, if this discontinuity is a global feature (Shearer, 1990) or if only locally (Gossler and Kind, 1996). High pressure experi¬

ments

reliably find the wadsleyite (/?-phase) to ringwoodite (y-phase) transition at the corresponding conditions (Rigden et al., 1991), which is another good example how high pressure mineral physics adds to seismic observations.
Another topic is the

sharpness

of the discontinuities, which is which the transitions
occur.

intimately
(2003)

connected to the pressure range

over

Frost

could show, that the a-olivine to

range that
considered

corresponds
occurs

to 6 km in
a

ite transition
as

in

wadsleyite transition is smeared out over a depth, whereas the wadsleyite to ringwood¬ pressure range of 20 km. Temperature effects were

well

as

effects due to water (H20) incorporation.

2.2 Seismic discontinuities and
It is well established that the

phase transitions

discontinuity at the boundary be¬ tween inner and outer core is due to the freezing of iron in that region related to the phase-transition of iron between liquid and solid (Anderson, 1989, p. 67). Other discontinuities could also be explained with minerals undergoing phase transitions through the variation of pressure and temperature that depend on the location in the Earth. Maybe the latest development in this field is dis¬ covery the phase transition of MgSi03-perovskite to post-perovskite (Oganov and Ono, 2004; Murakami et al., 2004a) which could explain the large shearwave anisotropy of the D" layer and the discontinuity at the D" boundary. The anisotropy of the D" layer has been a puzzle to seismologists for a long time and many ideas were introduced to explain it. They vary from structural lam¬ ination due to inclusions of melt, crystal alignment (Fowler, 2005, p. 347) to large
seismic

rafts of subducted material (Poirier, 2000, p. 266).
It is still under discussion if stable and

the existence of

plumes

is

a

these conditions heat transport

large through

thermal

large plumes exist. One condition for gradient (super-adiabatic). Under
convection is
more

efficient than it

through pure perovskite
is

conduction.

steep Clapeyron slope of 7 GPa/K for and 8 GPa/K pyrolytic material (Ono and Oganov, 2005) the

Because of the

29

2

Methodology and

open

questions

in

geophysical

studies of the Earth's interior

The Figure 2.4: MgSi03 posthas the power to structure perovskite explain several geophysical and seis¬ the shear wave mic findings. 1.) D" the of anisotropy layer by pre¬ ferred orientation of crystals. 2.) The

Vp/Vs anti-correlation in D". 3.)
lateral

The

Double
After

varying discontinuity present
et

thickness

of

D"

4.)
D".

in

(Hernlund

al., 2005).

mantle

geotherm crosses the stability field of post-perovskite. In hot regions (which would correspond to upwelling plumes) the D" layer would be absent or
a

restricted to

region

close to the CMB whereas in cold

regions (which

would

correspond to downwelling slabs) the D" layer can extend to 300-400 km of thickness (Sidorin et al., 1999a,b; Oganov and Ono, 2004, 2005; Hernlund et al., 2005). The same argument would imply that the D" layer was not exis¬
tent at the time the Earth formed 4.5 Ga ago: the

temperature

was

too

high.

After about 200 Ma the temperature of the D"
mation of the

post-perovskite layer

set in

region (Ono and Oganov, 2005).

decreased and the for¬

Many works (Panning and Romanowicz, 2004, e.g.) have reported on the strong anisotropy of the D" layer. Horizontally polarized shear waves (SH) travel differently than vertical shear waves (SV). The ratio of the correspond¬ ing wave velocities (Vsh/Vsv) is predominantly bigger than 1 although regions
with Vsh/^sv the
axes
<

1 exist. In the

of lowest activation energy for

convecting mantle shear is assumed to orientate slip (slip planes) parallel to the flow di¬

Many attempts have been made to explain this anisotropy: presence of aligned melt pockets, lattice preferred orientation of magnesiowüstite, The anisotropy of wave propagation velocity in MgSi03 perovskite (s.g. :Pbran) (Wentzcovitch et al., 1998) is too small and does not match the observed type of
rection.
....

being a layered material anisotropy. Post-perovskite timates requires 33% of averaged preferred orientation

according

to first

es¬

and 65% orientation in

the the fora

regions where the anisotropy is maximal (Oganov et al., 2005). Originally slip planes were assumed to be parallel to the planes of octahedra which

would result in

only 2.9% of anisotropy in propagation of SV and SH waves transversely isotropic aggregate. Later works by Oganov et al. (2005) us¬ ing the newly developed metadynamics algorithm could show that the true slip system is inclined to that plane. This raises the anisotropy for the SV and SH
to 4.1%.

waves

discovery of postperovskite heterogeneities. Oganov and Ono (2004) found that it can be attributed to the phase transition of MgSi03 from per¬ ovskite into the post-perovskite phase. Being a first order phase transition a region of coexistence with
was
— —

The anti-correlation of VP and Vs in D" attributed to chemical

before the

30

2.2 Seismic discontinuities and

phase

transitions

(ova

.

m..
(Ml)

+

/^
fys2-vsi
Ar

[dVs h
P

\àT)p,x

+ J

can

be found.
x

Here the thermal responses of the velocities

(at given
are

com¬

position
as

and pressure

P) and effects due

to

a

phase

transition

included

well

as

the volume fraction / of

MgSi03,

which is 75%.

From the calcu¬

lated elastic

properties and under the assumption that post-perovskite shows
as

the

perovskite, theory can reproduce the positive correlation between the shear and compressional velocities. They are found to be 3.3 (Masters et al., 2000) in seismic observations whereas the calcula¬ 3.36 (Oganov and Ono, 2004). Anti-correlation of VP tions give (d In Vs/dln VP)P and Vs in D" is not a global feature. The experimentally observed (Ono and Oganov, 2005) and theoretically predicted (Oganov and Ono, 2004) Clapeyron
same
=

thermal responses

explain this feature: anticorrelation should be absent where there is no post-perovskite (Fig. 2.4). slope
can

in hot

areas

body wave data that in the region of D" two discontinuities exist. These findings can also be explained with the phase stability field of post-perovskite. This is the so called double crossing hypothesis according to which the temperature at the CMB exceeds the stability field of post-perovskite and post-perovskite forms lenses inside the perovskite mantle. Further apart from the CMB the temperature drops and post-perovskite is stabilized. Even further away from the CMB the pres¬ sure is so low that perovskite is more stable than post-perovskite at any tem¬ perature. Hot upwelling regions would not consist of post-perovskite at all, whereas in cold regions the thickness of the post-perovskite layer would be some hundreds of km (see Fig. 2.4).
Hernlund et al.

(2005) found

in the refinement of

presented by Nakagawa and Tackley (2006): As the perovskite/post-perovskite transition is strongly exothermic it could have pro¬ pelling properties for upwelling plumes. However, further data from seismic tomography will shed light on this field. E.g. Wentzcovitch et al. (2006) dis¬
was

Yet another idea

agree that post-perovskite would be responsible for the D" anisotropy.
favor chemical

They

heterogeneities
reason

to

explain

it.

Magnesiowüstite

on

the other

hand turned out to be anisotropic (Yamazaki and Karato, 2002) and could at

anisotropy of the D". High pressure magnesiowüstite is strongly aligned after being plastically deformed causing a strong shear wave anisotropy. It remains to be seen if these results can be reproduced in theory. Since the D" consists of about 20 wt% of magnesiowüstite, in order to explain the anisotropic effects of D", a much higher preferred orientation of magnesiowüstite would be required.
least

partly

be the

for the seismic

deformation experiments show that

proposed by Gaffney and Anderson (1973) that Fe2+ could undergo This would a high spin (H.S.) to low spin (L.S.) transition under pressure. decrease the radius of Fe and thereby partially suppress the substitution of Mg in Mg-rich minerals by Fe. Rather than substitute Mg in (Mg,Fe)Si03 iron
It
was

31

(2006). Many other physical parameters influence sound velocities wave velocities such as temperature and composition.Fe)O contribute to the thermal isolation of the core. The example in this section might serve as an illustration for the power and the problems of these inversions.6) where 0 indicates ambient conditions for temperature and pressure (Trampert et al. p. 2. perovskite and MgO as main components. 1989. which would hamper convective flow in the mantle (Durham et al.. Recently it has become very popular to invert seismic data for these properties and many different ap¬ proaches can be found in literature. based on profiles calculated parameters from db initio calculations.2 Methodology and open questions in geophysical studies of the Earth's interior 800 1200 1600 Figure 2. Small fractions of Fe Q 2000 and Ca The were also are 2400 included (not shown).P) p=o Po exp| | {£ o a(T)dT (2. Thermal expansion [K := -l/(aKs)Ks0 dKs ldT\P) give rise to changes in density p and the adiabatic bulk modulus a and the Anderson-Grüneisen parameter 6S = Ks according to the potential temperature Tp P(TP.5: Graphs of temperature and composition in a model using MgSiO. FeO (Anderson. The resulting Fepoor MgSiOs perovskite would have high radiative conductivity and relatively low viscosity. In the meantime some evidence was found for the correctness of this hypothèse: Relatively low radiative conductivity of high spin (Mg. In the construction of PREM this fact used to inverted the measured sound using eqn.1) to obtain a density and pressure profile of the Earth. 2001).Fe)O on the other hand could pile up at the CMB and interact with the outer liquid core. Low radiative heat conductivity of (Mg. The much denser (Mg.2. (2. 66). which would diminish the cooling rate of the core. After (Deschamps and Trampert.1 Thermal and compositional distribution of a Pressure leads to wave hardening wave material which increases the was speed of sound propagation. 1979).Fe)O was reported by Goncharov et al.(%) might form a separate phase..P)\p=0 = Kso\ liM) (2. The shear modulus can be approximated linearly through 32 .5) Ks(Tp. 1500 2000 2500 3000 50 60 80 90 100 T„(K) . The gray shaded area 2800 symbolize the region of one standard de¬ viation. 2003).

The properties of a specific region are sampled by the linear superposition of the properties of the components weighted by their volume fraction..8) 27 = Kso(l-2e)5/2 can (5-3K's0)e--(4-K's0)ei (2.11) The Grüneisen parameter is well described by the formula (Al'tshuler et al. It can be using the Grüneisen parameter dT dP y yj_ Ks (2. To and ß' shows a are = y«.9) The shear modulus G Ks. (Robertson and Woodhouse. G0. can directly inverted to get the temperature and the composition of specific region within the Earth. (2. can be measured in experiment or calculated in ab initio simulations.. (Masters et al.12) is more appropriate. material Fig.P)\p=0 (l-2e) l + 3/2 (2.10) where the constants Ct and their are calculated in advance from the elastic moduli isentropic pressure derivatives. All the The measured seismic data be parameters G0. 2.12) dependent fitting parameters .7) temperature derivative of The pressure dependence of p.P) Ks = p(Tp. 1987) \ß' y(V) where y0. The same is true for the adiabatic contribution to the temperature calculated increase which is added to the potential temperature..9) is obtained from P = -(1 - 2e)5/2(Cie + C2e2 + l/6C3e3) (2.2 Seismic discontinuities and phase transitions G(TP)\P=0 and Go stands for the = Go + Go(TP-T0) G at constant pressure. 2005).. 1996) and (Panning and Romanowicz. The expression in eqn. Many different approaches have been made for this inversion whereof at least following should be men¬ tioned here: (Deschamps and Trampert. Ks and G can be modeled using the third order Birch-Murnaghan EOS (BM3) for adiabatic compression p(T. Assuming Eulerian strain be defined in the similar way as the bulk modulus that the pressure at any depth is known from the PREM.5 2In the work of (Trampert et al. 2004). (Soldati and Boschi. 2001) and many others y - y0 {—\ was used with y0 and q as fitting parameters. the e used in (2. (2..8) and (2. .2. 33 . 2004).2 resulting profile for temperature and composition. 2000). + (y0 - 7co) v_ V~o (2.

This procedure involves seismology given the sectioning of the Earth's interior which gave these techniques its name: tomography imaging by sectioning. 2003) may be helpful. (b) Temperature distribution at depth of 2800 km after (Deschamps and Trampert. 2. p. 2003). Seismic measurements be inverted to give a 3D seismic velocity model of the Earth which velocities assigns compressional wave velocity and two shear wave [VSH and Vsv) to any radius r. 157-p. Not only is it fascinating because it sheds light on a region that no human being has touched scale yet [ab initio simulations on a but also because it connects the results obtained ~ 1 nm. information about the distribution of temperature and composition would be desirable and actually much work has been done in this field (Oganov et al. each factor containing only the temperature T.l76).6: (a) Seismic a velocities after (Masters et al. 2001b.13). DAC experiments -10 on a microscopic jum) directly with effects large scale ( ~ lO'OOO km). The idea for this inversion is in tion = (a) (b) wave Figure 2. composition and partial melting (eqn. longitude À and latitude <p within the a generalization of the ideas about reflec¬ (Fowler.2 Seismic As as tomography out already pointed the PREM are by Dziewonski and Anderson (1981) radial models such Three dimensional (3D) approximations to the true Earth.2.. For computational details (Forte and Mitrovica.„ l(2 . 2000). 2001) and (Deschamps and Trampert. 2003). Forte and Mitrovica.. are negligible (Deschamps and Trampert. In a third step all the relative seismic effects due to velocity anomalies are assigned to temperature. or the com¬ position C or the amount of partial melt F. 2003) propagation Vp and Vs can be written in terms of a product. Deschamps andTrampert.2 Methodology and open questions in geophysical studies of the Earth's interior 2. 2005. Earth. As 34 . 2001. the perturbation of the propagation cross-terms Under the assumption that and therefore the velocities velocities can be written as dlnVp d\nVs = —-^dT+—-^dC+—-^dF. d]nVs ——- d]nVs . 13) ' dC can dC ——^ + dF dF . oT dlnVs d\nVp d\nVp dC d\nVp OF = ——^ dT dT + .

the D" could not be resolved with given in section 2. 1996). ... that the seismic Many agreed anomaly at the bottom of the Earth's temperature effects layer) or compositional effects as long only two phases (MgO and MgSiOs + Fe im¬ purities) were taken into account (Deschamps and Trampert. Several other effects (solar wind. ) lead to minor modulations of this field.2.2.14) This ratio characterizes the materials and therefore can compositional effects be distinguished works from temperature effects. netic induction has 1 I - Mag¬ ef¬ 3D especially large oceans. 2004 Kuvshinov and Olsen. A new phase (post-perovskite) was needed to resolve the anomaly.. This field is inclined 35 . gion. the assignment. One method to circumvent this problem is to work with the ratio of the relative shear to compressional seismic velocity instead: R dlnVs d\nVn (2. Conductivity [S/m] Deschamps for a and Trampert (2003) point out. 2006. The resulting dis¬ lower mantle cussion is (i.7: Earth's conductivity pro¬ files from satellite measurements. 2006 Kuvshinovand Olsen. with corrections - — Figure - 2. where dynamo process. This is mainly true for the effects of composition and temperature (see eqn.e. currents in the Earth's mantle.13): hardening of a material can be assigned to the composition (dominance of hard material) or to temperature (low temperature). 2. 10 10 — Constable & Constable. fects in the non-uniform L 1000 - modeling to of the ocean regions allows T 1200 - compute their contributions to the magnetic field.2 Seismic discontinuities and phase transitions 200 400 „ 600 £ g" Q 800 Ç. internal heat drive the convection of through the liquid metal. Different sources can have the same effects on wave velocities.3 Earth's The Earth's magnetic field is magnetic field generated by sources the Earth's core. are seismic data are not sufficient deterministic Therefore a probabilistic not inversion is done. 2003).2. satisfactory Instead the resolution matrix R should be computed. Several difficulties related to this kind of inversion: tests are Soldati and Boschi to determine (2005) show that usual checkerboard the resolution of the inversion. It can be shown that are Earth's core can cause constant currents which et permanent magnetic dipole field (Backus particle flow in the responsible for the Earth's al. 2. 2006). These corrections are considered in the third 1400 110 plot (with cor¬ rections) and significantly change the conductivity profiles in the upper re¬ After (Kuvshinov and Olsen.

This transition occurs at almost independently of the temperature (Oganov and Ono. Kuvshinov and Olsen. 2005. 2006).. which through the same process can induce new currents in the magnetosphere. The the measured conductivity for the lower mantle lies between 1 and 102 S/m. These ring currents through the resulting magnetic field induce currents in the Earth's interior. Satellite measurements on the other hand can fully cover the Earth's surface (Constable and Constable. 2006) and is accompanied with a sharp increase of the conductivity..7. that A1203 transforms into the CaIr03-type (postperovskite 130 GPa. A second minor induction system exists. The measurement of the temporal variations can be inverted to find the conductivity profile within the Earth. 2006). large currents the inner culet is the in the conductivity it of the lower mantle is still a puzzle in geophysics. 2. The authors infer from these results that the analogous MgSi03 postperovskite structure should also show high conductivity. The Earth's interior. and therefore could be respon¬ sible for the high conductivity of the lower mantle (see also Pushcharovsky and Oganov. 2004.2 Methodology and open questions in geophysical studies of the Earth's interior by only 10° to the rotation axis of the Earth and therefore can be used for navigation. et al. Ono et al. 1998). The solar wind induces magnetosphere. It can be viewed as two interpen¬ etrating which culets: The outer culet is the magnetosphere strongly fluctuate in time. structure) phase with space group Cmcm. Other studies point out the important role of the - 36 . Some of the latest results using satellite measurements are given in Fig. Some multi-anvil press studies find that can (Mgo93Fe0o7)Si03 at lower mantle conditions (Katsura explain post-perovskite phases of MgSi03 under high pressure: High pressure experiments show. Magnetic field measurement data from observatories or oceanic cables are sparse and irregularly distributed. The energy oscillates back and forth between the two culets.

pared of the of the most recent studies was — by Ono Despite perovskite phase + 0.485 to 3. The laser these shown that pressure stabilizes the of CaSi03 and that the lattice parameter at 16 GPa is 3. 1971) which suffered from amorphisation that it could observe sample upon pressure release — sample in-situ i. In the The new early experiments the experiments allowed to observe the 37 . follows cr\ || radial direction of DAC).e. i. Therefore they concluded it should be "invisible" in seismic observations. Liu and Ringwood.. Mao et al.g. One major achievement of this experiment and in contrast to older exper¬ iments (Ringwood (Mao the et al. not distinguish¬ GPa). S is defined as ^aSiCb perovskite undergoes amorphisation sample was depressurized after synthesis.50 heating temperature problems it could be À from one was roughly estimated to be 1440-1800°C. at high pressure.1 It also found that the 9 % higher density of the perovskite phase might contribute towards the stabilization of the perovskite phase against the oxides CaO and Si02. K0 and ^0') very similar to that of (Mg088Fe0i2)SiO3-perovskite.e. The material found to be cubic and able from the major mineral of the Earth's lower mantle. Diamond anvil cell (DAC) experiments were criticized to result in non-hydrostatic pressure because of the uniaxial arrangement of the experiment. (1989) have conducted was one of the first experiments for CaSi03 that reached the pressure of the core-mantle 134 boundary (experimental pressure equipped with properties (e.g.008 À (com¬ et al. which is assumed to be the major mineral of the Earth's lower mantle. p. Early experiments (e.3 CaSi03 perovskite at P-T conditions of the Earth's lower mantle 3. Therefore Shim et al. 2004). at low pressures. 1975) suffered from many experimental difficulties: the pressure was relatively low [P < 16 GPa) and had relatively poor accuracy of + 15 %. 1967. 1989) of the Major. (2000a) did a great effort to determine the uniaxial stress in their experiments. The uniaxial stress component is t = <T3 - (Ti (cr3 || axial direction of DAC..1 The Introduction experimental work on CaSi03 perovskite reflects the whole history of de¬ veloping diamond anvil cell experiments. crystals at directly at high pressure.

In my calculations (Adams and Oganov. They on pure CaSi03 and a mixture of found that the addition of A1203 stabilizes the low symmetry transition minum structure against the cubic structure and e. q In a = - = - = = they perform thorough investigation about the space group of CaSi03 perovskite.5 % apt to detect the small deviations from the cubic symmetry. (i. Combined with calculations for the elastic constants they give a maximal distortion of the unit cell of and indicate that the experiment was not perovskite of the order of 0. perovskite at P-T conditions of the Earth's lower mantle S = sn ~ s12 ~ -y • stJ are the single-crystal elastic compliances. (2002) published paper where the pressure range of the experiment which was 20 GPa < P < 46 GPa. (2004) did experiments CaSi03 and A1203.92 ± 0.05 and perovskite and unfortunately their Grüneisen parameter y0 0. 38 .6 + 0. (2002) and 0)-peak they found similar interpreted the diffraction 2The determination of the yield stress here is based on the shift of diffraction peaks. temperature from 600 K for pure CaSi03 to For the as at 50 GPa shifts the 1630 K for the alu¬ bearing phase.e. The data for CaSi03 perovskite have to be taken critically.g. This method fails. This that existing experimental data alone could not determine the struc¬ ture. The value of S -t can be obtained from the broadening and shift of the diffraction peaks relative to the positions platinum is known from quantum mechani¬ cal simulations whereas for CaSi03 perovskite the calculated data at that time were not clear. (2002) state that the refinement is insensitive to the choice of the means of the (tetragonal) space group. The authors do not consider any space group for the low temperature phase of CaSi03 1.2 For platinum the stresses ap¬ an of assumed cubic phase. following study Shim et al.996 for -a a a = Two years later Shim et al.e. when the structure in its ground state has lower symmetry than assumed in measurement.3 is not comparable with my findings (see page 58). c/a < splitting of the (2 0 intensities 1) Shim et al. It is a big achievement of these experiments that they were ac¬ 18 96 GPa) and at high complished fully in-situ i. S for pear to be reliable. The material was synthesized under pressure at T > 1500 K. 2006) these intensities are reproduced correctly using the orthorhombic space group Imma. From the splitting of the (200)/(002) peak they could determine the ratio of the a and c lattice parameters of the pseudo-cubic unit cell which is 0. under high pressure [P 17 GPa is 1238-2419 K. Therefore the given values for CaSi03 might not be trustable. (2000b) determined the thermal equation of state (EOS). The crystal struc¬ ture was refined with the PA/mmm symmetry which for the lower-angle peak split (211) line lead to a problematic low intensity. A low-pressure boundary of 15 temperature T found with a small dependence on temperature for the stabilization of CaSi03 perovskite against the decomposition into /?-Ca2Si04 and CaSi205.3 CaSiO?.9 GPa for platinum and 15 GPa for CaSi03 perovskite. The uniaxial stress components were determined to be max¬ imally 3. Finally Shim et al. Kurashina et al.

(1998) who also find the (1996).g. measurement via radiation measurement ~ Theoretical investigations were performed by Wentzcovitch et al. The parameters show that it is not appropriate to fix K'0 = 4 for the refinement of the experimental parameters V0 and ^0- The 14/mem structure of CaSi03 ground state. From the double-well model (1996) to be the perovskite was first found by Stixrude et al. (1996) determine the vibrational modes of cubic CaSi03 perovskite under pressures up to 150 GPa.3 The most recent study on CaSi03 perovskite is conducted by Ono et al. The distortion of the structure with the modes that are the most unstable yield the 14/mem struc¬ and ture and octahedral rotations of 7°. an orthorhombically distorted cell [Pbnm) converges back to the perfect cubic ar¬ rangement. high resolu¬ through ruby tion synchrotron X-ray diffraction and measurement of the temperature profile through the sample.3. temperature P the line-shift 106 < < (38 GPa). (1996) and Stixrude more all electron LAPW calculations. They find energy lowering modes which correspond to rigid octahedral rotations. to be accurate than their work.1 Introduction pattern using the space group Pbnm. From computationally expensive total energy 3Pbnm might be the correct space group for Al-bearing CaSi03 perovskite. Caracas et al. (2004). 2005) the Pbnm symmetry turns out to be of lower energy than the cubic one. For CaSiOs. Static on the other hand did not in rameters found good any problems to the study and the pa¬ agreement with experiment but also with later cause studies. The authors leave it modes EOS was open vibrational comprehensive enough are to find the lowest energy structure. One of them doubles the size of the unit cell. The same ques¬ applied a variable cell and who confirmed the Pbnm tion mark should be put to the work of Warren et al. It derives a phase boundary between the low symmetry 750 K at 40 GPa (assumed tetragonal) and high symmetry cubic phase at K 1250 110 GPa and at a c/a-ratio decreasing from 0.997 at increasing to 30 GPa to 0. a From the energy differences of the two structures transition as an the authors determined temperature (orthorhombic question if their study on —> cubic) of 150 K. who own use cubic structure to be the most stable the work of The authors themselves consider et al. pressure high T). In later and more accurate calculations (e. (1995) who shape optimization to CaSi03 and MgSi03 perovskite symmetry for the latter. P and It makes use of all available techniques: in situ measurement (high spectrum. The resulting structure has P4/mbm symmetry (a°a°c+ in the notation of Glazer. Chizmeshya et al. A space group refinement is not attempted prob¬ ably because of the small number of diffraction peaks.993 at 100 GPa. 39 . This raises doubts about the applicability of pseudopotentials and the accuracy of the k-point sampling (1 k-point) used in that early study.. 1972). one. linear-response calculations within LAPW and LDA they determined the unstable phonon-modes of the cubic Pm3m structure. Chizmeshya et al.

(1996) should be mentioned. 2005) and (Jung and Oganov. they find that CaSi03 and or even vanishing miscibility at geophysiMgSiOs perovskite have a low conditions. A.. While from the viewpoint of the most recent calcula¬ (e. Jung and Oganov. see also (Caracas et al. J and B coupling parameters • — depend on the The coefficient 4/(3 0. Although they do not go into the subject of phase transitions in CaSi03 perovskite and assume a questionable cubic phase. perovskite at P-T conditions of the Earth's lower mantle J ^ = nn 2y(ß^+öZ(a 1<J + ß^)2 Q4 {3A) Q2 V(Q)=A^- + B^- (3.g. cally interesting For — — similarity between the MgSi03 perovskite perovskite get additional information about these minerals.2) where U is the energy of the octahedra depending on the normal coordi¬ nates of the octahedral rotations Qt and the inter-site coupling term J.3 CaSiO?. Using this cluding Monte-Carlo simulations thermodynamic model the authors probably put forward what later turned out to be the most important mechanism of stabilization of high temperature phases for this material. From the viewpoint of later studies (e. shape of the doublein¬ thermodynamic studies of the double-well-problem. they determine the transition temperature at a pressure of 80 GPa to be T' = Y^Ö54lB'2200Kare (3-31 that well. Glazer. With fixed Pbnm symmetry which was found to be the ground state of MgSiOs perovskite they optimize the tilting angle of the octahedra which slightly in¬ and CaSi03 could be used to creases It is self-evident that the structural tions with pressure.. 2005. This is the starting point of a work by Magyari-Köpe et al.g. They dedicate one chapter of their paper to "Mg!_xCaxSi03 perovskite-like min¬ erals". This study also proves that the EOS is barely dependent on the symmetry of the structure used in the calculations and poses no major difficulties to sim¬ ulations. 2005a) the same analysis should be applied to a broader range of different phases. 2005) it is correctly found that the cubic phase at a T =0 K is unstable towards symmetry lowering was structural distortion it is not a ground state because of shortcomings strong constraints of the symmetry which excluded any other symmetry than Pbnm and Pm3m. 2005b). as clear whether the Pbnm structure found or of the FCD-EMTO4 method because of the fied The space group symmetry of distorted perovskite structures can be classi¬ by the tilting angles of the octahedra (e. All the distinct - ^ull Charge Density Exact Muffin Tin Orbitals 40 . Caracas et al. 1972)..g.5054) stems from — completeness the work of Bukowinski et al. (2002). Caracas et al.

4000 K and P 41 .g. (2006b) the lattice parameters to achieve perform hydrostaticity and to was to ab initio MD. The For the is found to be the lowest energy structure at all pressures. high temperature that the of the cubic found be that nar¬ is to phase stability region surprising row. The reac¬ tion enthalpy AH -#casio3 + #cao + HSlÖ2 is big enough (~ 1. Pressure turned out to stabilize CaSi03 perovskite rather than destabilize it. space group Pbnm). Ono et al.2 GPa. while the low pressure Pnam into the phase turned out to transform tetragonal [14/mcm) phase at 14. (2005) because pseudopotentials are used and enthalpies one all electron calculations instead of rather than energies are compared at any pressure. care taken in the k-point sampling tures (9) and the calculation of vibrational 14/mem zone are (4x4x4 Monkhorst scheme). One of the open questions is. space group not given) First it is > < 40 GPa (cubic. incorporates temper¬ structure in ature explicitly and therefore immediately gives T < < a picture of the direct space. This is in conflict with all experimental findings.65 eV at 100 GPa) T conditions of the Earth's for decomposition to be ruled out under the P = - lower mantle.. The interpretation temperature 1000 T remains difficult. Experimentally observed structures correspond to averages taken over whole MD runs. that find a cubic phase at 30 GPa and 750 K and at 150 GPa and 1000 K (e. This method is demonstrative as it uses MD instead of the calculation of vibrational modes. P4/mbm) that range of 0-150 GPa. 2004). cubic structure unstable modes at the R and the M points of the first Brillouin computed ture stabilization of already found by earlier works. Jung and Oganov (2005b) compared CaSi03 perovskite the enthalpies of the cubic (Pm3m) structure. The study study of Caracas et al.3. The methodology of Li et al. how long the minimum required in¬ terval for averaging is. optimize observe the tilting an¬ gles of the SiC*6 octahedra during the runs. temperature T 4000 K (tetragonal. In addition the enthalpies of the energetically lowest lying structures were compared to the sum of en¬ thalpies of the corresponding oxides (CaO and Si02) to check for a possible de¬ composition of the perovskite structure into oxides at high pressure. The cubic structure turned out to be unstable in the whole pressure range. The study found three sta¬ bility regions: intermediate and low 1000 K < (orthorhombic. The high tempera¬ statically unstable structures is suggested to be achieved as through an-harmonic fluctuations between structures and static disorder of octahedral rotations.1 Introduction structures listed in the pressure by Darlington (2002) were optimized by Great Caracas et al. I4/mmm. electron tures the orthorhombic [Pbnm) structure and the in the pressure tetragonal (14/ mem) structure of (PAW) calculations they [P42/nmc. In their all also calculated the enthalpies of three struc¬ in the turned out to be energetically preferable. because in the study the authors achieve better agreement with experiment by saying that a part of the stability field which they assign to the tetragonal phase would in experiment appear as cubic because of the averaging over long times and big volumes. Pm3m). (2005) is more advanced than the by Caracas et al. was (2005) range of -5 GPa to 164 GPa. This question is fundamental. the number of refined struc¬ modes for the cubic structure.

The c/a-ratio < 1 found in experiment is attributed to preferred orientation. T). the Immm. all atoms of one This increases the performed probability of In on a aggravated by the relatively small sample simultaneous movements of equivalent position. generalized for three possible tilting axes of the octahedra Stixrude et al. Other proper¬ are the Grüneisen parameter and the bulk modulus of the simulated cell. 2002. (2006b) is that it finds the c/a < 1 in prefer predicted however is in conflict with many other theoretical studies (Caracas et al. Any of the other 11 perovskite structures can be reached through the introduction of higher symmetry elements into one of the four starting structures. 1996) but in agreement with others (Magyari-Köpe et al. Even in small samples movements can be decrease by choosing a sampling cell with low symmetry. Wentzcovitch et al. V all corresponding = 2006).. Any non 42 . perovskite these at P-T conditions of the Earth's lower mantle Although arguments are plausible are it remains an open question what the basis of these considerations is. Jung and Oganov. were derived. P42/nmc. P2i/m and PÎ to a specific tiling system of the octahedra (a+b+c+. The derivation of the elastic constants remain the derivation is sensitive to the assumed ties such as ground state questionable because phase. Tc is the transition temper¬ a is Landau equivalent rotations potential parameter. macroscopic samples (> 1023 atoms) simultaneous movements have the probability of such vanishing probability. a+a+c". The Pbnm agreement with experiment and also it observes the Si06 octahedra to ground state In a companion paper (Li a et al. less affected by the specific symmetry Stixrude et al. The structural optimization with PAW potentials and within the LDA approximation finds the 14/mem to be the ground state at 35 A3. a"b"c").. (3. 1995). in the cate (2007) guarantee the generality of the structural optimization following way: The supergroup subgroup relations for perovskites indi¬ that four minimal subgroups exist. T).1) now l/2aa-T/Tc)(qî + <è where qt ature and are a + <è). 3. 2006a) further physical properties of CaSi03 the Grüneisen parameter such as the elastic constants ctJ(p.. anti-phase tiltings. The only temperature dependent contribution to the Gibbs free energy G is In a Landau model similar to the earlier work (eqn. Stixrude et al. of the A strength study by of Li et al... 2005a. the an- harmonicity parameter and adiabatic bulk and shear moduli Ks and p. y(p. This expression allows only for of the octahedra in all three spatial directions.3 CaSiO?. a+b"c".4) octahedral rotations about axis i. 2005. fact that all the MD calculations This question is further (10-103 atoms). (1996) and (Adams and Oganov. (2007) derive a phase diagram of CaSi03 consisting mainly of the tetragonal 14/mem phase at low temperatures and the cubic Pm3m phase at high temperatures with a phase boundary at 1150 K at 0 GPa and 2450 K at 140 GPa. as earlier found by Stixrude et al.

6) The total energy is dlnZ E = 1 3vV En- ~~dß~ (3. ~1nnT' The Mie-Grüneisen thermal equation of state can be obtained through aging of the mode Grüneisen parameters ^-e.k _ i (3.7) i.k and therefrom the pressure p dF = 1 + 3N -äv=Pm =Pst(V) ficolk + fia). T). As a good approximation the N atoms in solid are modelled as quantum oscillators. eßulk =E. all the other a material.9) .8) passed onto the mode Grüneisen parameter frequencies with changing volume.2. 3.10) 43 .T) = Pst(V) + V (3.2 3. T) as or G(P.2 Methodology cubic high temperature phase is excluded from the beginning.^ne cnange of the Here the derivation is ylk := aver¬ 7th(V) This = i dlnV (3.1 Methodology Thermal equation of state give the volume and one The aim of the thermal equation of state is to temperature dependent properties of is known. P(V.3. If of these properties thermodynamical properties can be derived from the initial one through relations such dE In = -P(V) dV sense (3.. yields the Mie-Grüneisen thermal EOS: P(V. The logarithm of the partition function then is quasi-harmonic (ß := jj): 3N 3N InZ = -ß(^ fa>.k) J] ln(X e^r) + - (3.T).5) the a narrower state' is the volume and a meaning of the expression 'thermal equation of temperature dependence of the pressure: P(V.

14) has 5 fitting parameters [yœ.13) whereas Al'tshuler et al. T) = yqh(V) - 1/2 a -^ T.13) to (3. (1987) and Vorobev (1996) function suggested a well behaved describing the quasi-harmonic Grüneisen parameter r*(V) = roo + (ro-roo)j^. For further details see also (Oganov. (3.14) a. 3 (AT.15) In MD calculations the total momentum of the simulated set to zero. y0.T) = 3/2NkBa(V)T2 and Pa = -^ oV = 3/2NkBT2 ^ ^^ y a . sample should be Therefore the number of degrees of freedom is reduced from 3iV to always be taken into account when any of the eqn. (3. 44 . (3. T) = Pst(V) + —^. 2003): give rise to an additional best split into a volume only and Dorogoku- o 1 7(V. (3.11).1). 2003): Fa<y. 2003).15) is used in connection with MD. Zharkov and Kalinin (1971) proposed maybe the simplest volume exact would be useful. ß and m) and results in the thermal EOS (Oganov and Dorogokupets. which is dependent part yqh and a temperature dependent part (Oganov pets. dependence of the anharmonicity parameter (3.10) and (3. The combination of eqn. (3. perovskite step at P-T conditions of the Earth's lower mantle In a next it turns out.3 CaSiO?. The remaining part is the temperature dependent contri¬ bution to the pressure as given in eqn. 2003) I have used for the fitting of the resulting data of CaSi03 at different P-T conditions : P(Y. that anharmonic effects dependence of the Grüneisen parameter.{yœ + (ro - 7œ) it' - 1/2 a0m Txm) . In y (3.12) expression the ideal gas pressure term 3NkB T/V can be iden¬ tified and isolated. (3. This should 2002) and (Oganov and Dorogokupets. In the second Although they not expressions for yqh(V) and a(V) are known.11) In the lowest order of classical anharmonic perturbation theory (see also Oganov and Dorogokupets.

3. 1972). View projected along the tilting axis. Octahedra are within the octahedra.). length) is not modified under tilting either.1: a.)—b.) Visualization of how the tilting of one octahedron determines the tilting of the neighboring octahedra and the tilting of the whole plane.e. The combination of all these elements results in the total of 23 different tilt systems. ß and y and the cell parameter of the ideal cubic unit cell £ the resulting cell parameters of the pseudo-cubic unit cell are mostly rigid objects and it length and bonding-angles is energetically unfavorable to 45 .g.2 Methodology • • *B' X . E. the space group of which is determined carefully in (Glazer. The tilt¬ change the bond ing along one axis decreases those cell parameters of the pseudo-cubic unit cell which are perpendicular to the tilting axis while it leaves the configuration within the octahedra unchanged (see Fig.) Outer square: unit cell before tilting.2.3. rigid the of the octaheda.) Figure 3. For rigid octahedra the tilting of all other octahedra in the plane perpendicular to the tilting axis is determined by the tilt of the first octahedron (see Fig. 3. For the tilting angles a. b. Superscript (0) stands for no tilting along that axis. Inner square: unit cell af¬ ter tilting. [100].1 a. 3. The optimal configuration Cations can within each octahedron (angles. denoted perovskite The tilting Along the tilting axis two successive octahedra can be tilted in phase or anti¬ phase which is denoted by superscript (+) or (-) respectively.B A • a. depending whether the angles tilting angles are the same or not.2 Classification of perovskite structures by Glazer — The notation introduced structures is still (1972) for the classification of perovskite widely used also in the literature concerning the structure and an properties of the Earth's mantle easy way to determine the space group of octahedra that are tilted along the fourfold compounds MgSi03 perovskite axes and CaSi03.). [010] and [001] structure of are axes of the undistorted cubic cell. This depicts the driving mechanism for the octahedral tilting in perovskites: are too small to fill the space between the octahedra (white). It offers structures with i. The ideal stoichiometry AMX3 has the cubic space group Pm3m. Tilted octahedra diminish the "wasted" space between the octahedra while the bond length between the corner-sharing octahedra remains unchanged (B-X-B). by one to three different letters.1 b. aac stands for equal tilts about [100] and [010] and different tilt about [001].

perovskite at P-T conditions of the Earth's lower mantle ap = £ cos j8 cos y bp cp = Çcosacosy ^cosacosyS . ward (2001) to optimize perovskite structures.1 b. a°b+c~ and a°b+b" cannot be accomplished without minor octahedral distortions. The idea of performing this optimization was Aleksandrov (1976) emphasizes that octahedral tilts can be considered These are as soft phonon modes at the reciprocal-space points M3 and R25. already presented in the ar¬ ticle by Woodward (1997b). over superconducting Ba(Bii_xPbx)03 to hightemperature superconduction in some cuprates. stress. a+a+c". However among other things this article points out that there is a huge interest in perovskite structures.2) all probable temperature-induced phase and some phase transitions predicted for real sub¬ stances such NaNb03. found that the sophisticated actually FORTRAN routines in his code POTATO5. beginning with the high dielectric constant BaTi03. who treats stabilizing mechanisms for perovskite One of these mechanisms was later used by Lufaso and Wood¬ structures. As visualized in Fig.3 Analysis of quantities obtained M in MD value of a In molecular quantity dynamics simulations (MD) only the time-average (e. because of the technical progress Woodward (1997a) could more implemented tilting systems a+b+c". Tilting of the octahedra and Jahn-Teller distortions are possible internal optimizations of the structure. displacement) has a physical meaning to given 5Program Originated Analyze Tilted Octahedra 6Structure Prediction Diagnostic Software 46 . Small distortion of the struc¬ ture can heavily change properties. For the mentioned tilt systems he listed the correct space group symbols.16) = While Glazer used imagination and wire models for the determination of the use space groups. a+b+b". He prediction Lufaso and Woodward (2001) designed a program SPuDS6 that could predict the tilt¬ ing systems of complex perovskite structures with the generalized composition AXA4_XB4X12. a+a+a". 3.2. SPuDS could predict both from the composition and the empirical ion radii.) tilting of octahedra leaves the B-X bond length unchanged and decreases the empty space filled space group determination to space group Turning from by the cations. CsSrCl3 and many others. From group - sub-group are as relations transitions derived (Fig. The structure that filled space best was assumed to be the correct structure. because many inorganic compounds are found in that structure. ir¬ reducible representations of the space group Ol associated with octahedral tilting belonging to the boundary points of the Brillouin zone M and R.3 CaSiO?. 3. (3.g. On the other hand these perovskites have a variety of properties. 3. While POTATO as an input needed the B-X bond distance and the octahedral tilt system.

Only after the so-called correlation loses the information about the initial starts.18) usually given is a good estimate for the to error of ulations it is not appropriate ion in MD is apply it.19) than the correlation time rc be If the total simulation time iV is much longer can further properties of the correlation function exploited 47 .17) T=l In order to compare different quantities an estimate of the error is needed. This function depends on the displacements &Ä of M from its average value. Full lines symbolize potentially phase transitions. time system independent sampling For the the configuration and a new analysis of this problem the error of a magnitude 3i from a simulation of given length N can be related to the correlation function (&Ä(0) &Ä(t)).2 Methodology Pm3m a a a b+b+a° lAlmmm PAImbm a°a°b74/ mem a°b"b" Imma a a a Im 3 . In MD sim¬ The velocity and the position of a an from the velocities and positions strong dependence of the velocities and positions of one step on the coordinates of the former steps.2: Possible second order phase transition in perovskites. Because of the quantities derived from them. deterministically derived averaged quantity. The error cr2run = ^ derived from the standard deviation m-un)2 T=l' (3. dashed lines first order phase transitions. (3.R3c a a c a°b V Cmcm a" a"c+ Pnma a"b"c+ Pmmm P2XI m Figure 3. The square of the error is On N i--\(&A(0)m(t))dt.3. the simulation steps are no independent measurements of these quantities and of all the tc of all other ions in the former steps. 1976) 1 N (3. After (Alek- sandrov.

2000.23). To check if two quantities.24) 99 needs to be specified (usually %). This level ascertains the probability of the prediction in eqn.5759 for the confidence levels 66 %. 1118-1119). The index is not used to indicate the simulation time errors in the section before.6449.20) and long simulations times (iV we get the exact result a22T.2\ = 0. 90 % and 99 % respectively). 1984. ecrm the (3. A statistical analysis problem. p. p. 90 % or (3. (3.i-&. 346).. 2000. (3. p. that suffer from statistical errors are the same.3 CaSiO?. (3. Another method to determine e interval ecrD can is the numerical solution of eqn. In this context the index i on cr. oo) the corrections of the order JV"2 vanish knowledge of the correlation time and the standard deviation the quantity J?T obtained from the averaging over a MD run can be expressed. Because of statistical is this unlikely to vanish. (3. p. For the confidence level 99 % the to be true.22) quantities J?Ti and J?T2 is computed.24) for the error function erf(jc) (i. crl being the individual error as of the quantities J?T.23) to the error cr0 = The difference is errors subject Jcr2 + o\. Further details are given in (Allen and Tildesley. 1.. perovskite at P-T conditions of the Earth's lower mantle o-2n»Tc For = ^ J <57l W)>dt - jp —> J ?<<M(0) W)>^ = -^ O(n~2) + . From the inverse predictions from this analysis will have a probability of 99 % reading out of the listed <D-values the confidence be evaluated. in (Bronstein et al. For D > 2. 194) and error crN on a With the (Jacucci and Rahman. assigns the crt to the quantity Mt. their difference D is = \&i-&2\ two (3.23) is the appropriate tool to deal with P = 2<D(e) - 1 = erf(4=) V2 66 %. prediction M\ ± J?T2 has probability P to be true (Bronstein et al.9674.. e = 0. Applied to the main problem in my thesis where J?Ti and J?T2 stand for averaged strain in different spatial directions I can give the following example: 48 . 1987.g. Therefore a confidence level the difference in eqn. The equality of the equivalent to the hypothesis that their difference vanishes: D = \&. where O(e) is the Gaussian distribution listed e. 798).e.

2 Methodology Figure 3.U. of the probabili¬ ties of all criteria. the hypothesis has probability have each the probability n pi to be true.] phase boundary on the T axis with chang¬ ing resolution of the simulation.9674 + Jo-j crj. The tem¬ perature was chosen as parameter that drives the transition. 7In (Adams and Oganov. However Mi and M2 have their individual errors cr\ and cr2 (computed from eqn. Low val¬ ues of / correspond to a low resolution in the simulation. probability for the structure to be cubic is the product . If the arguments be true. To - verify the hypothesis + ^-^2 For cf\ - = 0 with probability to 66 % I check if \MX use cr\ + cr2 Ji2\ > 0. 3. but any other pa¬ rameter could have been chosen. is based on the criteria for the stresses C"i 0~2 - cr2 0"3 = 0 0 or ©« = - = ®ß 0„ = (3.21). when the structure is (3.27) = or for the The tilting angles 0a 0^ and 0r respectively.5 would shift the 4 6 T-% [a. This should be taken into account. 2006) the sum errors the hypotheses were actually checked using the of the errors not their mean square.4le and thus repre¬ mean corresponds to a hypothesis checked with e V2 sents a higher confidence level. Pressure is hydrostatic a when Mi - M2 = 0. <r2 it is acceptable instead of Jcrj cr\ for the total One has to be aware that this shifts the confidence level because CF\ + <T2 2o~\ v^ crj + 2 ^ V2 (3.26) hypothesis cr. error.3: The probability to find a phase transition across the region where the phase transition takes place. that the cubic.7 a - Therefore There is an additional issue when a hypothesis is based on multiple mutu¬ pt to ally independent arguments. 49 .25) hypothesis checked with sum of errors instead of its geometrical 1. A different choice of the confidence level than 0.3.

<(r. perovskite a at P-T conditions of the Earth's lower mantle phase transition the probability that a phase transition actually takes place is proportional to 1/2 + I x 1/2 + erf(xpb / Vtt/2) where x is the that the The drives transition.30) the autocorrelation function loses its time-dependence because the vibrational displacements high symmetry structure is stable.g.) x <(r. However a symmetric choice for the phase boundary simulations and Molecular xpb is P(xph.-Ä. 50 . (3. ideal addition to the methods described in section 3. The position correlation function therefore is a sensitive indicator for phase transitions. (3. phase transitions using the position predict autocorrelation function Vocadlo et al.2.4 Prediction of from the reached precision of the direction the or sampling.2.(f - to) - Ä. the position correlation function vanishes for long t: pt(t) 0 since Rt))2 <(r. If the —> - —> - = 'Any other choice of the be seen phase boundary 3. Therefore quantities obtained from statistical sampling always suffer from uncertainties although the phase transition might be very sharp.3 would shift it with increasing sampling precision as can in Fig. In hydrostaticity of permanently from their auto¬ position in the bcc structure at fixed cell a parameters. high symmetry rt(t to) (. (3.) denotes averaging - is its position at time t in the simulation that starts run.3). (2003) used the position auto-correlation function transitions in bcc iron under to temperature driven phase pressure. instead of the whole ensemble of states. 3. over the whole For long times t A(0-><(r.) .28) In fact this is the most sensible choice because the phase boundary phase should And be set first independent second it should be independent from the implemented in the simulation (e.3 to check they analyzed whether atoms have shifted high pressure.. for harmonic about the oscillation 0 a mean position Rt..l) = l/2 + erf(xpb -Z/V2) = 1/2 . parameter temperature is a very typical param¬ Across • • • - eter that leads in the simulation to smooth transitions because Monte Carlo Dynamics simulations are designed to sample a certain number of lowest lying energy states.a0) - Ä. Rt)) become uncorrelated. heating 3.29) Rt stands for the position of the i-th atom in the undistorted structure whereas at to.8 transition is cooling). These uncertainties determine the factor / and are responsible for the steepness of the probability across the transition region.3 CaSiO?. For given atom it is defined through Pl(t) = <(r. The larger / the sharper the phase transition (see Fig.)>2 a->oo).

3. Although quency present for the of the the width.(0v.a)r. 1987. p. If Tc»Ta (3. It (3. from lattice by bonding type temperature only weakly oscillation times derived dependent. For quency where the amplitude drops to zero coq is ness of the spectrum and it is often considered in the to the power spectrum of the of the broad¬ fre¬ vanishes power a spectra the lowest fre¬ measure good the as highest significant never ex¬ spectrum. coo the spectrum Fourier transform that converts the power to the auto-correlation function spectrum (function of frequency) coq (function of time) converts r0 = to the longest oscillation time present tc in the := spectrum ^f. metallic. ionic) and the bond length. r0 is frequently used to define the correlation time: r0. that the atoms do not vibrate according to the restoring this is an force present in the bonding but additional effects permanently displace the atoms from their ideal position. 1987.(0)>^. (3. Therefore dynamics it is ideal to be or compared with MD simulations. 186) connects the diffusion coefficient to the ionic conductivity crd 51 . p. This oscillation time is characterized (covalent. The Green-Kubo velocity correlation function (v^Ov^O)} to the diffusion coefficient D D = f \ Jo j <v.31) indicator. 3. From phonon spectra on the other hand an average oscillation time the of It is ra can be determined.5 Conductivity through ionic diffusion can Transport coefficients relation connects the often be related to correlation functions obtained from MD simulations (Allen and Tildesley. 190). p. a mean (3.32) N For long simulation runs —> oo this expression is equivalent to o = ^-<|r.33) square deviation A2 from initial The diffusion coefficient refers to an position after a given time t A2 D = — .34) on The Nernst relation the other hand (Elliott. The indicator decrease and total is rate an actly. 60). 1998.2.(0)|>.2 Methodology Any auto-correlation function can be related data (Allen and Tildesley.

3 CaSiO?,

perovskite

at P-T conditions of the Earth's lower mantle

o-d

=

-r^P
kBT

D

(3.35)

applies for conduction by diffusion of charge carriers of charge q and den¬ sity n at a temperature T. If a given conductivity should be assigned to specific charge carriers which form a network with spacing A, equating eqn. (3.34) and eqn. (3.35) can be combined and D can be eliminated. The final expression is
It

solved for

t

resulting

in the

expected hopping

time

h

=

^ff2kBl
crd

.

(3.36)

3.3 Results
In

small to fill the space left p. and 15°.9

perovskite structures, tilting of octahedra takes place when cations are too by the octahedra (see p. 46 and Woodward, 1997a, 33). This explains the strong octahedral tilting in MgSi03 by at least 13°
The ratio of the ionic radii
~

0.65 rMg/rCa at ambient conditions is (Ashcroft and Mermin, 2001, p.489).This is the reason why for CaSiC>3 per¬ ovskite much smaller tilting angles are expected. This will also bring the a : b and b : c ratios closer to 1 and the energy splitting between different tilting systems will decrease. Therefore high accuracy is needed for total energy cal¬ culations so that thermodynamical modeling may take into account the small energy splitting between topologically different structures. Experiments are confronted with the same difficulties: They ought to resolve tiny splittings of pseudo-cubic peaks, which are diagnostic for small distortions from the cubic phase. How small the displacement is can be seen in Fig. 3.4.

(a) sg. Pm3m

(b) sg. Imma

(c) sg. I/Amcm

Figure

3.4:

Perovskite structures for CaSi03

(red: oxygen, blue: silicon, grey: calcium).

For better

visibility the tilting of the octahedra is exaggerated by a factor of 2. (a) Ideal cubic perovskite structure, (b) The Imma structure along one of the tilting axes. Tilting takes place in anti-phase. Oxygen atoms that would point towards the observer are shifted because of the presence of a second tilting system (c) In the I/4mcm structure only one tilting system exists.
Calculated from
a :

b and b

: c

ratios listed in

(Wentzcovitch et al., 1993) and using eqn. (3.16)

52

3.3 Results

Caracas et al.

(2005) and Jung and Oganov (2005a) actually showed how
are.

close the energy differences between the different structures
I

Therefore
used here,

performed

calculations of

great accuracy.
core see

The PAW

approach

includes the full information of the valence electrons treated in
a

electrons for the calculations of the

(for details

section

standard

setting
O:

for the PAW
radius
=

1.6). Silicon and oxygen atoms potentials (Si: core radius =1.5
1.52
a.u. core

were

a.u.,

configuration ls22s22p6;
for the treatment of Ca
an

core

great important role which is even amplified when pressure is applied and va¬ lence electrons approach the core (Kresse and Joubert, 1999). Therefore 10
care

must be taken: semicore

configuration Is2) but [3s, 3p) states play

electrons

are

treated

explicitly

for calcium (Ca:

core

radius

=

2.3 a.u.,

core

configuration

1 s2 2s2 p6).

0 04h!3c

"D

^0,0000
LU
P4/mb!TT

<
-0,0025-

-0 0050

-0,0075

-0 0100 28 30 32 34 36 38 40 42 44 48 48

Figure
K

3.5:

ble CaSi03

V(Â<)

Energies of the most proba¬ perovskite structures a T 0
=

(Caracas

et

al., 2005).

setup of the unit cell of the MD runs I used the results of Jung and Oganov (2005a). To obtain structural parameters of the cubic structure at 0 GPa, 50 GPa, 100 GPa and 150 GPa they optimized a 20 atoms cell using
the steepest descent and of 500 eV.

For the

conjugate gradient methods

and

a

plane-wave cutoff
was

Self-consistency

level of the electronic relaxation

10"9 eV and

for the structural relaxation 10"6 eV.
I used these cells for MD simulations at 500 K,

1500 K, 2500 K and 3500

K. The

temperature
a

was

controlled

commodate the different simulation box electrons
were

2

x

2

x

1

using a Nosé thermostat. In order to ac¬ possible symmetries [Pm3m Imma, 1/4mem) in the supercell of 80 atoms was used. After each step the

relaxed until the energy
zone

T-point
+

for the Brillouin

100 fs.

Equilibration
some

time

oscillations.10 In

cases

changes were below 10"5 eV using the sampling. The time for equilibration was 250 was determined when stresses started regular in the equilibrated atomic spatial configuration
are

10This criterion poses problems when structures
the

simulated in cells that do not

represent

symmetry of the actual stable structures and the simulated ensemble is small enough for the whole structure to be inverted totally e.g. I/Amcm simulated in a cubic cell of 80
atoms. Stresses

perform strong

oscillations

over

the whole

run

whenever the fourfold axis

rearranges.

53

3 CaSiO?,

perovskite
were

at P-T conditions of the Earth's lower mantle

the velocities

reset and used to start

a

simulation at different P-T
new

con¬

ditions. This reduced the

equilibration

time in the

simulation.

3.3.1
I

Phase

diagrams
runs

performed
a

MD

at 4

temperatures and

4 pressures for

CaSi03 perovskite

in

ture.

supercell that was adjusted to the cubic symmetry of the struc¬ was expected to exert non-hydrostatic stresses on the simulation box, when the cubic cell was in conflict with the symmetry the structure would spontaneously take under the simulated P-T conditions. The
80 atoms

The structure

where <tij is the sum of the individual errors of crl and cr,. The confidence level was set to 99.9934 % taking into account eqn. (3.24) and eqn. (3.25). The individual

non-hydrostaticity

was

considered

significant

when |cr,

-

cr,|

>

3AcrlJ

errors cr,

on

the other hand

were

computed using
zeros an

eqn.

(3.21).

For the calcu¬

lation of the correlation time the first
were

of the auto-correlation functions

used.

The

correlation time

appropriate way to determine the arguments are given on page 51. Fig. 3.6 (a) shows the resulting phase
a

that this is

diagram.
cubic
one.

It indicates

and 2000 K. Therefore

phase transition to the cubic phase between 1000 K the phase relevant for the Earth's lower mantle is the

t>e

-c*

*w
x>&

H

orthorhombic
00
-

m-f
O

500

#

CD

O

O

0_00
.

tetragonal
P

50

P

,

100

[GPa]

[GPa] (b)

(a)

vant to the Earth's mantle,

of CaSi03 perovskite at pressures and temperatures rele¬ (a) Phase diagram obtained from the analysis of stresses. Filled symbols (^cubic, »=low symmetry) derived from calculation. Open symbols (d, o) from experiment (Ono et al., 2004). (+/-) next to a symbol indicates that correlation

Figure

3.6:

Phase

diagrams

and anti-correlation

between the cubic Pm3m and the Imma

phase boundary phase is drawn according to the distribution of the square and round symbols. The phase boundary between Imma and I/4mcm is 1 meV, estimated from the enthalpy difference of the two phases [Tc &HkB, Aff(OGPa) 17 meV.) (b) Phase diagram obtained from the position autocorrelation func¬ A?/(100GPa) tion of oxygen atoms. Error bars on the phase boundary are relatively big for both methods (analysis of stresses/position correlation function). Runs that show a clear correlation or anti-correlation of the stresses are considered to be especially reliable for the prediction of the phase boundary.
respectively
were
^
= =

observed in the simulation. The

In the simulation I observe simultaneous oscillations of the stresses in dif¬

ferent

spatial

directions. Most obvious

were

the

anti-phase

oscillations at T

=

54

3}. 3. Corre¬ (correlation) rl} > lation of the stresses be interpreted as an indicator for the cubic are dependent oscillation of the pressure on distributed a spatial directions...g. To quantify lation between the normal stress jumps components these I calculated the cross corre¬ r<. It turns out that this criterion is more sensitive to phase transitions than the analysis of stresses. As a criterion for the phase transi¬ tion from cubic to a lower symmetry phase the averaged correlation time of the oxygen atoms <t^> was used. - dicator for the presence of phase diagram for CaSi03 perovskite is shown which is analysis of the position autocorrelation function of the oxygen atoms.6°] cannot be explained with the tetragonal 14/mem 55 . = ^ el oscillations TT' Uj {1. The simulated ensemble changes the alignment of the shorter axis from e.27°..54° at 3500 K and 100 GPa. If the averaged correlation time was significantly bigger than the overage oscillation time «-rf ) > 5 rvlb) the phase transition was assumed to take place. Shim et al. where small time in all 3 rtJ was can 0.15 + 0.7. in the cell. Oxygen atoms are suited best because the phase transition is expected to affect the structure through rotations of the Si06 octahedra that displace the oxygen atoms most.19° and 0. for anti-phase oscillation rl} < 0 considered to be significant when \rtJ\ > 1/3.25 0. Jung and Oganov.44 + yields tilting angles comes 0. was = a significant tilting = of the octahedra.2.. The statistics of the from standard deviation of the average of the tilting angles at 3500 K is given One of the main calculations was reasons why I performed were these that experiments still in conflict with computationally expensive theory concerning the c/a-ratio of CaSi03 perovskite at low temperatures. r„e[-l. 3. 2004. 2005a.8. The movement of an exemplary oxygen atom at dif¬ ferent temperatures and its auto-correlation function is visualized in Fig.37) For in-phase (anti-correlation). (3. The average vibrational period ryib was determined to be 50 fs according to (Caracas et al.9 shows that the diffraction intensi¬ ties in the structure. Ono et al. x to y and thereby reduces the strain in y-direction while it simultaneously increases it in x-direction. In Fig. 3. Fig.6 (b) a based on the • For the cubic phase This I averaged positions The aim a and from these I calculated the to find + tilting angles y = of the octahedra. 2002). 3. 2004. 0.. Stixrude et al. 14.3 Results 500 K and P = 150 GPa. In Fig. The tilting angles are small. 1996) experiments find c/a < 1 (Kurashina et al. 2005). 2005. ß 0. smaller than the uncertainty that tilting angles in Fig. While many calcula¬ tions find 14/mem and c/a > 1 (Caracas et al. region [14°..3.6 (a) significant correlation and anti-correlation are indicated by + and respectively.l]. Anti-correlation a the other hand is phase equally strong in¬ phase with lower symmetry than cubic. 3.

05 «0. lOOGPa perovskite compared with experiment. The prob¬ ability that the prediction a = 0 II ß = 0 || y < = 0 is correct when y < a<Aa ||/? A/3 || Ay is 68.8: Tilting angles averaged structures for runs cu the at T = 3500 K and P = S 0-150 GPa. symmetry than the starting structure Therefore low energy structure with lower are not automatically found. from Figure 3. 100 GPa CO CO <u e>0.2 % 50 100 P[GPa] Exp. The structure un¬ 1000 K the autocorrelation-function dergoes in a therefore phase transition at about 1000 K.4 indicator for the c/a-ratio. The error-bars are CT» Ö t bigger than the absolute tilting angle which indicates that no tilting takes place. (a) & (b) Displacement of an oxygen atom from its ideal position in the cubic (c) & (d) Autocorrelation-function of the same oxygen atom.6°] (X-ray wavelength 0.3 0. VASP preserves crystallographic symmetry elements through¬ out the structural optimization.3 CaSiO?. perovskite at P-T conditions of the Earth's lower mantle °f$ « 2 t Eps] t Eps] (a) x(t) at 3500 K.4 0. The re¬ gion [14°.413 À) is significant because it is structures an different 14. 14. whereas at T < 1000 K (c) its decay is slow (note the difference scale).2 0. lOOGPa Figure 3.9: Diffraction patters of of I4/mcm OK. r- -v^-^—"^••r' X3 -B—S ^5 0. 93GPa Figure 3.5 2 Eps] t Eps] (c) pit) at 3500 K.02 o -a—B CO \^ . 2 [deg.2 14. 100 GPa (d) pit) at 500 K. 300K. At T > decays fast (c).1 0. The emer¬ on gence of additional symmetry elements during the structural optimization the other hand is not ruled out.] Therefore I — performed an intense search for other — possibly low symmetry structures.7: structure. 100 GPa (b) x(0 at 500 K. In order to metry structures I combined the lattice produce parameters of the 20-atoms cell a multitude of low sym¬ corre- 56 .

(3. rates two cooling rates: fast dT/dt were -6 x 1014 K/s and slower dT/dt = -3 x The structures cooled from 2500 K to 0 K within 4 ps and 8 ps for the faster and the slower tively.) averaged fitting of an obtain an analytic expression for the Grüneisen parameter.993. The 14/ mem seems to be preferred at 0 K because it has the lowest enthalpy.38) use The conversion is related to MD-simulations and therefore I will reduced number of the degrees of freedom (JV - 1) instead of N. 89°.15) to ematica.3. in the high temperature config¬ 57 . T). try symmetry when fast The resulting structures had Imma symme¬ combined with any cell shape. Inserting these terms and introducing AP P(V.014. 100 of the resulting structures had the 14/mem symmetry. respec¬ different cell shapes having c/a-ratios 0. The temperature of the simulated ensemble is thermally stabilized is MDgradually lowered. The vibrational energy - (N 1) • kB T.10) is recast Teff = V . The calculation of this parameter Conversion of ters steps: 1. 4 Imma. In VASP the ideal on gas correction ((jV"^ar) is not included. 1972) 12The cooling rate is so high. therefore it has to be added to the the other hand is known := averaged to be 3 we pressure P(V.014 and rotated b.T)-Pst(V) ' (N-l)kBT + APV = APV ' ' 3(N-l)-kBT 3(N-l)-kBT 3(N-l)kB-T ( ' ' "Notation of (Glazer.3 Results sponding were to a pressure of 100 GPa with distortions to a. Then full relaxation performed at a pressure of 100 GPa. give c/a 5°. MD-quenches potential high temperatures. T) - Pst(V) get 7eff (JtfäL = + P(V. Another method to determine structures that are quenching. that often the structure freezes uration. 91° and 92°. The octahedra according to the a~a~a~ scheme with \a\ valent combinations of these parameters was were first non-equi¬ optimized for fixed lattice - All 104 parameters. These cooling were combined with quenching rate.014). c angles11 of 88°.12 = In my calculations I applied 1014 K/s. was shape because it appropriate cell appeared only when slow quenching was combined with the shape [c/a =1. (3. The fitting proce¬ dure is straightforward and implemented in mathematical tools such as Mathpressures into 2. ratios of 0. Imma). parameter at different P-T-conditions for consists of two I calculated the effective Grüneisen CaSi03 perovskite. 90°. These computer experiments therefore hint that between the high-r cubic structure and the low-r structure (probably sg. The 14/mem quenching appeared to be very sensitive to the quenching rate and the cell 1 and 1.986 and 1.) Least squares averaged effective Grüneisen parame¬ analytical expression such as eqn. 14/ mem) lies an intermediate structure have the stable at (probably sg. For the conversion expression (3. Slow quenching combined with the inap¬ in a propriate cell shape resulted structure with Imma space group to freeze in structures that are symmetry.

et al. To account for anharmonic effects temperature dependent expres¬ sions such as (3.6 1. This would give rise to a discontinuous jump for the Grüneisen et al.2 1. When pres¬ 2/3 is expected for jf -l/laomTx"1 (see eqn. perovskite at P-T conditions of the Earth's lower mantle 2. (1996) and Chizmeshya Stixrude et al.580 5.0 a / 500 K 1500 K 2500K 3500K S y A / *4-t *4-t 2 1. 3.29 x metallic state before infinite pressure P —> (y 10"5 K"1 —> o => ex)) is reached. The graph clearly shows that tem¬ perature gives rise to anharmonic effects that destroy the validity of expression (3.873 1.9185 1.4 1. The is 15 %.10: (a) The effective Grüneisen parameter yeS obtained from fitting the data expression (3.3 CaSiO?. From the 58 . 3. Neither is comparable with our findings and this has one main reason: there must be a phase transi¬ tion to a 0. (b) Comparison of Grüneisen parameters for different Earth's mantle forming minerals. (1996) presented the idea that the 14/man structure under the (2007) explored the energy surface spanned by the amplitude of the octahedral rotations (eqn.2 "" —- 130 150 170 190 120 140 160 180 v[i] (a) V (b) [fl Figure 3.1.1: The Grüneisen parameter is one sure an higher than the found by Li et al.15) must be used.4 /> */ Yeff 1.31 A Vo 7co To a0 composed of electrons and protons.15). to The resulting parameters (100 see in the least squares fitting procedure our are given in Table 3. electron gas and y«. (2006a).8 «4-4 «4-! _.1). Two data points at the lowest temperature (500 K) and the pressures is easy to highest GPa and 150 GPa) were excluded because aim is to find the behavior of the cubic that at one. A yf D 1. = = joo+(yo-y°o)x raises to infinity y«.14) at high pressures.63 parameter.0 «* / >° X©1-6 1. the cubic structure would transform into rotations of octahedra. phase. From the phase diagram on these specific conditions the structure the other hand it deviates strongly from the cubic Fitted parameters of the analytic expression for the Grüneisen parameter error on a Table 3. Stixrude et al. Shim (2000b) used a different parametrization and therefore the resulting pa¬ rameters cannot be compared with this study.8 D 1. Abbreviations stand for CaSi03 perovskite (CaPv). MgSi03 perovskite (MgPv) and MgSi03 post-perovskite (MgPPv). 1/2 for the plasma Parameter Value 187.14) which depends only on volume.2 2. ß m 4.

3.34 À. cases. place I can exclude 1 - 10"15. (3. 1995). The resulting expected hopping time th (eqn. 14More recent studies (Kuvshinov and Olsen. Here P shown which produces an energy barrier of 0.14 MD simulations is used in other cases 13The hopping rate obtained from to determine the as conductivity values of a perovskite In some structure.14 ps.3.36) is 0. At 0 GPa the barrier is only ume - 1 meV. 2006) find significantly decreased conductivity 59 . (nA13 The hopping was enhanced by the removal of one oxygen atom. Using eqn. In the second a case the VASP-code compensates the Now that in the ionic diffusion in charge of the cell with no uniform of 8. (1996).11: In the Imma structure vol¬ conserving shear deformation along e55 gives rise to lowering of the en¬ thalpy. 3. This corresponds to 200 K temperature that is needed to introduce the possibility to stabilize the Imma structure. The result was not affected when instead of a charge neutral oxygen atom a charged (2-) I = = = = the existence of this phase oxygen ion total MD run was removed.017 eV. The minima for the en¬ +1. the preducted conductifities lie above the experimental (Boyett et al. The introduction of defects such vacancies turn out to be useful. The energy surface consists of an energy barrier of 0. In order to check if the high conductivity of 102 S/m of the Earth's lower mantle could be explained with performed calculations under several conditions that would enhance ionic diffusion. The effect is more pronouced GPa is 100 at high pressures.2 ps CaSi03 perovskite with time would be even hopping a probability event takes p > background charge.11) as found for the Pm3m and the 14/mem by Stixrude al. While the Imma symmetry correspond to the ergy were found at 555 a°b~c~ the tilting system resulting 14/ mem structures correspond to a°a°c~ and a°b~c°. are = 0 16 0 12 QJ 0 08 0 04 - Figure 3..017 eV (per 20 atoms).8 %. The negative charge of the O2" an¬ structure are in a distance of A 2 mol%) was assumed to be charge balanced by the presence of Al3+ ions [n02 4 mol%). and one should rule out ionic density of expected hopping conductivity with still greater certainty. Therefore shearing the cell of the Imma structure by e55 activates phonons that lower the total energy of the structure (strains here were chosen to be volume conserving). see tion exists et interesting (see Fig. 13 With a realistic oxygen vacancies that lies below the value assumed here the shorter.3 Results coupling is term / and the — shape of the surface — condensed in the parame¬ It ters A and B the authors could determine the transition temperature. I observed no diffusion in CaSi03 perovskite.35) I assumed the diffusion of negatively charged oxygen ions [q -2) whose positions in the perovskite 2. In the calculations of the elastic constants I found that phonons a to that between the Imma and the 14/mem similar rela¬ strongly coupled to deformations.

12: calculations at 0.3 CaSiO?. Ono et al. The Imma structure thought not to appear in the phase diagram of 0 and because it has un¬ mechanically unstable at T stable phonons. 1987) the enthalpy can be written as CaSi03 because it is = be c F = Fn + '% c 2-T. drastically 0. which are strongly coupled to the elastic constants. Results of static 100. The of the lower mantle (1 S/m).3 ps to p the lower mantle order transition. that the distortion must be small because else it would leave the part of the potential well.11 shows. At high pressure [P determined from static calculation whereas at low pressure [P 50 GPa) they lie below it.40) This allows to compute the where c°55 is the elastic constant at T=0. (Tc-T)el + ß-^4 15 (3. The possibility to smoothly 3.T) of CaSi03 perovskite. 50.44. 3. However. 2006) 15As the space group Imma is not a subgroup of 74/mcm. Landau picture (Tolédano and Tolédano.2 on the other hand suggests a first connect the two phases as it is shown in Fig. the Landau potential should have a sixth-order term and the phase transition should be first order. Fig. and 150 GPa were also included in the determination of = 150 GPa) the thermal results lie below the expected value css(p. (3. 2005. Then the structures distorted by 655 = +0. 60 . parabolic regime 6 in resulting cells — that governs the central total were combined — This reduces the expected hopping rate to runs 14 ps. The elastic constants css(p. the deviations in the lattice parameters small that the character of the as well as in the ionic positions are so phase transition is very slightly first-order and therefore not easily distinguishable from second-order. In order to check if a possible entropy stabilization could occur in the Imma structure.5 %. constant temperature dependent elastic C55(T) d2F „0 ^c -55" Tr-T + Tr 0(4) . This - significance post-perovskite already could be more apt to explain conductivity (Oganov and Ono. perovskite at P-T conditions of the Earth's lower mantle 100 50 100 GPa > -50 100 150 200 ^ 200 400 0 200 400 600 800 T[K] T[K] Figure 3. 100 GPa and 150 GPa and 0 Kelvin. of 8.2 Hardening of the unstable modes in can CaSi03. = 3.41) the 2x2x1 Imma changes sign super-cell that It at the critical temperature Tc. diminishes the of conclusions derived from However. The sampled cell The cell was was contains 80 atoms..3. first optimized for the symmetry were at 50 GPa. In the I calculated the finite-temperature elastic constant of the structure. T).

The Nosé mass was were optimized produce an ing Oganov oscillation time of 40 fs.3. with temperatures of 300 K.21). The elastic constants derived follow¬ (2001b). these phase boundaries describe only of the Imma unit cell vectors could further stabilize this lower bound.6 a (dotted line). — from 6117 to 9264 fs. corresponding approximation to compute the strains corresponding to a MD run with the high accuracy sampling. The new method for the determination of the phase transi¬ boundary based on the elastic constants includes these interactions and therefore more reliable. A relaxation in the earlier phase.) computed of cr\ of MD It is a reliable run.) de¬ notes the average of the strain in the the cell.13: Phase boundary between the tic constants calculations Imma and the 14/mem phase from elas¬ (full line) and from energy considerations as given in Fig. It is advisable to make use also of static elastic constants calculations in or¬ der to refine the uncertainties. 3. However. 500 K and 700 K. Error bars were a derived from the mean square deviations of the stresses combined with as correlation time analysis such described in eqn. The ideal gas correction as well as the correction for finite Brillouin zone sampling and energy cut-off were included to deter¬ mine the actual pressure of each simulation. The corrected strain of for every MD = run - with the same (cr. considerations that concerned the interaction tion is depth of the energy well (dotted line) the intersite was neglected. However. The strain components are then calculated once with high accu¬ racy sampling of and once with low accuracy sampling cr\ as it is later intended for the ions. because errors due to k-points sampling and finite plane-wave cutoff to a very good approximation depend only on the volume of cell parameters can then be from + where (cr. (3. The final 12 MD on runs lasted to average 7800 fs et al.16 and the maximal error (one standard deviation) were is expected to be 9 The calculations performed in the 20 atoms supercell using 4x4x4 Monkhorst mesh 61 . possible phase boundary: they were run do not suffer from statistical at a The static calculations high precision GPa. zone The correction for finite Brillouin the sampling and energy cut-off is com¬ puted using sampled starting configuration kept fixed.3 Results 800 600 400 i- 200 0 -200 0 25 50 75 100 125 150 P [GPa] Figure 3. The cell is also to use in the MD run.

that the octahedra of a.6GPa. The phase boundary is given in Fig. 2005. (3..4 GPa. c55.361 GPa K"1. It is steeper than the one from first estimates from enthalpy differences (Fig. 17This available in constant P. (3.46P K K - 10_1P2 GPa-2 4. perovskite at P-T conditions of the Earth's lower mantle The pressure dependence c55(P) can = Co + d P + c2 P2 + c3 P3 .12 and eqn.. 2002) find a c/a- 1 at ambient conditions while in many static simulations the structure with et al.61 10"4 GPa"2 and ax =0.It is advantageous to use different amplitudes of strain = with the same sign c = 2^~e) ^"^ (e\. 16 irreducible k-points were treated. 2005.ß > rigid eqn. 62 . 3.4 GPa). and shows that the 14/ mem is stable only at P > 15 GPa.T molecular dynamics simulations.18 This many static for the Brillouin zone sampling. c3=1.T) was found from a least squares procedure to the thermal data. (3. phase boundary between the Imma and 14/mem struc¬ ture. 2007). Shim c/a > et al. e2 < 0)) distortions.0K 1. Jung is 4.41) suggest linear in temperature dependence of This contribution ax T to the elastic constant c55(p.42) including GPa"1 + the thermal contribution: c55(P. Therefore I reformulated for T eqn. The parameters were found to be c0=87. Error bars then runs can be estimated e2 > from slightly different elastic constants resulting from with positive (e\.52 10"2 GPa"1. c55150 GPa) a = -213. 1 appears to be the lowest tetragonal structure 14/ mem enthalpy (Caracas 2005. T) = 0 => TC(P) = - 243.3 CaSiO?.. Whenever this elastic constant vanishes it announces a phase transition. 2005b.g. Fig. of +0. Jung and Oganov. e2 > 0. c55(100 GPa) -187.9° exist. c2=5. ci=-6. Caracas et al.66.6a). The electrons was were converged Strains e to a threshold of 10"9 eV and ions to 10"6eV. 18One tilting system leads to c/a > 1 independently of the phase of the tilting. 1996. Stixrude et al. 0) and negative [e\.1% and +0. But it also proves that not only the cubic structure can which describes the be stabilized with temperature (which is but also an a hint for stabilization through entropy) state (probably 14/mem) the intermediate structure between the ground and the high temperature an > cubic phase. c55(50 GPa) = -127.4 Discussion and conclusions It remains ratio < a puzzle why X-ray experiments (e.13. 3. The energy cutoff were 500 eV. e2 < 0).478 • 1(T4P3 K GPa-3 (3 43) . are Under the assumption.5% applied taking into account the = narrow double-well behavior. If the energy surface E(e) is not smooth at e 0 elastic constants cannot be a(+ calculated from c (e > 0). or e\.6 GPa. (3.4 GPa. This shows anhar- that for the structure optimization it would be desirable to optimize structure for elevated temperatures by introducing entropy term including monic terms that stabilize soft modes at T 0..17 3.531 • + 18.16) implies that two tilting axes structure supported by assumption optimizations (Adams and Oganov. 3.42) = be determined from these data (c55(0 GPa) = 87.

Stixrude measured Several et al. 3. Otherwise the fluctuations between required to allow optimal fluctuations in Sienergetic minima require instantaneous distortions of the octahedra. or at least suppress ther¬ mal fluctuations to an adequate level. eters a symmetry an Note that the lowest structure [Imma) was found in which freezes instantaneous = = Several factors could aries as they are shown e.7d. from the experience with (2007) argue that from group theoretical considerations and phase diagrams of other perovskite structures. and Warren et al.3. in improve the reliability of predictions upon phase bound¬ if the cell Fig. Stixrude et al. The dimensions perpendicular to the tilting direction are reduced.4 Discussion and conclusions Oganov. The resulting decay rate of pit) after a phase transition occurs would be considerably reduced. Similar with the lower symmetry structure at intermediate temper¬ ature while the low temperature structure has can higher symmetry. which disturbs the relative orthorhombic Imma phase offers another way to 4. Variable transitions large super cells would allow to freeze phase permanently.19 Assuming two dynamical tilting sys¬ tems an average structure with tetragonal P4/mmm symmetry. Stixrude et al. that octahedral distortions are energetically costly. similar to the static displacements (eqn. is unlikely. axes are dynamical tilting perovskites.g. 1998).. X-ray explain experimental findings c/a-ratio as well as its pressure depen¬ Imma intensities. driven by thermal fluctuations and dynamic tilts can occur: instantaneously the octahedra appear to be tilted while in the time average the tilting vanishes. Fig.601 À (at 100 GPa) and c/a < 1 results. octahedral tilts on the other hand can be easily excited (some of them are related to unstable modes) and correspond to phonons at the M and R point (Caracas et al. 2006b) also refers to instantaneous tilting sys¬ This issue might be refined: octahedral tilts are tems in MD simulations. 2005. In fixed cell simulations — — shape ations is not fluctu¬ adjusted to the phase symmetry at the given conditions between neighboring local energy minima are enhanced when the initial are cell cell parameters fixed to values between true lattice parameters. (see also (Stixrude dence are et al. (2007) assumes that in experiments the tetragonal structure is with a preferred orientation. lattice param¬ 2. 63 .. However. 2007).627 À and c 2. various exceptions are known where phase diagrams do not follow be said about the these rules. 1996. strategies can be followed to explain this disagreement. MD-quenching high temperature configuration.16).2). things (2006b): No direct relation exists between Pm3m and Pbnm (see Fig. potentially The classification in (Li et al. 2005b. shape in distortions from methods in combination with 'Also the octahedra At least two in time average appear to be distorted. 1996. Long simulation runs on the other hand could decrease the fluctuations of pit). 3. Stixrude et al. phase diagram constructed by Li et al.. The best explained with the orthorhombic symmetry)... 3.. 2007) which show. a phase ordering.

3.6a and 3. with a variety of space groups (2002) [14/mmm. 64 . (2007) finds a 20Note: The shift of confidence level always shifts the phase boundary.6b findings. The graphical extrapolation of the phase boundary between the cubic and the tetragonal phase in (Li et al. phase presented by Li et al. perovskite at P-T conditions of the Earth's lower mantle Experiments olution is not cannot resolve the tilting systems can in CaSi03 because the on res¬ high enough. The because it involves refine their diffraction patterns in-phase rotations of the octahedra along two axes. while with the choice given in eqn. P4/mbm). the position of phase boundaries cannot be obtained from the comparison of stresses obtained from MD simulations alone. Indeed at 0 K the orthorhombic phase is found to be unstable (Fig. 90 % and percent can The choice is not unique. In the displacive limit overshoots the critical temperature of the phase transition. The limited stability field of the cubic The is in contrast with my Stixrude et al. Other tetragonal symmetries that even involve bond distortions (Shim et al.28) is a plausible choice for the open question which confidence level should phase boundary it re¬ be chosen to predict a Any choice of the phase 99 % transition. levels of 50 %. At static condi¬ tions agreement turns out to be even broader: Stixrude et al. P4/mmm. 14/man. Although for the prediction of phase transition MD is a powerful tool. 2002) cannot be ruled out even though at T 0 they are unstable: the structure can be considered as averaged structure with sev¬ eral unstable phonons at T 0. In my calculation the confidence level of 99. (2007) make use of the Landau theory to predict the phase boundary between the Imma and 14/mem phase. This is much higher than the upper estimate by Stixrude et al. (1996) which is 2500 K to 3000 K at 80 GPa. This impli¬ cates that in the calculations some problems might have been present. However. show a broader stability region for the cubic phase.28) the sampling precision does not shift the phase boundary and therefore is a unique choice. (3. 3. (2006b) phase diagrams in Fig. Arguments for confidence be found. 66 %.. e.g. and it is clear that this would broaden the stability field of the cubic phase. it does not apply for my work because whenever kpoint sampling and the energy cut-off were decreased. that the Imma phase is unstable at 0 K. a pressure correction that would compensate for the erroneous stress was applied. This assumption was also formulated by Stixrude et al.9934 % is chosen high. (2007). 2006b.3 CaSiO?. For the lattice parameters the other hand it is sufficient. space group 14/mmm is unlikely = = Even mains though an eqn.12).. Therefore Shim et al. confidence level shifts the level affects phase boundaries. 1) gives a transition tem¬ perature of 6000 K at 80 GPa. non hydrostatic pressure due to poor k-point sampling and low energy cut-off which was not corrected. Fig.20 The choice of the confidence as well as predictions from the position-correlation function. The authors also argue. The discrepancy remains sur¬ prising. (3. An intermediate phase was excluded from the beginning: only a single transition temperature Tc was introduced and coupling of two octahedral tilting systems among each other was ignored. It is known that this the¬ ory ignores thermal fluctuations.

3. (2007) negative. Both Adams and Oganov (2006) and Stixrude et al. The crucial difference between (2007) is the Clapeyron slope of the I4/mcm-Imma we find it to be positive. transition - temperatures. At lower pressure both works find the Imma structure to be the most favored. dubious initio or While Stixrude et al. Imma = (2007) also claim that the phase is found it may be stabilized at elevated our findings and those of Stixrude et al. where the static fitted to ab energies. (2007) find that the Imma structure is mechanically unstable at T 0 and positive pressures (at negative pressures it is more stable than other perovskite structures). This claim was not supported by any calculations and is unlikely to be correct. while Stixrude et al. to stem displacive initio only approximation). (2007) obtained their Clapeyron slope using part was arguments (Landau theory. without any proof from the soft modes. but the entropy differences limit validation. our Clapeyron slope molecular dynamics simulations. At high T the Imma structure is stabilized probably through the entropy terms. were assumed. because of insufficient erroneously k-point sampling.8 GPa. but in contrast to Stixrude et al. and to be derivable from the was determined using ab 65 .4 Discussion and conclusions minimal stabilization pressure for the tetragonal structure of 18 GPa while in my calculations this pressure is 16. (2007) we find that Stixrude et al.

perovskite at P-T conditions of the Earth's lower mantle 66 .3 CaSiOj.

Evidence is found from neutron diffraction and electron microscopy (Gavarri and Carel.1 impurities in MgO on Previous experimental and theoretical work Mg^Fe^O Magnesiowüstite Mgi_xFexO and wüstite Fei_xO have provoked many stud¬ ies on their properties. The defect ordering of wüstite might not have a direct geophysical implication. the rhombohedral phase boundary and the dependence of the HS-LS tran¬ sition pressure on temperature. This has many reasons. Welberry and Christy. V13T4 and V15T5. 1998). In the section I want to show some following Many of these difficulties can be resolved by theoretical investigations. However it has a great influence on the physical properties and the HS-LS transition phase boundary. 1995. defect ordering only as a At ambient conditions wüstite exists non-stoichiometric a compound while others need further clarification.1 Fei_xO. 1981b) and diffuse X-ray scattering combined with clus¬ ter modeling in order to reproduce X-ray data (Welberry and Christy.1. the origin of the defect ordering. Main cluster sizes are V10T4. second by Wel¬ berry and Christy (1997). wüstite is an extremely complex material. 1998. second. A short range order of vacancies and long range order. 1997. These clusters define surate or incommensurate on the — — 67 . agreement of scientists Following points belong to the first cat¬ egory: the sublattice of O2" in the rock-salt structure is fully occupied. the actual size and authorship of these clusters belongs to the second category of findings under dispute (Carel and Gavarri. Some points seem to be resolved under wide contains Fe vacancies and interstitials. 198 la. Gavarri and Carel. Welberry and Christy. 4. This is true for the type of bonding in wüstite (localized electrons and strong correlation effects) as well as for the defect or¬ dering. where V stands for y 1997). of the difficulties. The third one is another suggestion by Welberry a interstitials exists.4 Effects of Fe 4. 1998). 1998. While different authors seem to agree that VyTz vacancies and T for z tetrahedrally coordinated Fe interstitials are the pre¬ dominant clusters in wüstite. magnesiowüstite is thought to be one of the major constituents of the Earth. e. First one is preferred by Gavarri and Carel (1981a). which is commen¬ depending density of interstitials (Carel and Gavarri. pressure and Fe concentration. 1995. iron exists mainly in Fe2+ and in a small amount of Fe3+. It is obvious that most of the previous experimental and theoretical works have difficulties and contradictions among each other. Therefore it is one of the keys to the understanding of this material.g. The complete structure Fei_xO. First.b.

In zone-axis diffraction studies they observed the A reformation of defect clusters as well as the formation of a variety of low sym¬ which the well known rhombohedral structure (above metry phases. The authors concluded that the tional gradients which triggered the formation of different the other hand was sample might have showed local composi¬ phases. (b) The Vi0T4 clus¬ ter. which at the center has a positive net charge which is compensated by octrahedrally coordinated Fe vacancies in the surrounding. Redrawn after (Carel and Gavarri. through temperature increase. that the ratio of interstitials to vacancies explains the relative intensity of the diffuse peaks. The different phases were built in different regions of their sample. that the asymmetry in the diffuse peaks can be explained by the relaxation within the clusters. that the distribution of clusters affects the intensity distribution in the diffuse peaks.4 Effects of Fe impurities in MgO Christy (1997).1: (a) Diffuse scattering that sourrounds Bragg peaks in the observed ray diffraction patterns. Through modeling of the defect distribution Welberry and Christy (1997) could show: first.. From (Welberry and Christy. (2005b) (see also Ding et al. circles are Fe3+ impurities in tetrahedral coordination. 2005a). The change found to be reversible irreversible when induced a in the defect super-structure The former on when induced by pressure. among 19. 1998).8 GPa). The intensity distribution contains the information about the structural distortion in wüstite. and (a) (b) X- Figure 4. second. and third. but might be interpreted as that would increase the second order latter entropy whereas the in displacive originates from the diffusion of defect clusters resulting large defect clusters at high 68 . Clusters of vacancies and interstititals have to be surrounded by octahedrally coordinated Fe3+ ions while the position of the vicinity of surrounding ions depends strongly of the symmetry of the cluster. Cubes represent octahedral vacancies. phase transition pressure. 1997). strong compositional sensitivity in Fei_xO was found by Ding et al. Gavarri and Carel fects: the (1981b) gave the following reasons for the existence of de¬ charge neutrality of the whole system claims the existence of two Fe3+ in an Fe2+ vacancy. The authors prefer the Vi0T4 cluster.

measured the cell parameters from diffraction. (2004b). the other hand show 7 Jackson et al. Mgi_xFexO by Berger et al. The anisotropy factor 69 . Further findings of Knittle and Jeanloz (1991) concern the melting curve of Fe094O and possible coexistence of Fe and FeO.1. The amount of Fe3+ turned out to be small: 0.1. The authors found a large violation of the Cauchy law C44 This equality is valid for positions and interact crystals where the atoms occupy centro-symmetric exclusively through pairwise forces. they they X-ray measured a drop in the resistivity which they explained by a phase change from the antiferromagnetic semiconducting phase to a metallic phase above 70 GPa.02 + Fe3+/ 2 Fe 0.1 Previous experimental and theoretical work on Mgi-xFexO Knittle and Jeanloz relation of lattice (1991) found a mean composition of Feo940 from the in a parameters (Hazen and Jeanloz. The measurements were conducted at 1 atm and the results are given in Table 4.4. hexago¬ nal) observed later in Fe0954O by Murakami et al. they for pressure determi¬ spectrometer to determine intensities and line-shifts pressure medium. They grew samples of -3 cm3 volume and (pulse echo through the ultrasonic sound measurement overlap) measured propagation velocity of sound waves in different directions and for different polarizations.2 Elasticity of magnesiowüstite. A further conclusion is that the CMB has a temperature of temperature 102 GPa and 300 - 5413 K. 1984). At around 70 GPa ^4800 K. coupling in FeO is strong. The d-electrons in the t2g state turned out to be strongly localized. This was a result from the refinement of inelastic neutron scattering using a tight-binding model. Kugel et al. In a standard DAC experiment that included methanol- ethanol-water (MEW) nation and a as a in the Brillouin Fabry-Perot system. results are = = (2006) measured the elastic properties of Mgo94Fe0o60. Performing experiments conditions of 0 - to ion concentrations known from former works DAC at pressure and respectively. Although they measured a sudden volume change at 70 GPa they did not confirm the expected phase transition from Bl (NaCl-type) to B2 (CsCltype).64. Experiments on 2.01. C12 and C12 and the sound velocities VP and Vs. The work (1981) might be the wave most direct one to determine the elastic properties of wüstite. ruby chips determined the elements of the elastic tensor Cn. The given in Table 4. This transition can be explained by the high pressure/high temperature phase transition from the rhombohedral phase to the B8 (NiAs-type. From their findings they deduce that a chemical reaction between liquid Fe in the outer core and FeO in the lower mantle has a high probability to occur and this would result in the dissolution of O in the liquid iron.1. (1977) found that Fe-Fe 4.

2000) (Sinogeikin and Bass.2 + 0.82 P - Reference (Jackson and Niesler. 1981) Composition Pressure en. MgO 0 - 3 GPa + [GPa] [GPa] [GPa] 296..2 velocity ß's on dence of this value the iron concentration was found. ci2. 1982^) (Berger Fe095oO OGPa al. pure agreement with the data obtained from the (Fe-free) material at pressures P <20 GPa. The elastic constants could have a strong dependence on temperature.2 P - 0. MgO 0-55 GPa 297.7 P-0.8 9. With pressure it decreases and vanishes at the maximum pressure of 20. which is ß's 1.3+ 1. A vanishes for iron free MgO are 6. Theoretical values lie between 14 GPa (Karki violation is 1996) and 18 GPa (Oganov and Dorogokupets.0 + Mgo94Fe0o60 9.01 pressure.7+ 1.42 P 0.8+ 1. The mechanism that leads to the stabilized due to the following: Oxygen ions. Or there could exist a discontinuity of the elastic constants and their derivatives at the HS-LS boundary at around 60 GPa. However the pressure derivative of the shear in this duced sound experiments exceeds the value determined for the Earth's lower mantle by Jackson (1998).35 P 1. The displace¬ ment is induced by strain and would affect the stabilizing electrostatic field the 02+ ions are exposed to.. 70 . 2006) Composition Pressure en.89 P et 155. c44.063 P2 0.8 at 0 GPa and A=0 at 7 GPa. A linear depen¬ - by Fe-impurities 2.39 + 0..61 P - 0.2 GPa.. 2000).0047 P2 95. Zha et al.014 P2 A = 2£44+£i2 C\\ - _ j {42) materials C21 which vanishes for at room elastically isotropic This is in was found to be A = 0. The spherically symmetric breathing of the oxygen ion is the origin of the many-body forces leading to the Cauchy violation (for further details see Karki et al. c44. Oganov and Dorogokupets. the one explained in several ways: the iron concentration is smaller than found within the Earth. ci2.1 At 20 GPa the deviation in¬ is -10 %.4 Effects of Fe impurities in MgO Table 4. The anisotropy factor of pure MgO is much different from the materials con¬ taining iron impurities. Finally is should also be taken into account that magnesiowüstite makes only about 20 vol% of the lower mantle.5 GPa (Zha et al. and interaction strength) when the surrounding ions are displaced.030 P2 [GPa] [GPa] [GPa] 8.016 P2 125 57 0..1: Elastic parameters for MgO and different amount of Fe impurities. 2003). 2000) (Jackson 0-20 GPa 284 103 147 + + + et al.09 P -0. The Fe impurities seem to have a strong effect on the elastic properties of MgO. 2003) Cauchy electrostatic field. (2000) measured A=1.11 P 95. This mismatch can be experimental experimental composition is Mg094Fe006O whereas the estimates for the Earth range from Mg082Fe0i8O to Mgo72Fe0280. which are solely crystal change their physical properties (ra¬ dius.6. The ratio is even negative in the range from 10 GPa to 50 GPa (A ^he experimental values where and 22 GPa et al.059 P2 - 226 155. Reference (Zha et al.. 1996.

. Brillouin scattering methods on pressures. NRIXS first determines phonon frequencies.. (Jackson et Mg0. The method measures intensities and frequencies of phonons in a similar manner as the Brillouin measurement: neutrons are inelastically scattered by the nuclei and thereby absorb or create phonons. From (Jackson et al. 1982) amounts of Fe MgO. 2000) Small and (Jackson and Niesler. 2006) on (Zha et al.94Fe0. Hu et al.. respectively. (2006) with the He was exception that used as a pressure medium rather than MEW. 2006) sistent among each other but also with measurements at ambient conditions (Jacobsen et al... Brillouin spectra beam of neutrons: 0 = measured at different angles with respect (Jackson et to the incident are con¬ 50°. al...06O. The modification due to the iron impurities is fixed all the pressure range to +17 GPa (cn. The interpretation of the spectra from inelas- 71 .. impurities nearly double the anisotropy factor at 0 GPa.2000) 50 6 8 10 12 14 16 18 20 22 10 20 30 50 pressure [GPa] P[GPa] (a) (b) constants of are Figure 4. 2003.. 2002). 1982) o c 0. The experimental setup for the Brillouin inelastic scattering mea¬ was very similar to the one used by Jackson et al. 2002). Iron impurities have an anisotropic effect on the elastic constants: cn and c44 are increased. 90°.18. Lin et al.0]). 2006. 2004.2002)Mg0fe006O (Sinogeikin and Bass. g surement [-0. (Jackson et al. 9=80° . 80°. 2003) MgO (Jackson and Niesler. .2000). 2006) rQ n -„. (b) Comparison of the anisotropy factor A of different mea¬ surements.1 Previous experimental and theoretical work on Mgi-xFexO 450 400 350 03 9=90°. The method was based on nuclear resonant inelastic X-ray scattering (NRIXS). 2004). MgO (Zhaetal.25O in this study) is the one by Lin et al.. . This allows the measurement of phonon spectra (Sturhahn.. 1995). Struzhkin et al. rare With applied solely to single crystals.4 vm L„ M9o«4Feo»6° (Jackson 0. Full line: measured range. The measurement of the Debye frequency and the longitudinal and can be transversal sound velocities is rather indirect and connects the properties of the phonons to the microscopic macroscopic properties of the polycrystalline sample (Fiquet et al.Fe»»P + (Jacobsenetal.75Feo. (2006). dashed line: on extrapolation...2 200 c. sophisticated measurement of the elastic behavior of magnesiowüstite (Mgo. All measurements of al.n K c 0. while over cn is decreased.. Solid black lines linear fits to Mg0 94Fe0 oôO at room temperature as a experimental data (see also Table 4.2: (a) Single-crystal elastic were function of pressure. c44) and -17 GPa (ci2)..1). 2001.4.MgO J MgO (Oganov and Dorogokupets. pressures P >60 GPa can polycrystalline samples only.1 (Zhaetal. 2006) Of 9=50° '250- JM9o.3 * et al. This Maybe the most method is introduced because standard determination of elastic properties is difficult at high be obtained for the other hand the exceptions. latml. The energy difference of the neutron before and after scattering is similar to the phonon energy.1 0 100 -0. 2006). Sturhahn et al. E 160 < 0..

27)O + + range [GPa] 0-51 5. rhombohedral Fe093O and cubic Mgo 73Fe0 27O from single crystal DAC measurements (Jacobsen et al..195 77..41 9. (2002) at ambi¬ ent conditions. 2006.683 79. theory there are no difficulties to connect these microscopic features with as macroscopic properties such Lin et al.003 0.005 0. Kung et al.66 + + 0. 2002) originates from a different Better chemical composition.. K' is fixed to 4. The combination of the two shows discon¬ properties is at 33 GPa.0 for Fe093O.04 + + 0. the bulk and shear sound velocities. Above the spin transition pressure a (P=50 GPa).011 3 ^0 [GPa] 146+ 2 154 tic scattering in terms of phonon spectra is based on a deconvolution of the spectra and involves the average atomic mass and the mass of the nuclear res¬ onant isotope (Hu et al.018 0. 2002) and it gives different results for VP.93O P Pq rhombohedral Fe0.22 4. Vs and G.0 + 0. Kung et al. 1995). 2006.72 9.4 Effects of Fe impurities in MgO Table 4. Further experiments and 4. 2003.. At the was phase boundary difference of VP of 0. 2005).53 km/s found.036 4 0.73Fe0. (2005) and by Kantor (2005) for Fe0. and high pressure phase transition Fei_xO not have in Low in temperature properties of materials do because Earth's minerals an are geophysical application room general observed at temperature and are above. 2002) could chemical composition. Fe093O reported by Jacobsen et rhombohedrally distorted al. Sturhahn et al. discontinuity in all elastic and thermodynamic properties They assigned it to the HS-LS transition of iron that should appear at that pressure (Lin et al. On the other hand it finds good agreement with single crystal and ultrasonic measurements It is an by Jacobsen et al. The elastic constants cannot be measured In directly - instead the acoustic phonons are measured.78 km/s a to 1. cubic Fe0. cubic NaCl structure to a was The transition from structure for et al.2: Equation of state of cubic Fe093O. in the pressure range of 0 GPa to 52 GPa a splitting of the cubic (2 2 2) line into two rhombohedral (110) and 72 .95 134 + + cubic 0-51 (Mg0. In DAC measurements. 2005). The study shows many dif¬ ficulties at relatively low pressures: it is incompatible with other ultrasonicand Brillouin-measurement studies (Jackson et al.3 Low temperature. agreement with (Jacobsen et al.1. be based on the very similar theoretical work should clarify these issues..9: O 23-51 5. The study consists of two dif¬ a (2006) found - at 60 GPa.005 0..1.. For Mgo73Feo270 it is found to be 4.926 + + + [g cm"3] Vo [A3] V0 /atom 0.. Wüstite is connected to low exception because high pressure properties a directly temperature features.92O..09 [À3] 0. the other at 33 < P < 120 GPa) which are incompatible among tinuous each other.30 9. the study fully consistent. study (Jackson et interesting question if the disagreement between this al.667 59. ferent runs (one at 0 < P < 33 GPa.

The a splitting coupled significant with comparison (Mg0. 2005). The spectra are normalized and shifted in order to cancel the line shift of the maximum induced by pressure.8 GPa and 27. amount of Fe in the HS state.27JO and K0=146 GPa and ^o=134 GPa for the low-pressure and high-pressure phases of Feo. The 15 GPa).2.7 GPa (Jacobsen et al. These satellite peaks disappear at -40 GPa. The compressibility changed across the spin transition. At the it 'hardens'. In of the He as a pressure medium which the best guarantee for hydrostatic- addition hydrostaticity as was attested through ruby changes of the fluorescence line. The transition is smeared out over a broad (b) EOS of Mg0 vsFe0 25O.25O in the (110) direction. (2005) by the appearance of incommensurate satellite peaks in the X-ray pattern.. EOS The phase transition is shown in Table 4. This is more likely due to the disappearance of the long range ordering of defects than due to the disappearance of the defects themselves. The mechanism that drives this transition is assumed to be of the 73 . (b) inset: Normalized stress (/ ) against eulerian strain (/). While below 55 GPa the material 'softens' with pressure above 74 GPa 55 GPa and 67 GPa. The experiments conducted at ambient was temperature conditions the very small to using ity.1 Previous experimental and theoretical work on Mgi-xFexO (a) (b) Figure 4. From (Lin et al. were 2005).73Fe0.3: (a) X-ray emission spectra of the Fe-Kß line of Mgo. In the HS regime even more subdivisions of the EOS could be necessary because sample is likely to contain regions with different local Fe concentrations which undergo spin transition at different pressures. shows which does not undergo phase transition in this pressure range.930 respec¬ long range ordering of defects in Fe093O found by Gavarri and Carel (1981b) and Welberry and Christy (1997) is confirmed in the work of Jacobsen et al.P= 0 GPa) or at high pressure {TN= 300 K.73Feo. that the increase of Fe content in MgO decreases the bulk modulus (from K0=160 GPa for MgO to K0=154 GPa for (Mgo. The intensity of the satellite peak is proportional to the region between spin transition region the EOS of the different spin states cross each other.75Feo..4. P= tively). Fei_xO was found to undergo a phase transition from cubic to rhombohedral at low temperature (7^=198 K.27)O. (104) lines was observed between 22.

4 Effects of Fe impurities in MgO magnetoelastic type: the magnetic subsystem couples to phonons and the to¬ tal system can minimize its energy through a magnetic ordering and static ionic displacement (Struzhkin et al.h the only free parameters least squares fit.eD)-9nRT[-) I from a — and ^ y \-7 . The experimental parameters are the Grüneisen 500 K parameter y0=l-50. (2005) found the structural phase transition to be independent of the magnetization induced through cooling in Feo920.3 GPa. 0D)] (4. The was experimen¬ was mea¬ tal method for the measurement of the elastic constants travel time measurement in sured in could or a a the ultrasonic DAC while the local magnetic field spectroscopy experiment.4) where the energy is calculated in the j Debye model I \3 r&o/T 3 j E(T. (2005c). Low temperature seems to have a similar effect on Fei_xO as pressure: it enhances magnetic order.5) yo and q can be found From the measured thermal pressure P. the structural distortion (measured through the angle a of the pseudo-cubic cell) set in at 160+5 K.2 The experimental bulk modulus and its pressure derivative are KT0 =157 GPa = 2The volume dependence of the Grüneisen parameter was modelled using (4. 74 . Therefore earlier results might have to be reconsidered. The reason for these findings be experimental: sluggish kinetics could hinder the phase transition Mössbauer non-hydrostaticity might suppress magnetic ordering in the work of Ding et al. While the magnetization set in at 201+0. The experiments were conducted in a DAC with a thermocouple heating and white synchrotron X-ray radiation. Kantor et al.455 rhombohedral from experiment).Fe04)O was found by (1992) who stud¬ ied the thermal equation of state of this material up to 30 GPa and 780 K. the Debye temperature at ambient conditions ®D0 and #=1. 2001)..3) r = ro(0. c/a 2.1 K. from the mag¬ netization. (2005c) on the other hand found no long range magnetic ordering in Feo930 at high pressure.450 cubic. experimental parameters - The determination of involves the Mie-Grüneisen relation: Ah = | [E(T.1 which gives the volume dependence of y. = <^o(-) (4. (2004) observed a softening of the c44 elastic tensor component in the pressure = = range between 0 GPa and 10 GPa and at the same time an increase of the hyperfine field that acts on the Fe nuclear magnetic moment. The structural distortion could originate No from the electronic reordering in the Fe independently Fei et al. Ding et al. High pressure ab initio simulations could answer these ques¬ tions from the comparison of enthalpies of the rhombohedral and the cubic structure and the electronic DOS of the two phases. the neutron c/a diffraction experiments showed magnetic superlattice reflections. ®D) / £(300 K. The pressure range might have been too limited for a phase transition. Al¬ though a structural phase transition from cubic to rhombohedral was ob¬ served (at highest pressure 20. phase transition in (Mg06. Kantor et al. the magnitude of distortion is small: 2.

where the transition sets in at 85 GPa and complete at around 145 GPa.5 % and 18. The authors claim. For comparable Fe concentrations the phase transition is broad and at a lower pressure [Pt 40 GPa.10) were performed by Ono et al.. V« = 44.1 Previous experimental and theoretical work on Mgi-xFexO and (dKT0/dP)T Based pose a on = 4. Fe positions were chosen to be at a maximal distance. A3.4. (1997) pro¬ volume conserving HS-LS transition in Fe094O that sets in at 85 GPa and 240 K and 120 GPa and 50 K. widening the transition pressure upon Fe concentration and - Fermi level and the of the gap. 4. 1999) suggest.. The transition appears to be complete when the pressure is further increased by 60 GPa. Speziale et al.b) calculated electronic band 3.1. The transition pres¬ sure appears to be low (85 GPa) compared to former Mössbauer spectroscopy = studies is (Pasternak et al.4 Theoretical work In LSDA+U calculations on magnesiowüstite Tsuchiya et al. Two rhombohedral phases were found with different volumes (at 85 GPa. that the transition is first order and that the results in the study by Pasternak (1997) are based on misinterpretation: differential stress smeared out the critical pressure. that the magnetic in Fe092O is preserved up to a pressure of 143 GPa. Band struc¬ tures for the HS-state showed that states of Fe in the through the strong coupling term the 3d t2g-state was were shifted out of the Fermi level to higher ener¬ gies. (2006a. Mössbauer spectroscopy measurements Pasternak et al.125 %. x The Hubbard coupling coefficient U was determined in an self-consistent way (Cococcioni and de Gironcoli. Further investigations on the pressure induced phase transition in Fei_xO [x 0. The = = 3The authors of this study put forward 4Pressure medium NaCl an inverse B8 structure to be the ground state. However. structures of magnesiowüstite (Mgi_xFexO. of U For the LS-state the electronic was rearrangement through in a the introduction minor and reflected mainly decrease of the DOS below the study found no dependence of a sharp HS-LS transition at 20-28 GPa. 75 . 1997). 12. x 20%. which can be observed up to the highest pressures of this study.5 %). (1999)3 they propose a paramagnetic state to be the high pressure phase.83 et al.4 Great care was taken to guarantee the hydrostaticity of the pressure: the samples were annealed using laser heating to 1500 K. X-ray emission moment of Fe spectroscopy (Badro et al. (2007) in a synchrotron DAC measure¬ ment. experiments using comparable or higher Fe concentration [x =20 80%) found increasing transition pres¬ sures upon increasing iron concentration. Ions were relaxed to their equilibrium = positions.. VHS =44. 2005). In disagreement with previous theoretical studies by Fang et al.14 A3). 2005). At higher concentrations [x=25 %) an unexpectedly high transition pressure of Pt >125 GPa was found. This is de¬ rived from the splitting of the Kg line.

(2005) confirmed the HS-LS transition first found by Badro et al.2 %.. 60 and 80 GPa Mgi_xFexO [x 0.5 % et al. The amount of Fe3+ was found to be be¬ For low the detection limit of 1 % of the total Fe..904. (2003) InK is = In (xFe/XMg)mw - In ((XFe/XMg)pv = -(AG/NkBT) 12+2 across (4. 1989) was finally shown by complete electronic rearrangement of Fe in Mgi_xFexO pressure could be proven. (2006). that Mgx_xFexO could act as an insulator for infrared computed transition and = = = = = to shift from 0 (equal partitioning) to confirms the predictions radiation. The Clapeyron slope of the HS-LS transition is computed to be 56 K/GPa which would shift it to 120 GPa at 2500 K. 76 . 2001. The intensity of the satellite peak was used to tion: of the Fe-Kg determine the fraction of the HS-LS states.5 HS-LS What was spin transition a magnesiowüstite Badro et al.4 Effects of Fe impurities in MgO in 4.1. (2003). The NaCl-type structure was found to remain across the phase transition. 2002. With their results the authors confirm what was later found by Goncharov et al. Note that several works observe no shift of the partitioning throughout the HS-LS transition (Andrault. 250 GPa for the LS phase (under the assumption of ^T Furthermore it was found that the addition of FeO in MgO shifts the HS-LS transition pressure to higher pressures. The extracted intensi¬ ties from the Mössbauer spectra reflected the = ratio of the corresponding spin change AV across 5Unfortunately the contributions to AG were AU + pAV - T AS due to the volume by change the picture. The transition was smeared out broad pressure range. The logarithmic partition coefficient Based on crystal field calculations Badro et al. Great care was taken in the sample preparation. In Mössbauer spectroscopy a HS-LS transition in and 0. The high-spin configuration collapsed be¬ suggested (2003): the The experiment was tween 49 GPa and 75 GPa.6) the phase of Gaffney and Ander¬ thereby also son (1973) who predicted a harder material with a smaller Fe-radius when the phase transition from HS to LS in Fe was complete.5 Lin et al. Kesson et al.8 %) was observed at 40. Mao transition can phase not included Badro et al. 1997). and significant changes of the bulk modulus and its pres¬ Vols/Vohs 160. The presence of a satellite peak of the Fe-Kg line indicated the existence of the HS phase..38 for the HS phase and ^0t sure derivative: K0T 4 for the LS phase). respectively (Speziale = 0. under stable long time before (Anderson. In the DAC MEW (16:3:1 volume ratio) was used as a pressure medium as well as Ar. over a reason for this broad transition range could predict. based on the measurement X-ray emission spectra in a sample with typical mantle composi¬ Mgo83Fe0i70. The ex¬ perimental EOS suggests a ratio for the volumes at ambient conditions of 0. The not be found. Fe09?O the transition pressure was found to be 90 GPa.7 GPa. ^T 3. The consideration of these contributions étal. (2003) using the same methods and a slightly different composition (Mg075Fe025O) The HS-LS transition set in at 50 GPa and was complete at 60 GP. 2005). that the spin collapse would be responsible for the almost expulsion of iron from MgO to MgSiOs when Fe is in the LS state.

.Fe)O narrows under pressure in favor of (Mg. pressures (4 K. of (Mg.7) the phase transition and AS the change in entropy.6 Further The topics D" has stimulated many competing theories about its ori¬ gin. This interpre¬ tation is suggested by many works that found clusters of Fe and vacancies as a ferric iron content is decreased. Welberry and Christy. The latest theory explains the anisotropy with layering of post-perovskite in the D" region (Oganov and Ono. stability of the LS configuration in (Mg. Using the 0 K transition pressure and an estimate of the Clausius-Clapeyron slope Hofmeister (2006) questions the dP/dT = AS/AV across (4. Multianvil press and DAC experiments showed that with different initial Fe3+ content (ferric iron) at high pressure the samples samples were later equilibrated at high pressures (up to 40 GPa) and high temperatures to study the equilibrium iron content at these conditions. 1981b.4. The a experiments showed broad transition dependence on temperature and pressure. It would be interesting to reconsider these calculations inserting the Si-corrected elastic constants for orientation of FeOandMgo75. Yamazaki and Karato tion 1373 experiments Mg075. 1996) they com¬ puted a maximal VSH > Vsv anisotropy of 1-2%. 2004a). 4. The volume change — across the transition found to be 4..6 The stability field et al.6 %. where AV is the volume difference 77 . In terms of iron impurities in MgO this result can be interpreted as a discharge of Fe3+ interstitial impurities and their transition to Fe2+ that would occupy crystal sites instead of interstitials. Murakami et al. One of the previous causes anisotropy of suggestions on is the layering of (Mg.g Gavarri and Carel.Fe025O K) and high shear stresses (70-164 MPa) they measured the preferred and FeO. 2004.Fe)O due to shear strain that preferred orientation. 6 K) were extrapolated and combined with region (ÀP > 25 GPa) and The low temperature transition room measurements to obtain transitions pressures at ambient temperature temperatures and was high pressures. she gave the phase stability region of the possible spin configurations. For the magnetic entropy the expression 6Alternatively the elastic constants obtained in DFT+U calculations could be used. Combining the measured amount of orientation computed elastic constants of MgO (Karki et al. The substitution mechanism in wustite (e. Under (2002) performed deforma¬ high temperatures (1073- with the crystal grains..Fe)Fe204 (McCammon in 1998). 1997).1. The authors conclude that in the lower mantle be present and the spin transition centration and the wide transition mostly LS Fe should because of its sensitivity to the Fe con¬ should not cause a discontinuity region — within the Earth's mantle.Feo250.1 Previous experimental a and theoretical work on Mgi-xFexO states.Fe)O under lower mantle conditions.

. with low excitation energy. Gon¬ commonly assumed charge transfer between Fe and O.u. Core radii were 2. t2g and eg).200 a. the absorption spectrum does not significantly change. respec¬ tively.u.1 Analysis methodology were PAW-GGA PAW-GGA calculations tials performed using the VASP code. 14 and 6 electrons on Mg. Based the considerations of Zaanen et al. The coupling between the Fe-d orbitals sensitively depends on the local surrounding of the ions. These were the 2p63s2 (Mg). respectively. (2006) measured the radiative conductivity in a DAC experi¬ on ment up to 80 GPa. Sp^d^s1 (Fe) and the 2s22p4 on O (Kresse and Joubert. coordination numbers and Second k ionic radii. et al. Upon pressure the density of states orig¬ inating from the d-orbitals increases. 0. 1999). 2. (1985) about the mechanisms of chemical bonding in transition-metal compounds.g=Rln(2S + 1) (4.2 Data And 4. Furthermore when the LS configura¬ tion is reached upon pressure. All of them predict the HS-LS transition pressure to be below the mantle geotherm which 84 to indicates the 102 GPa for instability of LS iron in the mantle. 2005). 2006) were chosen between 49 to 58 GPa for Mg083Feoi70.7) and (4. proportional to R~5 or R~9/2 depending on the The empirical point model used for the determination of the radius.4 Effects of Fe impurities in MgO Sm. where R is the gas constant and S the Two ways First were used to estimate the volume difference the spin transition. 2003) and Mg0 4oFe0 6oO according to (Lin et al. In the using the structural parameters. They can be provided by the HS state that includes an addi¬ tional magnetic state. (2006) doubt the 4. charov et al. 78 . which decreases the optical gap (and increases the absorption).520 a. charge model is using the splitting between energy levels k. In the measurements the LS state shows a lower radiative conductivity than the HS state. Instead they put forward the electron transfer between neighbor¬ ing d orbitals on Fe sites as the key to understand the electronic structure of Mg!_xFexO. This results in Clapeyron slopes of 0. for Mg. Fe and O.31 GPa/K.000 a.20 and 0. 54 to 67 GPa for Mg075Feo250 (Badro et al.2. The radiative Convection Goncharov conductivity of Mgi_xFexO is of major interest in geophysics. (4.. underlying idea behind eqns.18.8) is that temperature favours configurations with many energetically low lying levels. The PAW poten¬ selfconsistently treated 8. and 1. This indicates that the absorption is mainly governed by the shift of energies of the spin states (Fe 3d. This serves as a stabilization mechanism for the HS state at elevated temperatures. Electrons of the lower lying states were fixed in the core. Therefore can take place only in a limited range of conductivity.. Absorption edges and absorption peaks are shifted under pressure until the LS state is reached. Fe and O re¬ spectively. across is used.8) spin quantum number. The transition pressures in (Hofmeister.u.

for two impurities 5 arrangements are possible: While the first impurity is fixed in position 0 the second impurity can take positions with numbers 1 to 5 in the table below.04 eV. For more than 1 Fe impurity per 64-atoms the remaining atoms can be distributed on sites with nonequivalent distances. Â # sites 3. The constant of proportionality decreases with the order of the smearing scheme.8 12 5. Fe Table 4.3: Nr. with pressure increment of 10 GPa. The pro¬ configurations settings a appendix [xFe = B. 31 Mg.4. A plane wave basis set with an energy cutoff of 700 eV was used. Ions conjugate gradient method up to the self-consistency threshold the total energy of 10"6 eV. computational meth¬ ods: one with standard GGA treatment of the total electron density and one with separate treatment of the two spin components using the interpolation for the correlation part of the exchange correlation functional developed by settings were These three 79 .3 and ^2 = 3. On the other hand it introduces errors T S \Efree Etot\ that should be smaller than 1 meV/atom. Further possible configurations of 3. MgO significantly re¬ duces the band gap.6 3 The electronic relaxations relaxed with the on were iterated to self-consistency. which tions were k-points. were as Three different rangements possible spatial configurations cedure how these for the Fe atoms chosen in order to as cover a wide range of well were different concentrations. 4.125 %).2. and 2 settings with with the = longest 12. 4 and 5 atoms are given in appendix B.32 1 dist.111 meV/atom. The energy differences between the HS and the LS state were converged to an accuracy of 8. The procedure to find all non-equivalent configurations (under the assumption that Fe substitutes for Mg) will fix the first Fe atom in one of the possible 32 positions.38 3 7. Real space local used in order to speed up the evaluation of the non projec¬ part of the potentials. 10 0 1 1 2 3 6. e. The errors are pro¬ portional to the cr-parameter.6 12 4 5 9. one determined is in table 4.2 The Clustering 64 atoms in total were supercells containing a optimized in the range of ar¬ 0 GPa to 200 GPa. 1 Fe and 32 O atoms 4 Fe atoms. Equivalent configurations of Fe atoms are characterized by equivalent distances between the Fe atoms involved. were which was con¬ sidered to be achieved when the total were energies stable to 10"9 eV.5 Fe-Fe distance possible the other with the shortest distance [xFe combined with 2 different ^ = %).5x 10"5eV. A 4 x 4 x 4 Monkhorst scheme was applied for the resulted in 4 irreducible k-point sampling.2 Data And Analysis Lattice sites in a 64-atom supercell. The three consisted of the centration possible in 64 atoms given setting with the lowest Fe con¬ supercell. i.g. Smearing works optimally was used with a smearing parameter cr when the smearing parameter is big. Therefore the second order Methfessel-Paxton smearing 0.e. Using the present settings the error term In the DFT calculations the substitution of Mg with Fe in = = - was TS = 0.

configuration only at the three lowest pressures [O GPa. polarized GGA calculations.g. 4. that even in regions where unpolarized electron configuration is energetically preferable. In the cell. The pressure range is an 50 GPa to 90 GPa where the low spin configuration is the correct from energetical point of view. states e. 20 Fe-d-electrons in Fe concentration. 4.3 GPa and 63.4 GPa 4. lFe.1 % Fe concentra¬ always found to be metastable. a Several local energy minima exist. lFe. 80 . It is remarkable that the increase of the Fe (clustered Fe). Fig. 4. The energy minimization process end in local minimum. Fig.5% shifts the HS-LS transition pressure from 26 GPa to 30.1% to 12. GGA calculation. 4.6. a polarized (metastable) solution is often found.4 (a) — concentration from 3. .4 shows — samples of the resulting DOS.6) are The comparision of the Fig. (Fig. The minimization schemes for the total energy apparently remain in local minima located between the fully polarized (4 ßB) and the unpolarized electron configuration. that the energy minimization in the presence of electronic when the polarizations difficult and not always can successful. As Fig. . that the GGA treatment of these the iron Fermi level. SIC-LSD calcula¬ states is correct. 7This solution is probably not stable. respectively.4 Effects of Fe impurities in MgO Vosko et al. that the structure with the lowest lying energy (or enthalpy) is always found.5 shows (region between 634 kbar and 1750 kbar) the the polarization enhancement was so effective. On the other hand. (1980) and initial magnetic moments of 4 ßB on each Fe ion.16 (c). It reflects the is fact.5. the states at around -3 eV below the Fermi level in the uncorrected LSD appear below the valence band in the SIC-LSD calculations - compare Fig. starting electron a minimum. 4.7 and enthalpies at different pressures is shown in Fig. 4. Fig. The second treatment enhanced spin polarization. This fact is motivation for configuration procedure is more related to that minimum than to the true described in this paragraph.4: (a) Density of GPa]. 4. while the first one completely suppressed it. polarized and in the unpolarized calculation.16 (a) and Fig. the density of the the vicinity of the Fermi level is low mainly because of the low — Pressure does not shift the electrons away from the Fermi level. i g a E-EF [eV] g a -10 -8 -6-4-2 0 2 4 E-EF [eV] (a) (b) states: 64 atoms unit Figure 4. 4. !fi -zu -ö -D -i -z u z i !fi m . the 3 ßB state in the Intermediate tion spin case of 3.8. (b) Density of states: 64 atoms unit cell.7 Applying the procedure described here guarantees. the lowest pressures Fig. . The structure is stable in the HS 10 GPa. 4. At impurities introduce half-metallic states at the tions suggest.

This method is more robust against small to a straight line that crosses the AG deviations of the data points from the linear behavior. which is the lowest concentration feasible in a 64 atoms supercell. Above 850 kbar this state collapses to the correct LS state.5: Mgo 96875Fe0 03125O. 4. The vanishing of the enthalpy difference announces a phase transition from the polarized to the unpolarized phase and can safely be extrapolated from two neigh¬ boring data points with opposite sign. where the Fe atoms build a cluster of the smallest distance possible (i.e. 5. Up to 260 kbar the HS state has the lowest enthalpy and therefore is preferred. which clearly has higher - enthalpy that the LS phase. where the Fe atoms avoid each other at maximum distance (i.2 Data And Analysis < P [kbar] GGA-PAW calculations: GLS) for Enthalpy differences (AG := GRS Figure 4. Be¬ tween 250 kBar and 850 kbar a metastable HS state is found. > 2 2000 P[kbar] GLS) for Mgo 875Fe0125O. Either method could be applied equally safely. P[kbar] Figure 4. transition = = 81 . However. The HS structure is stabilized up to a pressure of 634 kbar.6.4. Although the concentration is the same as in Fig. Note that every data point is computed from the enthalpy difference between the calculation with a polarized electronic starting config¬ uration and an unpolarized starting configuration (in the unpolarized calculation any polarization was suppressed by constraint even during the energy minimization proce¬ dure).37 Â at 100 GPa). Above 634 kbar an intermediate spin (n 3^iB) is found which in fact is not stable at any pres¬ = sure.e.8 Aat 100 GPa). the HS-LS phase Figure 4.6: GGA-PAW calculations: Enthalpy differences (AG := GHS - GLS) for Mgo 875Fe0125O. The energy difference between the origin of the enthalpy (AG 0) and the actual data point is an exact result and is not based on an extrapolation of the data points at high pressures (> 600 GPa) as the arrangement of the data points in the plot might could suggest. 3.7: GGA-PAW calculations: Enthalpy differences (AG := GHs - occurs already at 303 kbar. the transition pressures given were calculated from an extrapolation of the data points which could visually be connected 0 level.

1}. 42: Fe avoid each other. 1986.?\ {{0.1/2)) and 2 empty spheres (at (3/4.3/4. The LMTO-codes distinguishe between low.21176 {â.3/4) and (1/4. included in the Hamiltonian high waves. The prim¬ itive cell contains 1 Mg (at the origin). while at high pressures the Fe atoms attract each other. lattice vectors of the face centered cubic cell (Fm-3m.0}}. The 3d states on the O site as well as the 2p states on E were represented as intermediate waves.. HF calculation). 0. On E states were considered. only implicitly.1/4)) resulting in maximal overlaps of The 13. 8 and 32 formula units of MgO were space of the secular equation that is 82 .05313 À.3 SIC-LSD methodology were SIC-LSD calculations merman performed uses with the Daresbury LMTO code (Tem- et al. 0 250 500 750 1000 64 atoms cell comparision 1500 1750 1250 P[kbar] Figure 4.83 eV (Whited and Walker. experiment) and 8. 1974.71 eV (0. Zenia. 1998) which structure constants and screening constants determined in the reproduce experimentally found band gaps between 7. LS 0 CD < 2 MgO+4 Fe. 2003) was used throughout all the cal¬ = culations. The resulting band gap was 8. At low pressures a close setting of the Fe is preferred.{1. the HS configuration is stable to much lower pressures. 3s and to On Mg only the put 3p and 3d states were core treated as valence-states. 1.751847 À for Mg.2.1 % between atoms and the empty spheres. The numbers count the Fe configurations.8: GGA-PAW calculations: Comparision of the enthalpies of the different Fe spin configurations to the 42. whilst the 2s and no core 2p states states. 3p and 3d states of Mg. This indicates the existence of a hysteresis in experiments: Once the atoms are equilibrated at high pressure. were On O the Is states treated as into the core. {1. High waves are This is done in order to reduce not explicitly considered in the waves Hamiltonian. 1 O (at (1/2.1}. 225) were chosen of MgO were Stuttgart adjusted in order LMTO code to (Andersen.22 the value À (4. empty sphere).4 Effects of Fe impurities in MgO > 2 41.2 aBohr) was necessary to increase the band gap given above (the resulting clusters contained 66 scatterers). intermediate and the size of the Hamiltonian.9% for atoms and 15.b. The valence 3s.. Best agreement was found with radii of 1.1. and the Is states on E were treated as low waves. valence whereas all the other states constituted the were states. valence 2s and 2p on O. An increase of the cluster size radius for the structure constants determination to 2. 1975).1/2. Partial information on the intermediate waves is through their tails.1.1/4. O and the interstitial spheres (E.34646 À.9 eV (Pantelides et al. 1969. while the low build the fully diagonalized (Lambrecht and An¬ dersen. sg. 41: Fe at smallest distance possible. The theoretical lattice constant of À (Oganov and Dorogokupets. In a second step supercells containing 4. HS setting. The muffin-tin radii as follows 4. and 4.32 Hart). 2006) to provide the eigenvalues and eigenvectors.0.

25 x 10"7 Ryd/atom).7 x 10"6 eV/atom (1. This guaranteed the convergence of energies and energy differences to more than 1. beginning which of the orbitals are - yz. all out. 1 1 e* 1 1 1 1 1 J?. 1 e* 1 1 1 J?.2 Data And Analysis built keeping all atomic parameters fixed including the sphere radii. are re¬ Fe2+ or Fe3+. 1 1 1 1 1 1 1 1 1 1 1 1 1 1 e* 1 1 1 1 1 t2. 64 atoms supercell. In addition another state without any SIC-corrections used. If 4p and 3d states treated as low waves. For Fe the 4s. — applied to delocalized states the self-interaction correction vanishes or in contributions to the total energy. It is not clear from the (3z2 r2. 1 1 1 1 1 1 1 1 1 1 1 1 1 1 e* 1 1 1 1 1 1 1 1 t2. xz) levels localized and which delocalized. t2. 0 0 1 e* 0 1 t2. which have spectively. At the beginning of each elec¬ tronic optimization procedure the charge was normalized to obtain a chargeThe radial neutral cell. Fe3+. K-point sampling ranged from 16 x 16 x 16 and 8x8x8 to 4x4x4 for the 8. t2. 0 0 0 0 0 0 0 0 0 0 0 0 0 1 e* 0 0 1 J?. 4p and 3d states were treated as the valence states. They were labeled a-n for Fe2+ and A-N for Fe3+. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 e* 0 0 0 0 0 1 0 0 0 0 1 0 0 0 0 0 0 0 1 b c 0 1 1 0 0 1 1 0 0 0 1 1 1 0 1 1 C D E F 0 1 d e 0 0 1 0 0 1 1 1 0 1 0 1 1 0 1 1 f 0 0 0 1 0 1 1 1 1 1 1 1 1 0 0 1 0 0 0 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 1 1 1 0 1 1 g h i 0 0 1 1 G H I 0 0 1 0 1 1 1 1 1 0 1 1 0 1 1 1 0 0 0 1 1 1 0 0 1 0 0 0 0 0 0 0 1 1 0 0 1 J k 1 m n 0 0 0 0 0 J K L M N 0 0 1 0 1 0 1 1 0 0 0 0 1 1 0 0 0 0 1 1 0 0 1 0 0 0 0 0 0 83 . All the valence 4s. In order to find the correct electronic structure of Fe. t2. t2. which is also the scale limit of the code. 16.and channels are treated as majority and nel the number of corrections is at least minority channels. x2 y2) and 3 t2g (xy. with the lowest energy Fe has 8 valence electrons and is 5 localized electrons. In equal to the number of down-spin the majority chan¬ corrections in the minority channel. while the assumed high spin state corresponds was to configuration b (HS). 2005) low spin state (LS) corresponds to configuration n. For the d electrons 2 eg exist. was dependence of the charge density within the muffin-tin spheres sampled on a grid containing 250 points. 0 1 e* 1 t2. The correct configurations have to be tried (or enthalpy at pressure) is the assumed to appear as configuration 6 or one. The commonly assumed (Speziale et al. Majority channel Fe2+ a Minority channel Majority channel Fe3+ A B Minority channel J?. In these supercells 1 to 4 Mg atoms were replaced by Fe.8 Under the assumption that the eg and the t2g can indistinguishable among themselves 14 different correction schemes In order to take the be found for Fe2+ and spin symmetry into account the up. This state is labeled lsd. respectively. Therefore the self-interaction correction should be applied only to localized numerical treatment give small erroneous states.4. while the rest were as core states.. 8A11 the different spin configurations can be found below.

The errors from the numerical inversion of the expression of the pressure (eqn. Yet numerical inver¬ The latter was used to find expressions for the enthalpy are possible.2. net). Energies at in¬ compressions (typically 10 different volumes) were calculated and fitted to the third-order the different spin the Birch-Murnaghan EOS. 4. inverted for 10 electronic configuration).9.9) = ^ (xlß Vo x5ß) 11 x + (B' 4) x (x2/3 - 1)] x:=v auxiliary program : / / (http exciting. (4. Therefore it is advantageous to make polynomial fits to sets consisting of enthalpy differences (pt.1% to 40. sourceforge.25 eV/atom in the given pressure range).4 Transition pressures in the SIC-LSDA calculations Total sion energies were - calculated at highest compression in and at one no compres¬ (typically belonged to the termediate 200 GPa and 0 lowest GPa).9) and the fitting of second order polynomials to the enthalpy differences resulted in errors is almost 2 orders of magnitude: the of the order 10"8-10"12 eV in total.10 84 . Structures that of these listings energies were then further considered. 1947. using an provided with the EXCITING code sions The pressure in eqn. 4. 4. AH^) rather than those of enthalpies (p^H^).7% typically responds The EOS to pressure range of -20 GPa to 285 GPa. 2000) E(x) P(x) = E0+ 9-^ (B'(x2/3 - - l)3 j + (x2/3 - - l)2 x (6 - 4x2/3)) (4.4 Effects of Fe impurities in MgO The lattice parameters of 2%.10) on enthalpy strong dependence pressure. 4. resulting energies were then fitted to the third-order Birch-Murnaghan (Birch. subscript s the differences AH(P).9) is not invertible analytically. enthalpy two differ¬ between different electronic electronic configurations reflect only the small shifts raising from the setting (the difference between the amplitudes - enthalpy typically changes by 9 eV/atom while enthalpy differences change by 0. The were scaled in the range of-10% up to +16% in or steps cor¬ resulting a volume in- decrease of -33. Poirier. The resulting graphs are given in Fig. These volumes were used to calculate enthalpy dif¬ ferences between different structures at 10 pressures: AHM While the ences = jjsçys) _ Hf(yf) has a . Transition pressures between configurations were calculated from the intercept points of enthalpy differences. Fig. For any spin configuration the pressure P(x) was numer¬ points in the range of 0 GPa and 210 GPa to provide ically the corresponding volumes V" (index i counting the volumes. (4.

1% Fe). Increased Fe concentration shifts the along transition (intersect between a A and 132 GPa (12. Two scenarios are possible: first.2. the electronic configuration of the A corwas range of concentrations (3. a 4.5% and 3. Dif¬ ferent treatments of the exchange-correlation energy (SIC-LSD/GGA). 2005). SIC-corrections) the magnetic moment linearly range between -10 GPa and 56 GPa.1%. A wide sampled to cover most of the range that has been investigated by experiments (Lin et al.1% respectively.5% Fe) and 35 GPa and 57 GPa (3.11 for Fe concentrations of 25%.5 Equation of state The equation of state (EOS) is strongly connected to the phase diagram.2 Data And Analysis 0 50 100 150 200 P [GPa] at a Fe concentration Figure of 25% 4. at a Fe concentration of 25% to 4. treatment. struc¬ common sampled cells to the concentrations) that A. Speziale et al.. 83 between 67 GPa and 97 GPa (12.1% Fe). which in this section should be those of the SIC-LSDA. 12..4. At lower decreases concentrations in the (no SIC-corrections) a sudden collapse from 4 ßB to zero takes place Fe) respectively. electronic configurations and It is Fig.5% Fe) and drops from 131 GPa 86 GPa (3. The linear func¬ tion fitted to the magnetic moment in that region vanishes at 63 GPa. 25% 50% and 100%) 85 . 2005. Structure A retains its magnetic moment of 4 ßB the whole pressure range and so do structures b and C. In the lsd setting at ambient con¬ no ditions Fe carries magnetic moment of For 25% iron concentration (and 4ßB at any concentration calculated.5%. feature of all n 12. the spin (ferro-magnetic/anti-ferro-magnetic) and the ionic relaxations result in differ¬ It is advantageous to compare results from only one ent phase diagrams. two lowest and lsd belong (corresponding energetically lowest lying are to different Fe- tures and that at low pressures A and at elevated pressures lsd in fact the lying structures.5% Fe) and 192 GPa lsd) pressure from 143 GPa (3. Settings n and N never show magnetic moments.9: Enthalpies of the different compared to the lsd.1% The intersect of b and n Gpa (12. to (25% Fe).

electronic 3.5 2 lsd^\ . 0.5 : -"-If" ^— A 40 60 80 100 120 140 P [GPa] configurations at a Fe concentration Figure of 3.11: Enthalpies of the different compared to setting A. electronic 86 . 2.10: of 12.1% 4.5% Enthalpies of the different compared to setting A.4 Effects of Fe impurities in MgO ^\lsd 3- ^\N > CD \ M90 875^0 12P ^"^ j2~~-~-~~~~~~~ A 0 20 40 60 80 100 120 140 P [GPa] configurations at a Fe concentration Figure 4. : ><^^Mq \.5 - 5 1. »96 9% Fe 3 1°/o O > = 0^ 1.

16(d)).45 175.51 173. The changes due to pressure well due to differences in — the SIC-correction scheme. 4.122 -54 -54 -25 4.4.19 GPa (A50 in better with the scenario is experimental findings that show hard¬ agreement ening across the critical pressure.45 GPa to 175.16.632 9.6 SIC-LSD calculations: The total spin Density of states was density of states for different SIC-correction schemes cal¬ culated.671 4. while in the setting n they are strongly hybridized at the bottom of the highest occupied band). An overview of the most DOS is submitted to interesting cases as is given as in Fig.9 170.16 (d) and Fig. the in of the Fe-d 4. although the magnitude of the hardening is much higher [AB0 +90 GPa) in experiment (Lin et al.271 163..129 4. At high pressure the occupation in the up and down-channel is equilibrated and the magnetization is lost (Fig. At concentration of 25% the bulk modulus B would decrease by - lower concentrations the HS-LS transition has the second scenario A is assumed to be and the transition takes an on significant introduced artificially ground no effect B.371 9.015 8.93 169.084 9.125 4.198 9.19 164. second case 87 .353 9.16 (c) visualizes the mechanism that leads the a successive depolariza¬ tion of the lsd structure when pressure is applied: the electrons in the Fe-d up and down channel approach each other in energy.16 (f) (notice. 4.009 9. 4.39 -208 -90 0 4.8 169. 2005). Fig. the Fe-d (up channel) electrons are just below the Fermi-level. highest strongest +12 GPa).234 [À3] B [GPa] B' ^Sr^ [meV] 0 -446 -384 -116 0 -217 155.04 4. The second jumps from 163.19 3.96 9. Fig.108 8.19 170.69 172.895 3. The — at com¬ can particular parable conditions simply shift the position of one band compare e.16 and 4.16 states (a) (c): in the first case position Fig.736 9.g in Fig. Fe concentration.959 rection scheme is the one ground state at ambient pressures which turns to the obtained from lsd at elevated pressures.4: Parameters of the most important phases of Mg!_xOFex from the third-order Birch-Murnaghan EOS derived from SIC-LSD calculations. while in the — correction scheme they are below the first fully occupied band or lead to a complete re-hybridization of some specific bands as e.2. Composition Mg3Fei04 (lsd) Mg3Fei04 (A) Mg3Fei04 (b) Mg3Fei04 (n) Vo/atom 9. =* ^ The be found for the 4. place between b (ambient conditions) effects can and n (elevated where B0 pressure).031 168. 4.g.2 Data And Analysis Table 4. that in the lsd case the Fe-d electrons are unhybridized close to the Fermi-level.63 171.124 9.162 4. In this scenario at the high Fe 15 GPa.6 Mg7Fei08 (lsd) Mg7Fei08 (A) Mg7Fei08 (b) MgyFejOg (n) Mg31Fe1032 (lsd) Mg31Fe1032 (A) Mg31Fei032 (b) Mg31Fei032 (n) 3.095 4. In state.2 3. 4.

16 and 4. while at the lowest concentration (3. (g)). 4. From an energetical point of view it seems to be preferable not to apply SIC-corrections to the Fe-d electrons that lie on the the lsd • In the SIC-LSD calculations Fermi-level.5%) symmetry conserving relaxations of the Fe be observed.16 (j)). 4.16 narrower (more localized) Fe- (a) (compare Fig. type for these relaxations spin polarization though this relaxation is present up to 200 GPa in the no configuration: al¬ cluster configuration of of Fe atoms.16 (h)) where the Fe-d bands are unhybidized below and above the Fermi-level appear to be more favourable energetically than the state n with strong hybridization of the Fe-d electrons at high pressure (Fig.2. (a - b)/a < 10"10). The idea was to calculate the self- interaction corrections 88 . They both have the correction scheme 2eg. 4. In parallel the total energy of the ergy same ionic configuration was computed using the LSDA-ASA (Daresbury) code was and the PAW-GGA (VASP) calculations. This explains the remarkable similarity of the DOS in Fig. The relaxation an depend on the Fe concentration: In the GGA calculations at intermediate concentration ions can (12. 3t2g in the majority channel of the Fe-3d electrons.1%) the relaxations do not take place. The decrease of the Fe concentration introduces d states 4. whereas in the minority channel b corrects leg [x y) and A corrects none. relaxation takes maximal distance. Fig. although it place when Fe ions are in positions at the unpolarized calculations no significant relaxation was is allowed by symmetry. For observed. For the electrons the self-interaction en¬ removed according to scheme b. These symmetry elements are not affected by the relaxations described here nor is the on cubicity of the cell [a are = b = c. At low pressure the settings A and b are compet¬ itive.16 (g) and Fig. The iron-iron 10 % is distances the other hand strongly affected by the relaxation: the reduction of the Fe-Fe distance in the from a arrangement and the where the iron atoms The prerequirement tetrahedral cluster are are second nearest neighbors.4 Effects of Fe impurities in MgO possible for the HS-LS transi¬ polarized A-configuration to the unpoare For a concentration of 25% Fe two scenarios a tion: transition at 197 GPa from the (as predicted by the SIC-LSD calculations) or a transition from the polarized b configuration (DOS not shown) to lsd at 131 GPa. Fig. 4.7 Ionic relaxation Static ionic relaxations were different treatment of electronic turns out to investigated for different Fe concentrations and exchange-correlation energies. In both scenar¬ larized lsd ios the Fe-d electrons never hybrdize with other electrons but form separate bands. was The Jahn-Teller distortion tration investigated for a relatively high Fe concen¬ (25%) using a combination of SIC-LSDA and GGA for the treatment of the exchange-correlation energy.16 (i). configuration (no SIC corrections. 4. a The addition of 4 iron impurities in tetrahedral configuration reduces the number of point group symmetry elements of the 64 atomic supercell from 48 to 24.

The energy was by 25 meV.11) It is not sufficient to just compute the SIC corrected total energy £sic-lsd for configurations among other things the amount of atomic sphere overlap also contributes to the total energy.81% for the Jahn-Teller 89 .12) giving the energy of the system with Since there is SIC-corrections.4. It is based on the approach of learning the inverse Hessian matrix of the landscape during the run and features step size control. preserving the volume and the tetragonal symmetry.7 % and 0.02 %. 2001). these erroneous contributions from sphere overlap cancel out when corresponding energies are subtracted from each other. Unter the assumption that the cell would remain orthogonal the length of the cell parameters were optimized keeping the volume constant. (1994) two kinds of relaxation could be ex¬ pected: a uniform breathing of the oxygen atoms that surround the Fe ion and an tetragonal squeezing of the octahedron spanned by the same oxygen atoms.2 Data And Analysis A£sic = £sic-lsd - £lsd • (4. approach was applied to the 16 atom supercell containing 1 Fe atom. In the final 1 - configuration l-b/c for correction scheme b = following lowered ratios were found: fl/c = 0.6 meV. The distortions can be expressed in percentage were of lattice vector 3% for the a. applied to the 8 atomic sampling cell using the correction scheme A. The electronic DOS was not significantly changed: the Fermi surface Another crosses the bands resulting from Fe-3d orbitals and the DOS remains half-metallic. If the total energy with the same configurations in the LSDA approximation is computed. The tetragonal distortion of the energetically most favorable structure was 1 -0. The first distortion is caused by the difference in the ionic radii between Mg and Fe: If Fe substitutes for Mg it would repel the surrounding oxygen atoms. Following the ideas of Korotin et al. The resulting distortions for the correction scheme A breathing and -1.33 % [a being the tetragonal axis). The remaining term carries only the energy due to the SIC corrections. The second distortion is due to the Jahn-Teller effect. This term can be added to different ionic in the LMTO frame because the total energy derived in full potential calculations E = £pAW-GGA + AE'sic (4. In the 8 atomic sampling cell no internal free parameters exist but the cell parameters. we need to ap¬ technique which can operate with the limited information available from pure energy calculations. and lead to a lowering of the a/c Similar calculations were - = total energy of 4. no ply a minimization way to calculate forces in the LMTO-ASA. We applied the CMA-ES algorithm (Hansen and Ostermeier.

that the amplitude of the squeezing are is chosen positive. While 4 atoms oxygen atoms are affected only by the breathing. a. (2006a). Jahn-Teller distortion 1. 10The reduction due to the Jahn-Teller distortion 90 .8 The endmember FeO in the SIC-LSD frame.e.2. — 4. energy reduction 14. This state is stable over the whole differences antiferromagnetic [a] configuration.9 The resulting energy reduction the electronic structure is 13. + TT _ -"LSD ~ I ^PAW-GGA + WSIC-LSD I TjLS . t/LS TT _ \ -"LSD ) _ f/HS f/LS _ -"PAW-GGA -"PAW-GGA -L ~*~ /f/HS _ \n SIC-LSD \ f/LS "SIC-LSDJ (4 141 ' • This an procedure leads to an increase of the transition pressure of 26 GPa for iron concentration of 3.28 eV per Fe atom. 4.62 eV.16 eV. Note also. is 0. The schemes that resulted in combined to a magnetic moment magnetic [m] and an The are resulting enthalpy magnetic configuration (AAAA[m]) turns out to be the most fa¬ vorable when the enthalpy is considered.12. Therefore the cell pa¬ rameters determined earlier could be used. A N) were ap¬ plied system of 4 Fe and 4 oxygen atoms in the cubic arrangement. For the correction scheme b the results - similar: Breathing 3 %. The structure remains half-metallic.4 Effects of Fe impurities in MgO was distortion. b.10 It turns out.1% found in the GGA calculations to 91 GPa in this combined computation scheme. that hardly affected by no this distortion. The density of states of the SIC-LSD calculations shows visible deviation from the DOS of the undistorted structure. the breathing and the squeezing are not inde¬ pendent from each other. The enthalpies are calculated for the different spin phases separately TjHS TT ~ TjHS M r/LS _ - TjHS ^PAW-GGA . The A correction scheme in the 9Note that in this choice of the distortions. previously suggested because the enthalpy difference between the two phases increases more quickly with pressure in SIC-LSD used here more quickly than in the LDA+U calculations applied by Tsuchiya et al. As shown in section 4. can methodology be used to find the self-interaction corrected tran¬ sition pressure of the HS-LS transition.2. phases The total energy difference between the two (HS/LS) at 0 GPa increases (4 eV/ 64 atoms) and the spin collapse than in any of the two calculation schemes taken the transition will be smeared out over a smaller region than even appears to be sharper for itself i. Fermi surface A similar are In the correction scheme A the electrons at the not shifted. The number of configurations were is so high (of the (14+ 14+ l)4 ^ possible electronic 106) that it is impossi¬ a ble to compute all of them. + ^SIC-LSD ^LSD TT H t/LS ~ . when the oxygen atoms increase their distance to the central Fe ion. for two atoms the amplitude of the breathing and the Jahn-Teller distortion are added.8 %. The most x =1 and promising electronic configurations (lsd.7 the influence of atomic displacements and the cell relaxation on to the the electronic configuration order of - is only minor. given in Fig. n. -"PAW-GGA + r/LS ^SIC-LSD _ -"LSD • From these expressions the SIC-corrected enthalpy difference t/HS WSIC-LSD is computed: \TT AM - t/HS «PAW_GGA .

bb[m]. has to be restrictive because the number of the quadratically schemes with and the combinations grows with the number of correction schemes chosen. aA[m].9 Two Fe Two Fe impurities were in the 8 atoms supercell. Ab[m].5 impurities introduced in the Mg and 4 O ions in order to supercell originally containing 4 for check charge disproportionation between Fe ions and collective figuration (a.194 NNNN[m]: .b. bN[m]. aa[a]. NN[a]. A. AA[m].12: Enthalpies a of the different electronic tion scheme is combination of the individual corrections schemes for the Fe-ions and index for the the A scheme was antiparallel to magnetic [m] or antiferromagnetic [a] configuration. NN[m]. B' = Vo =9. (NNNN[m]/bbbb[p]. For a reference applied to all Fe ions. The correc¬ Figure an 4. N) for single Fe impurities were combined for the Note that the choice of correction schemes calculation of the total energy.A. AA[a]. aN[m]. Ab[a]. magnetic effects.18 The = change 4. Pressure was nn. ab[m]. b. B' 4. bN[a].N) in addition the magnetic [m] antiferromagnetic [a] has to be checked. ab [a].454 GPa.964 À3/atom. The most promising lowest energy con¬ lsd. through a scaling of the lattice constant in the This typically corresponds to pressures of 0 to A with a The magnetic configuration of scheme resulting spin a moment of 8 ßB turns out to be the energetically most favored up to pressure of 296 GPa where all the electrons become delocalized (lsd). nN. AN[a].732 GPa. 230 GPa. x =0. aN[a]. pressure range and shows at 202 GPa a half metallic density of states (not shown).2. AN[m]. while magnetic moments of 2 Fe-ions were set the one of the other 2 Fe-ions (antiferromagnetic setting [a]).2 Data And Analysis u: AAAALaJ AAAA[m] 50 100 150 200 : P [GPa] configurations for FeO. Following 25 schemes were used: aa[m]. The electronic phase tran- 91 . The resulting schemes are with the symbol of the schemes of the individual atoms optionally fol¬ termed lowed by the index for the geometry.4. B0 152. an. For correction possible expected spin polarization (a. n. B0 = 162.8136). in the elastic = minor (bbbb[p]: V0 À3/atom. =11. bn An and introduced range between 100% to 86%. If the one a correction scheme b is considered to be the correct occurs phase transition) properties is 4. bb[a]. aA[a]. lsd.

It crosses the n configuration (nn) at 83 GPa.Fe0 s)0.16 (i)).5%) SIC-LSD calculations show. For a applied to all Fe ions in the antiferromagnetic arragement AA[a]. sition goes 4. 4. At 207 GPa the lsd even lies lower in enthalpy than the n.4 Effects of Fe impurities in MgO 50 100 150 200 250 300 P [GPa] configurations for Figure 4.16 (g) In the GGA calculations at low pressure (Fig. At low pressure (12. The main difference between the position of the localized Fe-3d elec¬ the first case they appear well separated and 92 . The bulk modulus would show a discontinuity of 88 GPa and the ground state volume a collapse of -14 %. where any Fe3+ ion is not allowed to appear in the phase dia¬ gram. SIC-LSDA treatment of the Fe-3d electrons in Mgi_xFexO A crosscheck between the resulting DOS from different treatment of the ex¬ nature of the electronic iron concentration change-correlation energy (GGA or SIC-LSDA) might help bonding in Mgi_xFexO. In a scenario.13: Enthalpies a of the different electronic (Mg0 s.3 Discussion 4. the magnetic b configurations is the energetically most favored (bb[m]). that localized — to understand the at it relatively low is energetically — favorable not to correct for the self-interaction energy of the localized but apparently weakly and Fig. 4.3. The correction scheme is ions and an combination of the individual corrections schemes for the Fe- index for the reference the A scheme was magnetic [m] or antiferromagnetic [a] configuration. As already seen for other Fe concentration the n and the lsd schemes yield potentially good high pressure configurations.4 (a)) the 2 eV localized electrons in the Fermi-gap be found as well as ones in the region above the Fermi-level can SIC-LSD and the GGA treatment is the trons below the Fermi-level: in again.1 GGA vs. along with an increase of the bulk modulus B0 by 53 GPa and a decrease of the ground state volume by 14 %. Fe-3d electrons at the the Fermi-gap (Fig. 4.

more important than the corrections for the electronic self-interaction energies. where iron impurities high pressure treated without any corrections for possible strong correlations of the electrons. that the GGA at high pressures could treat correctly the exchange - comparison of the DOS between SIC-LSD results and GGA results (Fig. (4. 4. These alone.15) a This results from least squares fit to the experimental data. Therefore the GGA treatment of the tant. relaxation effects cannot be treated in the frame of LMTO-ASA 4. that the LSD treatment — without any SIC corrections is the energetically most favorable. that the Fe-3d electrons being semi-localized be treated best in the scheme of the At dynamical mean-field might theory (DMFT). out that the SIC-correction respectively. which the GGA calculations is might a good approximation a were be hint that the total to the real total energy of the structure. This already indicates. — Furthermore it — cannot be ruled out. applied Si-correction schemes and the Fedepend strongly the arrangement of the Fe on The extrapolation of the experimental a transition pressures imply transition pressure of 30 GPa at lowest Fe concentration (eqn.. This could also endorse other calculations (Li at 2005).3 Discussion unhybridized are 3 eV below the valence band.g. I checked on for low concentrations the dependence of the transition pressure the iron concentration.15) would investigated (3. 93 . of these electrons at the bottom of the valence band.. that structural relaxation (e. (2005) find a linear dependence of the Pa.16 hybridization (j). and fully occupied.100 GPa) could indicate. atoms.4. The disagreement of the SIC-LSD results (hardly any dependence of the HS-LS transition pressure on composition and relatively high transition pres¬ sures (. while in the second case situated between the Fermi-level and the valence band.4 (b)) also corrrelation energy for the Mgx_xFexO structures. Jahn-Teller distortion. In both they are cases they en¬ unhybridized ergy resulting from et al. theoretical HS-LS transition pressures HS-LS transition pressure Speziale et al. ) and the relaxation of the atomic sphere radii might be impor¬ . exchange-correlation energy might be a good treatment for Fe-3d states in Mg!_xFexO. — high pressure SIC-LSD calculations indicate. Good agreement with these results is found from the GGA calculations.in Mgi_xFexO on the amount of impurities x: pŒ = 28 + 0.63* .1%). 4. 4. 4. applied From to the an Fe-3d electrons of intermediate localization below the Fermi-level creates incorrect see Fig.3. The shows that the valence bands resulting from the different treatments are well treatments appear comparable (regions just below and an energetic point of view it turns between -10 eV and -4 eV) while the Fe-3d states in both above the Fermi-level. at low as well as at high pres¬ sures. The calculated transition pressures concentration.16 (h) and Fig.2 Experimental vs..

18* (4. high pressure). In the second scenario (b-n) the A is considered to be introduced artificially. phase diagrams for various Fe concentrations: A-lsd and b-n. configuration where structural relaxations were enabled at any pressure. In the first scenario the A configuration is as¬ sumed at low pressures and no Si-corrections are applied to electrons at high pressures.. lozenges () GGAPAW calculations (low concentrations). circle (o) X-ray diffraction (Ono et al. 83 GPa (12.1% Fe)...5 % Fe). scenario A-lsd (electronic configuration Si-corrections at A at low pressures. 2006b).FeJO # Q_ CD 150 Û- 100 .14: Experimental and theoretical transition pressures. SIC-LSD for xFe < 25% does not monotonie dependence of the HS-LS transition pressure upon Fe concentration as it is found by Speziale et al. The low¬ est lying configurations in the corresponding pressure regions are b (low pres¬ sure) and n (high pressure).. 192 GPa (25% Fe) 296 are (3.g. 2005). not corrections (o) SIC-LSD calculations scenario b-n (electronic n at high pressure). 2007).16) (Jahn-Teller distor¬ is the iron concentration. Two scenarios unexpectedly high transition HS-LS pressures. stars (•) LDA+U calculations (Tsuchiya et al. A least squares fit to the calculated transition pressures gives Pc(x) where x = 19 + 2. Speziale 2005).'::^i 0 20 40 60 80 100 50 0 XFe[%] Figure 4.. arrow (|) Mössbauer spectroscopy (Pasternak et al.5% Fe). triangles (a) Mössbauer spectroscopy (Speziale et al. circles configuration b at low pressures.4 Effects of Fe impurities JUU in MgO ß 250 / 200 __ CO y (Mg^. (2005).. 1997).. 131 GPa (25% Fe). Structural relaxation tion) could play an important role. This allows to reestablish a phase diagram that is in better agreement with the experimental findings. pressures eg states In the scenario A-lsd the transition (50% Fe) whereas 86 GPa and 202 GPa in scenario b-n the critical pressures lie significantly give the lower: (3. However. when high Fe concentrations xFe > 94 . which are: Fe appears can SIC-LSD calculations show be identified present in all in the Fe2+ state in the whole pressure range and the low pressure structure pressure structure has 6 has one t2g and 5 eg states while the et al.1% Fe). 143 GPa 132 GPa (12. 83 GPa (50% Fe) (100% Fe). Squares () SIC-LSD calculations. Energetically these configurations are the most preferable. high occupied (see e.

a.4 GPa in the calculation). — hybridization O. served magnetic moment This ionic relaxation could also on (p.2. where the configurations schemes A.7 64 atoms. f = state with ß 2ßB is found. the D correction an is true for the SIC-LSD calculations where e. N. above 63. This is scheme results in electronic states of 2 ßB above 70 GPa for a pressure. h and n Fe concen¬ are more resulting from advantageous energet¬ lie at least 4 eV above ically. They on rise to considerable reduction of the total energy. i. 95 . could supercell containing play an important role for the trations transition pressure. clustering of Fe-impurities arrangments is are 4. In the Mg3iFei032.5 %) the Fe ions build clusters.5% in the spin polarized = calculations. b.4 GPa). The observed relaxation of iron ions for clusters of 4 atoms in the as they are described in section 4. 4.4 GPa. stable at different pres¬ while at high pressures Fe prefer to be separate from each other. The same GGA regions where they are found (e. Intermediate spin states e.3 Probable Fig.8 indicates.e. Exten¬ sive heating of these clusters during the assembly would prevent the formation of these clusters because temperature would prefer a random distribution of the ions on the crystal positions.g. K. other spin states exist having lower enthalpies. I.3 Discussion 50% are included in the analysis clear trends are visible. At relatively high Fe concentrations [x > 12.g. Therefore one could expect that experimental setup. where the sample is assembled at low pressure [P < 50 GPa). turn out to be metastable — the energy minimization procedure not beeing able to escape local minima. which the other hand stabilizes the the Fe ions. C. tration of 12. ß = 3ßB on one 1 Fe impurity. The most preferable configurations have either no magnetization or ß 4ßB in the = pressure range where they have a probability to actually appear. But the enthalpies the best structures in the whole pressure range between 0 and 200 GPa. B. At intermediate heating clusters would mix with Fe ions randomly distributed. c. H. The HS-LS transition pressure could then be smeared out over the whole region between the upper and the lower atoms an in — value. because at the conditions of the assembling the clustering is preferred. that different Fe At low pressures Fe sures. the transition pressure is shifted more to the higher value (63. e. which stabilize the be it through pressure local magnetic moments. Energetically and relaxation is dominated by the valence electrons of where they mutually optimize their positions and orbitals.3. D.4.3 GPa and 63. E. 4ßB on the ob¬ explain experimentally each Fe atom) dependence of the — HS-LS transition pressure: at low concentrations Mg and because the of their low amount the Fe states play a mi¬ their This destabilizes the magnetic role and to nor are adapted surrounding. These relaxations arise at concen¬ higher apparently give than or equal a to 12. G.g. J. d. between 30. moment on Fe and the HS-LS transition sets in at relatively low pressures.5%. clustering preferred. A large amount of energy in thermal order to compete with sta¬ increase or through is needed energy — — bilization energy of these magnetic clusters. and g For the a same Fe-concentration in the scheme F.

4 Is there LS iron in the Earth's lower mantle? On the basis of the Clapeyron slopes given in phase would dominate in the Earth's mantle. 4. For low concentration (Hofmeister. (2006a) proposed sonable approximation for the Gibbs free energy with includes the contribution magnetic Smag as = kBXFe(l - n) \n[m(2S + 1)] (4. Tsuchiya et al. S the iron spin quantum number [S for HS. that the transi¬ configurations resulting from the correction schemes A (HS) and lsd (LS). m LS).17) well as configurational contributions Sconf = -kBXFe[nlnn + (1 - n)ln(l - »)] (4.4 Effects of Fe impurities 3500 in MgO 3000 2500 < 25% LS S h- 2000 1500 1000 500 >75% LS 0 0 50 100 150 200 P [GPa] Figure 4. S = 2 0 for LS). n is the = low-spin 3 for the iron fraction and m the electronic = configuration degeneracy (m 1 for t2g orbitals.10 derived from static tion takes enthalpy place between the phase of Mg87 5%Fei2 s%0 given Fig. the Clapey¬ Under the assumption ron slope is too steep to cross the mantle geotherm.18) = where kB is the Boltzmann constant. of spin transition pressure of 20 GPa and a minimal Clapeyron slope of 0.15: Field of coexistence between the HS and LS differences electronic in 4. It is interesting to extrapolate these results from static calculations to temper¬ a rea¬ atures of the Earth's lower mantle.3. assuming.05 GPa/K the spin transition phase boundary meets the mantle geotherm a at 140 GPa and 2500 K. The minimization of the Gibbs free energy gives 96 . 2006) the high spin [x 1/32) = where the spin transition pressure is between 15 and 25 GPa. As a first approximation contributions due to changes in the vibrational spectra as well as due to differences in the Fe/Mg configuration entropy for minority HS different spin states with respect to n are neglected. well at the bottom of the mantle.

. see also Fig. 2006. 2003. layer a compilation of published data for (Mg. although the material is known to be an insula¬ tor. Fig 4.5 Densities of (Mg.16 (h).. assumed to scale linearly with the iron concentration as well as with the pressure. possible layering at the of iron rich CMB Deschamps and Trampert. Oganov and Ono. 4. 97 . (2006).4. In the HS phase the absorption place for these electrons located close to the Fermi surface. see e. Fig. 2005) was combined with pressure/volume date from the present calculations to compare densities of different minerals at Earth lower mantle conditions. Ono and Oganov. 2003) pro¬ magnesiowüstite at the bottom of the Earth's pose a heavy layer In order to check the possibility of the existence of such a lower mantle. 4. The The thermal level in the LS absorption of Fe could result from the excitation of electrons from the Fe-3d band below the Fermi-level to the Fe-3d band above the Fermi- phase.Fe)Si03 post-perovskite. which corresponds to a wavelength of 490 nm.3 Discussion l + m(2S + l)exppfgf2} = where À#LS hsCP) the Hvs(P) - HHS(P) denotes the difference per atom between enthalpies of the two spin states at 0 K.Fe)Si03 post-perovskite (Mao et al..15 gives the field of on coex¬ istence between the HS and the LS state of Fe based the static enthalpy = 1/2) phase boundary [n is remarkably steep predicting a gradual spin collapse at a pressure of around 152 GPa. The excitation energy does not shift with pressure and overlaps only weakly with the radiation spectrum of the black-body radiation at a typical mantle temperature of 2200 K. efficient the be for would small a quite ever. differences derived from SIC-LSD calculations. 2004. This scenario would explain the findings of Goncharov et al. In the SIC-LSD calculation Mgx_xFexO (for the A correction scheme providing the low¬ est enthalpy at low pressures and at ambient conditions. absorption of splitting allowing the HS phase. In the LS phase the thermal absorption would be weak: the excitation energy is 2. 4. that Mgi_xFexO turned transparent to infrared radiation at pressures corresponding to the would take HS-LS transition of this material.3. Table 4. (Mg.Fe)Si03 perovskite and (Mg. In the DMFT calculations the bands crossing the Fermi surface could be split How¬ into an upper and a lower band removing the half-metallic behavior. 1994) and (Mg.5 eV. Pressure/volume date at different concentrations were used to determine these dependencies in a least square fitting procedure.16 (g)) appears to be a half-metal. It remains to be seen.g. which has its maximal intensity at 6500 nm.Fe)Si03 perovskite (Wang et al.Fe)0. if DMFT calculations could solve this problem. In the Earth's the pressure is limited to 136 GPa and according to these calculations would be free of LS Fe. The vol¬ ume was Different authors (Badro et al.5 shows the resulting densities.

which is reasonable approximation for the Earth's mantle region under discussion.6041 appears to be heavier than the other two a phases iron concentration of 10%. 2005) and (Mg.3 and 2. This phase of FeO could have strong seismic effects and could be responsible for a quite efficient absorption of infrared radiation from the Earth's core due to it metallicity above 70 GPa. MgSi03 post-perovskite and pure FeO) would yield a wüstite phase.4785 5.Fe)Si03 post-perovskite (Mg.8096 6.Fe)Si03 postperovskite (Mao et al. Iron concen¬ tration assumed x=10%. 100 GPa 150 GPa 5. disproportionates strongly between the phases. 1994).Fe)Si03 perovskite (Mg. This does not enough to cause a density difference is approxi¬ phase separation.Fe)Si03 perovskite (Wang et al.Fe)0 magnesiowüstite Magnesiowüstite always at a 5. seem The mately 4%. can The picture change when Fe 98 .3980 5.4 Effects of Fe impurities in MgO Table 4.0793 (Mg..5: Densities of (Mg. Complete dissociation (MgSi03 perovskite. Ono and Oganov.7969 5. (Mg. 2006.Fe)O magnesiowüstite at a pressure of 100 GPa and 150 GPa in g/cm3. which is between 2. Oganov and Ono.5 times heavier than the other phases.. 2004.

106 GPa <1) 50 1 11 J 1 1 total DOS MAL Y1Y ' 1 1 1 " 1 25 ^ . 102 GPa total DOS (i) Mg7Fei08. total DOS (e) Mg3Fei04. lsd. 7 GPa (f) Mg3Fei04. Figure 4. setting b. Ö (c) Mg3Fei04. 99 . lsd.3 Discussion >—\jjUT" total DOS total DOS E EF [eV] E EF [eV] (a) Mg3Fei04. . The meaning of the codes of the correction schemes A-N and a-n is given on page 83. setting A. 7 GPa (d) Mg3Fei04. 2 GPa (h) Mg7Fei08. setting n.a-^vm-y^ ^-^yw^ 0 <1) j\y ] total DOS > ^ C^ y - ^/ 25 M < 1 r 0 50 i i . 183 GPa (g) Mg7Fei08. lsd. H 75 . setting A.16: localized Fe-d orbitals. setting A. (d) shows the typical situation when no sic-corrections are applied: The band gap is tiny or even disappears. 1 GPa 2 75 (b) Mg3Fei04. 124 GPa Spin Density of states (DOS) for different SIC-correction schemes on the Comparison between the total DOS (black) and the DOS arising from states on Fe. 2 GPa (j) Mg7Fei08.4. setting n. 197 GPa "\j>f total DOS . setting n.

4 Effects of Fe impurities in MgO 100 .

density (SIC-LSD) calculations have success¬ fully described the collapse of the magnetic moment of Fe impurities in MgO. Indeed for high Fe concentrations [xFe > 25 %). which could be reproduced. crystallography are expected although they would have a high impact. The with good agreement experimental findings. Another geophysical implications of my work is that the material can be ruled out as an ionic conductor at the conditions investigated: hopping processes are not likely. my calculations in — — critical pressures derived from PAW-GGA calculations are the first conducted. The Jahn-Teller distortion turned out to give a considerable contribution to the total energy. In a different series of calculation the experimentally found lin¬ ear dependence of the transition pressure upon Fe concentration could be reproduced quantitatively and it could be shown that locally varying Fe con¬ figurations can explain the experimentally found broad transition region. MgSi03 perovskite and postper- 101 . Another good agreement concerns the experimen¬ tally found hardening of the material across the transition. Well founded lated electrons. Its further application to problems at the boundary between geophysics. The SIC-LSD formalism turns out to be compelling for high Fe impurity con¬ centrations.Fe)O: high pressure physics and the theory of strongly corre¬ were a In the present thesis modern ab of Earth's initio simulation techniques minerals. Geophysically important parameters such as the bulk modulus. These are important results for the geophysical model of the Earth. whereas the SIC-LSD results always predict higher critical pressures than the experimental ones. solid state physics and high pressure to be fruitful. trends are and es¬ the of the critical well Fe concentrations dependence pecially pressure upon reproduced. as CaSi03 perovskite is considered to be the third most abundant mineral in that the Earth's lower mantle. The statisti¬ cal analysis of quantities obtained from molecular dynamics simulations was refined. The ab initio molecular dynamics (MD) simulations provided the Grüneisen parameter and the thermal phase boundaries between the particular high and low temperature phases of CaSi03 perovskite. its first pressure derivative and the zero Self-interaction corrected spin pressure volume are were derived. Among these the lower mantle minerals things are the partitioning of Fe. However. Two domains were combined to theoretically study the magnetic spin collapse in (Mg. A number of issues remain open. The standard DFT (PAW-GGA) method was combined with the SIC-LSD formalism to allow for structural relaxations. The thesis shows the power of ab initio methods in the field of high pressure crystallography. K and U between (magnesiowüstite.5 Conclusions and Outlook applied to concepts mantle-forming variety major were presented to solve the long standing controversy between experimental findings and theory predictions in the case of CaSi03 perovskite.

5 Conclusions and Outlook perovskite) and liquid Fe-based alloys and effects of these impurities on the thermal phase boundaries under high pressure.and /-electron systems in DFT. which would partly require new computational techniques. ovskite and CaSi03 102 . a convenient calculation of the free en¬ ergy in crystals and reliable prediction of high pressure crystal structures. It would be useful to investigate more thoroughly these subjects. such as the straightforward treatment of d.

g. . eki + 0(etJ • e« • emn • epq) k. 2000. (A.3} and j e {1.. contributions proportional to en vanish since the structure is assumed to be at the energy minimum.1) The constant contribution [/0o can always be set to 0.A Elastic constants from the energy surface The internal energy depending on the strains el} and i up to second order is a long expression e {1. e\2. The coefficients cljU be accessed through second derivatives d2U cnn d2en = Cii22 t—ä— 06110622 (A-Z> d2U C1223 Ô612Ô623 indices are index Using Voigt notation where pairs of Cartesian a according to the scheme ij a replaced by a single = 11 1 22 2 33 3 32 or 23 31 or 13 21 or 12 = 4 5 6 et al.2) become 934) 103 .2. [A'Ö) and numerical the derivatives in expressions for derivatives (Bronstein eqn. É31) = 1/2 2_j cijkieij 1. while linear contri¬ butions e. p. 632.2. This expression is correct to order 3 in the strains. j.. 1 h = 1/2 + + + + + + + jeu 6n + + C2222 % + C3333 % + C1212(^2 C\\\2 C2212 4l) + c2323(^23 + 4>) + c313l(4l ^3l) ) + + + + 4s) 611(632 ^22(^32 633(632 + + + C\\226\\ 622 + C2233É22 633 + C33 11^33 £ll 6\\{6\2 ^22(^12 e"33(^12 621) ) + + C1113 611(613 + C1132 C2232 623) ^23) 623) + ^21 + C2213 £22 (^13 + £31 C3312 £21 ) + C3313 633(613 + 631) É3l) £32) C3332 C1213(^12 C1223(^12 ^13 £l3 + £l2 £31 + £21 £l3 + £21 £23 + £l2 £"32 + £21 £23 + £21 + 23(^13 £23 + £23 632 + £31 £23 + £31 £32)] + 0(eij ' £« ' 6mn * £p?) • (A. This is denoted can by the Landau symbol O.3} U(en. • .

104 . e6 0) where all the strains but e2 and e4 vanish.A Elastic constants from the energy surface d2U cim= d2U -^ol6i = t^= dl6n 1 —[Ufa)-2U(0) \ei\ 1 + U(-e1)] d2U cii22= T—«—= d2U ^~^~ 061062 = TTTi-T^6!'^4" ^(-^1. -£4) - £/(<%. 64). e4) + £/(-<%. -e*) - t/(-6s.62.g.e5 = vanishing = strains 0.-62) -U(-e1. e4)] (A. I write Ufa.4) For are simplifying the notation in the argument 0.e2)] 06\\d622 4|ei||e2| 1 d2U Ci223 = 2-—-— d2U = = 06120623 Ö66Ö64 4|e4| |e6| [£/(<%. 0.63 neglected e.-^2) -f/(ei. instead of Ufa = = of U all the e4.

32 exist: À ex¬ 111 112 122 113 123 133 114 124 115 125 135 145 225 235 245 335 345 445 134 144 222 223 233 224 234 244 (B-3) 333 334 344 444 Finally the 53 configurations of 5 atoms are 105 . For 4 impurities already 30 only 1 site in the distinct configurations distance of 9.B Possible configuration of Fe Table 4. and 5 possible configurations for 2 impurities: 01 02 03 04 05 (B.l) following I configurations are: In the will neglect the leading 0. To find all the non-equivalent configurations I fix the first atoms and place the remaining atoms on the unoccupied sites.3 gives the possible sites for Fe in a 64 atoms super cell. This gives 1 possibility for 1 Fe. For 3 impurities the possible 14 11 12 22 13 23 33 14 24 15 25 35 45 (aZ) 34 44 The configuration 55 is futile because ists.

B Possible conßguration of Fe 1111 1112 1113 1114 1115 122 222 1123 1223 1124 1224 1125 1225 1133 1233 1333 1134 1234 1334 1135 1235 1335 1144 1244 1145 1245 1345 1445 1344 1444 2223 2224 2225 2223 2333 2234 2334 2235 2335 2244 2245 2345 2445 2344 2444 3333 3334 3335 3344 3444 3345 3445 3445 106 .

critical questions: A. Garcia: cubic to orthorhombic transition not Fe at 1500 K not probable Temmerman: magnetism of probable 107 .

B Possible conßguration of Fe 108 .

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Daniel grateful for these Daniel Y. TH-27033. Their family and friends. and I H. Racic. support for my research was provided by ETH Zurich Research fund Grant No. my parents. M. Gabriella and my Heer- Adams and Alfred Heer-Adams. am grateful colleagues Daniel Y. munications of the results of the static Jung and Colin Glass for the com¬ optimizations of CaSi03 perovskite and asa the implementation of the VASPpaw+SICLMto am total energy minimization. Cornio- I have had conversations with my am colleagues about physics. Financial Numerous success was people have encouraged out of me in the time of my PhD. Walter Temmerman and Dr. Jung. Without their support the simulations could Mario Valle STM4) which were extremely useful to provided the develop visualization tools new ideas and check their lidity. The computer code by them. also when ley Carin and sight: Andreas Wehringer. help. Sutter-Widmer. I am also indebted to Prof. Alberto Garcia Landau strongly provided for encouragement in theory and ferroelasticity. 123 . to my discussions: Kai Very special thanks go Briner. I want to my interests in I especially group theory. who hosted correlated electron me for one month and initiated SIC-LSD ASA me into the field of was systems. Hassenteufel. Walter Steurer for outstanding research conditions. Computer facilities were provided by the Swiss National Supercomputing Centre (CSCS) and ETH Zurich. my brother Michael. are never partner Maja support and encouragement ending. Artem Oganov throughout R. excellent computer facilities and opportunities my PhD studies and Prof. for encouragement. stimulating Paul and Berta Truttmann.Acknowledgements I would like to thank my PhD thesis advisors for their support: Prof. Veronika Wyder. Sigut and N. mathematics and computations. G. Stringfellow for computational (STM3 and va¬ assistance and technical not have been done. I grateful to T. to my thank Dr. Dzidka Szotek.

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Budapest specifications on Modern solid-state Physics (theory) 1998-2003 Study in Physics. "Laboratorium für Festkörperphysik. R. Artem R. Zug. 2003 Physics. Oganov at the - "Laboratorium für Kristallographie. ETH Zürich". Swiss Federal Institue of Technology (ETH) Zürich. ETH MSc [Diploma] in Zürich" 2001-2002 Affiliated with study at Eötvös Lörand University (ELTE). Switzerland 2004-2007 Accomplishment vsion of Prof. Diploma topic: "Electronic structure of 2D solids with competing periodic Potentials" under the supervision of Prof. 1991-1998 Grammar school at Kantonsschule equivalent of A-levels. Monnier. Swiss Federal Institue of Technology (ETH) Zürich. of the present PhD thesis under the super W.Curriculum Vitae Donat Jozsef ADAMS Born March 19th 1977 in Baden (AG). Matura typus specification: latin) C (Swiss 1984-1991 Primary school in Baar (ZG) 125 . Steurer and Prof.