Leibniz-Institut fr Festkrper- und Werkstoforschung Dresden Institut fr Theoretische Festkrperphysik

Spin Density Wave in Chromium

Diplomarbeit zur Erlangung des akademischen Grades Diplom-Physiker

vorgelegt von

Mathias Bayer
geboren am 28.02.1981 in Bblingen

Institut fr Theoretische Physik Fachrichtung Physik Fakultt fr Mathematik und Naturwissenschaften der Technischen Universitt Dresden 2008

1. Gutachter: Prof. Dr. Helmut Eschrig 2. Gutachter: PD Dr. Peter Zahn Eingereicht am 20. Mrz 2008

Kurzfassung
Der magnetische Grundzustand von Chrom zeigt eine inkommensurable Spindichtewelle (SDW) mit einer Periode von etwa 21 Doppellagen. Krzliche Berechnungen der elektronischen Struktur fanden einen antiferromagnetischen Grundzustand bei der experimentellen Gitterkonstante. In dieser Arbeit wiederholen wir die Berechnungen mithilfe des full-potential local-orbital Codes FPLO in der LSDA Nherung, welcher uns eine gute Genauigkeit in der Gesamtenergie ermglicht. Wir konnten Probleme, die auf ungengende Dichte des

k -Netzes zurckzufhren sind,

ausschlieen. Weiterhin haben wir

die Eekte einer an die SDW gekoppelten Verzerrungswelle (SW) studiert, und konnten keinen Einuss auf die Gesamtenergie entdecken. Die Ergebnisse werden mit Experimenten und theoretischen Daten aus der Literatur verglichen.

Abstract
The magnetic ground state of chromium displays an incommensurate spin density wave with a period of about 21 atomic double layers. Recent electronic structure calculations for Cr found an antiferromagnetic ground state at the experimental lattice constant. We have used the full-potential localorbital code FPLO, which has allowed us a high accuracy of the total energy in LSDA. We have been able to rule out the inuence of insucient

point

sampling. Further, a lattice distortion has been applied to simulate the effects of the concomitant strain wave (SW). We have found no inuence of the SW onto the total energy. The results are compared with experimental and theoretical data in the literature.

Contents
1 Introduction and Motivation 2 Theory
2.1 2.2 Density Functional Theory . . . . . . . . . . . . . . . . . . . . Spin Density Waves . . . . . . . . . . . . . . . . . . . . . . . .

3 5
5 9

3 Literature
3.1 Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.1 3.1.2 3.1.3 3.2 3.3 SDW with higher harmonics . . . . . . . . . . . . . . . CDW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . SW . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

13
13 16 16 16 17 18

Theoretical descriptions

Band structure calculations

4 Calculations
4.1 Technical details 4.1.1 4.1.2 4.2 4.2.1 4.2.2 . . . . . . . . . . . . . . . . . . . . . . . . . Dependence on

21
21 22 24 26 26 31

k -point

number

. . . . . . . . . . . . .

Scalar vs full relativistic version . . . . . . . . . . . . . NM and AFM Cr . . . . . . . . . . . . . . . . . . . . . SDW . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Results and Discussion . . . . . . . . . . . . . . . . . . . . . .

5 Summary and Outlook

37

Chapter 1 Introduction and Motivation

Density functional theory (DFT) has been used on a variety of metals and compounds to successfully describe their ground state properties. This work is focused on the transition metal chromium. Cr is the prime example of an itinerant antiferromagnet, its incommensurate spin density wave (SDW) is a truly many-body eect. The origin of the SDW is commonly attributed to the nesting properties of the Fermi surface, which determines the wave vector

of the SDW.

Bcc Cr and fcc Fe seem to be the only

3d transition metals for which high

precision DFT calculations predict the wrong bulk magnetic ground state. This is in contrast to earlier band structure studies that have managed to describe the Fermi surface of Cr including the nesting feature. This work pursues three issues where there may have been shortcomings in the past works and which might help solving the puzzle. One item is to get a really accurate resolution of the Fermi surface. By the help of the processing power of our computer cluster we were able to reach a high resolution in the Brillouin zone integrations which has not been reached in this eld yet. We have analysed if Fermi surface nesting performs. The second point is the consideration of a lattice distortion that occurs in the real metal and is potentially responsible for the stability of the SDW. Such strain waves (SW) have been examined within a large range of amplitudes around the experimental value. The last point examines the validity of neglecting the inuence of spinorbit coupling. After a presentation of the basics of density functional theory, this thesis gives a short overview about the literature status of the SDW in Cr, both theoretical and experimental, followed by our main results. Finally, the work is summarised and an outlook is given.

Chapter 2 Theory
Density functional theory is nowadays a crucial method for the study of electronic structure. We give a short introduction into the fundamentals serving us as a working basis. Details about density functional theory can be found superiorly reected in the literature [1], [2]. Subsequently, the origin of the spin density wave is discussed, its explanation is embedded into the picture proposed by Peierls. We close the chapter by a short remark about the generalised Stoner condition, being a test for instability against evolution of antiferromagnetic (AFM) order.

2.1

Density Functional Theory

An ideal metal is a crystal with atoms around their equilibrium positions and their electrons surrounding them itinerantly. They inuence each other via Coulomb interactions. We consider the non-relativistic Coulomb Hamiltonian for a xed number of atoms together with their

Na

with masses

Ne

electrons, in natural units :

and charges

Z ,

H = Ha + He
Na

Ha =
Ne

1 + 2M 2
2 i Ne

Na

= Na

Z Z |R R | Z 1 + |ri R | 2
Ne

He =
i
The Hamiltonian

i=j

1 . |ri rj |

(2.1)

He

is expressed through the operators of the kinetic

1 h

= m = |e| = 1,

energy unit is 1 a.u. = 1 Hartree

6
energy tion

CHAPTER 2. THEORY
T,
the potential of the external eld

V,

and the two-particle interac(2.2)

W: He = T + V + W .

The external eld consists of the part created by the nuclei from (2.1), in

addition we allow for an external magnetic eld acting on spin only, with V = Ne i=1 v(xi ). We have combined electronic spin and real space coordinates into xi = (ri , si ), with +1/2 3 dx i d ri . (2.3)
si =1/2
The rst important approximation is the neglect of the inuence of ionic motion onto electron energy levels. We let the total ground state energy, and the electronic wave function, parametrically depend on the nuclear positions

R .

Electrons are light compared with the nuclei, so they move more rapidly

and can thus follow the motions of the nuclei quite unhesitatingly. We can decouple the full Schrdinger equation from the nuclear motion and assume that electrons are always in the ground state with respect to the motion of the positive ions. This is called the This brings us to

adiabatic approximation

[1].

He (; R) = (; R)E(R) , x x
where we have employed the short notation

(2.4) and

x = {xi }, i = 1 . . . Ne

R = {R }, = 1 . . . Na .

The Hamiltonian (2.1) is not spin-dependent, but

we have to full the Pauli principle when constructing the wave function mension of the order of the Avogadro constant. dedicated to greatly simplify the problem.

Unfortunately, the Schrdinger equation for our problem (2.4) has a diThe following steps are

Due to the large number of particles, for macroscopic systems, our Hamiltonian produces energy levels having tiny distances no experiment could ever resolve. One accessible quantity of interest is the ground state energy as a reference, together with state density

0 as the ground state wave function and the ground

n0 (x) =

(x, x2 . . . xNe )0 (x, x2 . . . xNe )dx2 . . . dxNe . 0

(2.5)

The essential insight is to make a change from basic variable. of information. a functional of

the ground state properties and introduce the density

(x1 . . . xNe )-dependence of n = n(x) as a new

Hohenberg and Kohn [3] showed that this entails no loss In general, we can write the energy and wave function as

n,

where

is a single particle density, as in (2.5).

This

2.1 Density Functional Theory

functional

7
n0 ,
and

E[n, v]

possesses a minimum at the ground state density

is equal to the ground state energy

E0 [v]

at this density. In order to nd the

ground state energy, we have to apply a variational principle. We follow the way given by Levy [4] and Lieb [5], the constrained search method. We x a trial density

n,

and vary over the class of wave functions

that trial density. In a second step, we vary over the

n , which densities n,

yield

E0 [v] = min He

(2.6) dx nv dx n

= min FHK [n] +

n

= Ne

(2.7)

has to full the criterion of being a normalised fermionic wave func-

n. The unknown ingredient is the Hohenberg-Kohn functional FHK [n], which is independent of the external potential V , and is thus a univertion of density sal functional, valid for any many-electron system. This constrained search functional introduced by Levy has shortcomings and was replaced by Lieb by a more general functional based on Legendre transforms. Since both lead to the same form of the Kohn-Sham equation and have to be modelled anyhow, we do not dive into these subtleties.

FHK [n] = min

n

def

n T + W n | n n

(2.8)

As we are allowed to consider an arbitrary interaction cular set

W , we can in parti-

W = 0.

The ground state kinetic energy functional of an interaction-

free electron gas

T0 [n] can be written as a single slater determinant, assuring

the correct fermionic antisymmetry with respect to permutation of particles:

Ne

T0 [n] = min

{i }n

i
i=1

i Ne

i | j = ij ,

{i } n ,

(2.9)

where the sum runs over the states

lowest orthonormal single particle eigen-

Kohn and Sham [6] perceived that it is of advantage to decompose the Hohenberg-Kohn functional, to extract the noninteracting ground state kinetic energy and the interaction energy between the electron and the density as they can solely be expressed through the density,

FHK [n] = T0 [n] +

1 2

3 3 d rd r

n(r)n(r ) + EXC [n] . |r r |

(2.10)

8
Hartree energy to

CHAPTER 2. THEORY
The term in the middle on the ride hand side of equation (2.10) is the

EH ,

which describes a time-averaged repulsion through an

electrostatic eld created by all electrons. The unknown parts are reduced

EXC ,

the exchange and correlation energy.

The variational principle is now carried out, fullling the boundary conditions contained in (2.9) by the method of Lagrangian multipliers,

+ v(x) +

n(r ) EXC [n] + |r r | n(x)

i (x) = i (x) i .

(2.11)

The result is a Schrdinger equation in an eective one particle picture where particles are considered in an This eective potenn(r ) 3 tial consists of the external potential, the Hartree potential vH = d r |rr | and the general but unknown exchange potential vXC , which is the last term in (2.11). The density is obtained by summing up over the

eective potential.

Ne

lowest states,

Ne

n(x) =
i=1

|i (x)|2 .

(2.12)

The Kohn-Sham equations (2.11) are nonlinear and must be solved iteratively. Each step puts out a new density, which again forms a new Hamiltonian. The occurring eigenenergies can in a weakly correlated case be regarded as the approximants of the band energies. (2.11) by To yield an expression for the total ground state energy, we multiply (x), integrate, sum over i and consider (2.9) i

Ne

E[v] =
i=1 i EF

EH [n]

dx nvXC

+ EXC [n] .

(2.13)

We need to add the nucleus-nucleus interaction term to (2.13), to x the diverging electrostatic energy of the electrons. One step further towards applicability is to draft a model for the unknown potential

vXC .

An approved one is called the local spin-density approxi-

mation (LSDA) [7]. It starts from a homogeneous electron liquid, including interaction. An external magnetic eld evokes a spin split with the degree of n(+)n() spin polarisation = . We take the exchange and correlation energy n density of a homogeneous Fermi liquid as a basis:

LSDA EXC [n, ] EXC [n, ] =

def

3 d r n(r)

(n(r), (r)) .

(2.14)

2.2 Spin Density Waves

This is a good approach if the density varies slowly in space. It is not realistic in an inhomogeneous solid, where we have nuclei and space in between, but experience shows that it yields good results, particularly for 3d transition metals, which are exclusively in the focus of this work. One reason for the good behaviour of the LSDA describing metals is the exchange and correlation energy being small compared to

EH

and

Ekin .

It is known that LSDA tends to the so-called over-binding, which means equilibrium lattice constants are predicted too small, compared with experiment. The exchange and correlation potential is taken from analytical ts by Perdew and Wang [7] to numerical simulations by Ceperley and Alder [8].

2.2

Spin Density Waves

We intend to explain the origin of the spin density wave (SDW) by using the picture of the one-dimensional Peierls distortion. For a detailed introduction, we refer to [9]. We consider a linear chain of equidistant atoms with distance a. The basic cell in the reciprocal space is the interval k . If a a a distortion is introduced, for example by displacing every r th atom by a small amount in the same direction, translational symmetry is reduced. We then have to regard a new unit cell containing r atoms, while the reciprocal space k ra . More general, we apply a periodic shrinks to the interval ra potential U to our system which opens energy gaps that can be expressed in second order perturbation theory. The energy level of the unperturbed free 0 electron state ekK is connected with the energy level of the perturbed state 1 e with a correction of order U 2 ,

e=

e0 1 kK

+
K

|UK K1 |2 . + O(U 3 ) e0 1 e0 kK kK K =

(2.15)

This equation holds for states which exhibit no degeneracy. where

2 neK , ra integer, is a reciprocal lattice vector, Uq is the qth Fourier component

of the potential. xing the sum.

free electron energy

K1 is a particular reciprocal lattice vector, for which the e0 1 is far from the values e0 kK kK compared with U. By potential to U0 = 0, we incorporate the condition K = K1 in the e0 1 , e0 2 kK kK
are

Now let us consider the case where two electron levels within order With

of each other, but far compared with and

from all others. We

need to apply degenerate perturbation theory to express the energy gap.

k K1 = K

K2 K1 = Q,

10

CHAPTER 2. THEORY
2 1/2

1 e = (e0 + e0 ) KQ 2 K

e0 e0 K KQ 2

+ |UQ | =

(2.16)

n , n = 1, 2, . . . , r 1). ra The distortion separates two states which have been formerly close together
This has the eect of splittings occurring at (kn in energy. When we neglect the interaction with more distant states, the mean value of the two energies does not change. In other words, the energy does not change in lowest order. The splitting becomes only important when occurring at the Fermi level.

K and K Q, having nearly the same energy, the magnitude of the gap is 2 |UQ |. The gain in energy is greatest when r is a small , which holds for a half-lled band, every second atom number. If kF = 2a
For states will be displaced. The energy gain, however, may be compensated by deformation energy. In three dimensions, the additional degrees of freedom raise the cost in elastic energy, so that the energy gain becomes less favourable [10]. In the case of the SDW, the periodic potential is caused by a sinusoidal P(R0 ), j

variation of the spin polarisation

P(R0 ) = P1 cos(q R0 ) = P1 cos(qz ) .

This describes a linear polarisation with wave vector

(2.17)

parallel to the is also at low

z -axis. The direction of P1 is arbitrary, but it turns out, that it the z -axis in our case, as chromium has a longitudinal polarisation q
is incommensurate with the lattice in chromium.

temperatures (Fig. 3.3). For further details we refer to [11]. It turns out that

A linearly polarised SDW is the superposition of two helically polarised SDWs with

q.

Each

K q,

opening a gap

q, as in Fig. 2.1, connects two states at K and q at in the parabolic bands. The linear SDW, as 2 EF ,
so that the

a superposition, opens both gaps, and is thus energetically preferred. The energy gain is considerable high, if the splitting occurs at shown in greater detail in Fig. 2.2. The gap is broadened, if many states are involved in the mixing process. This is called Fermi surface nesting. The mechanism works with large parallel parts of the Fermi surface, which can be translated into each other by understood by taking a look at the states raised in energy are unoccupied. The electron and hole surfaces are

q [13].

The eect is again illustrated in Fig. 2.1, in the middle section. It can be

q-dependent

static susceptibility, which

can be derived from second order perturbation theory [2],

2.2 Spin Density Waves

11

hole

electron

hole

energy k

-q

+q

Figure 2.1: This sketch shows a cut through the Fermi surface of Cr. The shaded area in the rst part is an electron surface, the unshaded are hole surfaces. The picture in the middle depicts the Fermi surface nesting: large parts of the electron and hole surfaces are parallel, and can be connected by the nesting vector

q,

this causes the SDW instability. As the electron area

is slightly larger than the hole area, q is a little bit smaller than half of the a . Below is shown how the free hole reciprocal lattice vector a : q = (1 ) 2 0 bands at eKq are folded back into the rst Brillouin zone and open energy q gaps at . The picture is inspired by [12]. 2

12

CHAPTER 2. THEORY

0 (q) =
K

[f (

f ( Kq )] iqr 2 | K|e |K q | . K + i Kq
K )

(2.18)

A large area, containing many states which are separated by enhances the instability.

q in the BZ,

With the susceptibility, one can dene a generalised Stoner condition,

I0 (q) 1 .
When the product of the

(2.19)

q-dependent static susceptibility and the Stoner q.

Op-

exchange constant I, exceeds unity, then the paramagnetic state is unstable towards antiferromagnetic (AFM) spin polarisation with wave vector posed to the Stoner criterion for ferromagnetism where simply the density of states (DOS) at the Fermi level (EF ) gures, it is demanded that the susceptibility is large for the SDW instability to occur. This is the case for Cr, exhibiting a half-lled

d-band.

Figure 2.2: Cut through the Fermi surface, containing the points There is an electron surface centred at calculation.

and

and a hole surface centred at

H. H.

The picture reveals more details of Fig. 2.1, it is taken from a nonmagnetic

Chapter 3 Literature
We give a short summary over experimental facts forming the fundament of our work. As a source we refer to the excellent review article by Fawcett [14].

3.1

Experiments

The rst neutron scattering experiments on Chromium by Nel (1936) [15] found that the magnetic ground state is described through antiferromagnetic (AFM) order. Upon a deeper view though, Shull and Wilkinson (1953) [16] detected that the ground state is rather a spin density wave (SDW), meaning that the moment is varied sinusoidally. This is a generalisation of the AFM state, which can be interpreted as a special case of a commensurate SDW a 4 z , az = e being the unit vector in z state with wave vector of q = 2 a z direction in the reciprocal space. Today we know that below T = 78 K, Cr shows a longitudinal incommensurate SDW state with a wave vector of q = (1 ) a2z = (0, 0, 0.952) 2 (Fig. 3.2), which corresponds to about 21 a double layers (dl) of length. The amplitude of the moment is 0.62 B at the

= 2.884 . = 123 K (Fig. 3.3), where the polarisation changes from longitudinal with P q below TSF to transverse with P q above. For T < TSF , we have (0, 0, 1 ), above we have (0, 1, ). At the Nel temperature TSF = 311 K, there is a phase transition from the
experimental lattice constant of aexp There is a spin-ip transition at TSF incommensurate SDW to a paramagnetic state.

14

CHAPTER 3. LITERATURE

(a) SDW

(b) mirror planes

Figure 3.1: (a) is a sketch of the variation of the magnetic moments along the direction of the wave vector q. The sketched unit cell contains n atoms, n n or double layers in a bcc lattice. As is not an integer the node of the 2 2 SDW will not rest on an atom. Below T = 78 K there is a longitudinal state with the magnetisation vector parallel to the wave vector P q, with a z q = 0.952 2 , according to Fig. 3.2. For sake of perspicuity, the sketch illustrates a transversal state. (b) shows the symmetry of the SDW supercell. We can assume one mirror plane at the centre, two at the edges.

Figure 3.2: temperature dependence of the wave vector a of ; slightly modied from [14] 2

q, q

is given in units

3.1 Experiments

15

(0,1,d)

(0,0,1-d)

Figure 3.3:

phase transition from longitudinal to transverse SDW phase.

Plotted are the magnetic satellite reections in AFM Cr. I is the integrated density under the Bragg peaks at the satellite positions; slightly modied from [14].

|P3/P1|

Figure 3.4: the ratio (absolute value) of the amplitude of the third-harmonic SDW over that of the fundamental SDW,

|P3 /P1 |, plotted over .

The circles

indicate measurements taken from alloys, the solid line comes from a model calculation, according to [14] (slightly modied).

16
3.1.1

CHAPTER 3. LITERATURE
SDW with higher harmonics
Higher harmonics inuence the shape of the SDW. The two

Parts of the Fourier spectrum of the spin density have been determined experimentally. anti-nodes of the SDW are symmetric to each other, resulting in a mirror symmetry at the centre point. This property cancels the even terms in the Fourier expansion. Let us consider the rst higher harmonic,

P3 .

A negative

P3

will result in a more rectangular waveform, whereas a positive coecient

will cause a triangular waveform. The ratio of the third harmonic SDW over the fundamental SDW P3 /P1 has been measured to be negative with a value 2 of 2.1 10 by Tsunoda 1985 at 144 K. More experimental details are collected in Fig. 3.4. The Fourier expansion, knowing that the polarisation points in the

direction, can be written as

P (z ) = P1 cos(qz ) + P3 cos(3qz ) = P1 cos() + P3 cos(3) .

(3.1) (3.2)

We have rewritten the last equation using cos[qz ] = cos[(1 )] = (1) cos() and have considered only the envelope. z = a are the xed 2 lattice positions in the unit cell of the bcc lattice, is an integer counting through the atoms in the unit cell, as in Fig. 3.1.

3.1.2

CDW

There is a periodic perturbation of the electron charge density in addition, a charge-density-wave (CDW), with half the period of the envelope of the SDW. We may express the CDW as a variation of occupation numbers

0 N (z ) = N0 (z ) N2 (z ) cos(2z ) ,
with

(3.3)

N2 (z ) as the amplitude of the CDW, and N0 (z ) as the charge around the site z without CDW. The CDW has been determined experimentally to 2 be N2 0.3 2.0 10 .
3.1.3 SW

A magneto-volume eect in Cr causes the atomic positions to be shifted sinusoidally, called strain wave (SW). The result is the lattice spacing being maximum when the SDW amplitude is maximum. The period of the lattice distortion is again half the period of the SDW, as in Fig. 3.5. We treat only shifts in the

direction and write the SW as

3.2 Theoretical descriptions

z = z A2 sin(2qz ) .
the lattice spacing, (3.4)

17

Experimentally observed values for the SW amplitude are, relative to A2 /a 1.7 103 and A2 /a 3.5 103 for 293K and

130K, respectively. We prefer the lower temperature value, resulting in

A2

4.5 103

(a) without SW

(b) with SW

Figure 3.5: (b) depicts the periodic distortion as is caused by the magnetovolume eect. It is compared to the xed lattice (a)

3.2

Theoretical descriptions

Overhauser (1962) [11] called a static SDW in account for the AFM state in Cr, instead of a modulation of localised spins. A SDW wave vector

should

connect two pieces of the Fermi surface. A linearly polarised SDW should be lower in energy than a helical SDW, as described in 2.2. This result is in contrast to the isotropic Heisenberg model, used for localised spins, where the ground state is helical [17]. Lomer (1962) [13] found that the stability of the SDW state is enhanced if the Fermi surface has the so-called nesting property, i.e. electron and hole surfaces can be superposed by translation through the nesting vector hole area, is responsible for the incommensurate SDW.

q.

The

shape of the Fermi surface, where the electron area is slightly larger than the

18
3.3

CHAPTER 3. LITERATURE
Band structure calculations

Early band structure calculations were performed by Asdente and Friedel (1961) [18], Loucks (1965) [19], Asano and Yamashita (1967) [20], Rath and Callaway (1973) [21] and Laurent Cr. Early spin-polarised calculations, assuming a commensurate SDW state (AFM), were carried out by Switendick (1966) [23], Kbler (1980) [24], Skriver (1981) [25], Kulikov and Kulatov (1982) [26], Ukai and Mori (1982) [27] and Nakao

et al.

(1981) [22], on non-spin-polarised

et al.

(1986) [28].

et al.

Considerable importance can be assigned to the calculation by Marcus (1998) [29]. They used the augmented spherical-wave (ASW) method

(LSDA) with the exchange-correlation potential by von Barth-Hedin. They found that LSDA predicts a nonmagnetic (NM) ground state for Cr, but when expanding the lattice by a small portion one obtains an AFM ground state. This detail is delicate as we know that LSDA tends to over-binding, predicting a too small lattice constant. They suggested that a strain-wave distortion (SW), caused by a magneto-volume eect, could stabilise the SDW ground state. SDW with larger unit cells have rst been considered by Hirai (1998) [30]. He used the KKR method (LSDA), non-relativistic, with

9 10

2 k

points and the exchange-correlation potential by Janak, Williams and

Moruzzi [31]. He performed calculations for supercells with sizes 12, 16, 18, 20 and 22 (dl), and found a SDW ground state for 20 dl with

ESDW EAF =

5 Hartree/atom.
The picture seemed to t, until new calculations by Bihlmayer and Cottenier emerged. Bihlmayer

et al.

(2000) [32] applied the FLAPW method

(GGA), with the parametrisation by Perdew 91 [33], employing

661
and

points. They conned their calculations to 12 and 14 dl, due to compuThey obtained

tational limitations.

ESDW EAF = +360 Ha/atom

180 Ha,

respectively, at the GGA lattice constant of 2.85 . They con-

cluded that, by tting the energy with a function quadratic in q, they would 18 , and thus having reproduced the obtain a SDW ground state with q 19 Fermi surface well enough. Cottenier

et al.

(2002) [34] used the WIEN2k program with GGA, with

the parametrisation by Perdew

k -mesh of 662 points. They found an AFM ground state, with ESDW EAF = +250 Hartree/atom
96 [35], and a for 20 dl, thus contradicting the results by Hirai. Vanhoof (2006) [36] again used the WIEN2k code with LSDA+U, with U=0.15 Hartree, and the parametrisation by Perdew and Wang 92 [7]. She improved the to

et al.

21 21 1

and obtained

k point sampling ESDW EAF = +300 Hartree/atom, again for

3.3 Band structure calculations

20 dl, thus conrming the value by Cottenier

19
et al.

Those last three authors found an AFM ground state, although they obtained Fermi surfaces with the correct nesting feature. This led Demangeat (2006) [37] to the conjecture, that, assuming that the DFT calculations were correct, nesting could not be the ultimate driving mechanism for the occurrence of the SDW in Cr. Part of this work will be the question, if the values obtained by these authors are coarse due to limited problem can be discarded.

sampling, and if this

Chapter 4 Calculations
After the presentation of experimental details, this chapter focuses on our results. It starts with the explanation of calculational details and proceeds with the justication of the specic parameters used. Finally the results are presented and discussed.

4.1

Technical details

FPLO 6 is used, with the parametrisation of the exchange and correlation potential by Perdew and Wang 92 [7]. The calculations have been performed scalar relativistically. To model the magnetic ground state of Cr, we have employed 3 dierent pictures: First, nonmagnetic (NM) Cr in a body centred cubic (bcc) unit cell containing one atom (space group 229, I3M3). Second, the antiferromagnetic (AFM) conguration uses a CsCl unit cell with 2 atoms (space group 221, PM3M) having opposite collinear spins with the same absolute value. For obtaining zero total magnetisation, a xed spin moment procedure (FSM) has been employed. We have set up a high initial spin split (1

per atom),

to ensure convergence to a spin split solution with high local moments. Third, the SDW conguration uses supercells varying from 15 to 23 dl (space group 123, P4MMM) in order to model the SDW wave length. Closest to experiment is the wavelength of 21 dl. The moments are still collinear, but vary sinusoidally. Spin-orbit coupling has been neglected, so the direction of the spin moment relative to the crystal lattice has no eect. This is discussed in detail in section 4.1.2. The magnetisation was again stabilised by the FSM method. We set up a sinusoidal variation of the moments with an initial amplitude of

1 B .

Further specic details concern the convergence criterion of FPLO (6.00-

22
24):

CHAPTER 4. CALCULATIONS
in all three cases the density+energy convergence criterion has been applied. While in the NM and AFM case the energy has converged with an 8 6 accuracy of 10 Hartree and the density to 10 , we were confronted with 6 problems in the SDW case. Energy convergence was put to 10 Hartree, 3 density to 10 only.

4.1.1

Dependence on

k -point

number

In the process of calculating the total energy, one imposes an equidistant mesh onto each direction of the Brillouin zone (BZ), whereupon the band energies are computed. variation of the of To ensure that the selection of the

k -mesh

is ne

enough, one has to consider the behaviour of the energy with respect to

k -mesh. For the NM and the AFM calculations, the number nk has been chosen isotropically in each direction, so the total NM AFM 3 number of k -points nk,total = nk,total is nk . We have considered the NM case for checking the convergence, and applied the same nk in the AFM case. At nk of 48 the energy convergence is sucient at about 106 Hartree (Fig. 4.2). k
points In the SDW case where we have the nesting feature, it is important that the

space is sampled accurately. The BZ of the SDW states is a slice of

the simple cubic BZ of the AFM state, we have an extremely at

z -direction.

Additionally, due to the tetragonal symmetry of the SDW states, we have a mirror plane in that direction. As the bands have to have zero gradient at BZ boundaries in our case and in between they have to be continuous, they are in a good approximation cosine like. The points are checked the convergence for

and H . We have nk = 32, and there is only 0.2 Hartree energy dierence between sampling the z direction with 2 and 4 points. We have SDW 2 concluded that it is enough to sample with 2 points, nk,total = 2nk . The k convergence has only been considered in the 21 dl case. At nk = 24, we nd the energy to be accurate enough with an error of 10 Hartree, which is
enough for our considerations and limits the computational eort reasonably.

4.1 Technical details

23

(a) bcc unit cell

(b) BZ

Figure 4.1: (a) shows the extended bcc unit cell as it is used in the supercell setup. (b) sketches the Brillouin zone of the supercell. Notice the at

direction

-250

-610

SDW NM
[Hartree] [Hartree] E - E0
NM

-275

-615

E - E0

SDW

-300

-620

-325

-625

-350 0

25

50 nk

75

-630 100

Figure 4.2: Energy Dierence over

point number. The black line shows the

convergence behaviour for the NM calculation at a = 2.791 , the red line is SDW the SDW calculation with 21 dl at a = 2.884 . E0 = 1048.880 Hartree, NM E0 = 1048.883 Hartree. Note that both graphs are separated from each other and scaled dierently.

24
4.1.2

CHAPTER 4. CALCULATIONS
Scalar vs full relativistic version

We compare the band structures for the full relativistic (fr) and the scalar relativistic (sr) calculation to justify the use of the CPU time saving sr version. The dierence between the band structures in Fig. 4.3 and Fig. 4.4 is only slight. The degeneracy of one of the bands going from

to

is lifted

and causes a small split of that band into two which are separated by an energy in the order of a tenth of an eV. This value is explained by the atomic spin-orbit split of the Cr

3d

states,

E3d3/2 E3d5/2 = 78

meV. The band split

causes one band to move up in energy, whereas the other band declines, so in lowest order of energy, the split is compensated. The total energy dierence fr sr between fr and sr, on the other hand, amounts to E E 1 mHartree only, and a large part of this value contains a constant shift with respect to dierent magnetic states. But the value of the split is comparable to the split occurring at the Fermi level in the density of states (DOS) (Fig. 4.13). Changes in higher orders of energy might result in a shift of the Fermi level. Additionally, the isotropy in the fr version is broken. It could be possible that the SDW shows a higher anisotropy than the AFM state. We can put this argument forward by considering an AFM state to be a special case of a a , where = . In a SDW with wavelength , but also with = 2 between, if not constant, the anisotropy can be either lower or higher. As there is a reorientation transition in Fig. 3.3, the anisotropy should be rather small though. No band gaps are opened at the Fermi level in Fig. 4.4, and the value of the band split is small. This is the reason why we have decided to employ the sr version.

4.1 Technical details

25

2.0

1.0 Energy n(k) [eV]

0.0

1.0

2.0

Figure 4.3: bands for NM Cr at

a = 2.884

, scalar relativistic

2.0

1.0 Energy n(k) [eV]

0.0

1.0

2.0

Figure 4.4: bands for NM Cr at

a = 2.884

, full relativistic

26
4.2

CHAPTER 4. CALCULATIONS
Results and Discussion

This section starts with the two cases NM and AFM Cr, which are moderately demanding with respect to computational eort. It continues with the SDW and concomitant eects.

4.2.1

NM and AFM Cr

In the following the selection of the lattice parameter and the reference energy of the NM and AFM ground state is determined for further consideration.

Energy Minimum
We are interested in the LSDA ground state for Cr. equilibrium volume. We nd a NM ground state at the equilibrium lattice parameter of a = 2.791 , the LSDA underestimates the lattice constant by approximately 3 % (Fig. 4.5). From about a = 2.86 on, there exists an AFM state, and from a = 2.87 on, it is lowest in energy. The energy dierence between the NM and the AFM state at the experimental lattice constant is about As the Kohn-Sham equations depend parametrically on the nuclear positions, we have to nd its

0.1

mHartree. The check with literature values gives quite good agreement, Vanhoof

(2006) [36], obtained gave

a = 2.79

(LSDA), and Cottenier

et al.

(2002) [34]

a = 2.794

(LSDA).

4.2 Results and Discussion

27

LSDA

= 2.791

a exp = 2.884

-1

AFM NM

-0.1

-2

-3

-0.2

-4

2.75

2.8 2.85 lattice parameter []

Figure 4.5: Energy over lattice constant at Energies are normalised with a 4th order polynomial.

nk = 48

on the left hand scale.

E0 = 1048.880 Hartree per atom and tted with

The right hand scale shows the energy dierence

between the AFM and NM state.

a exp m LDA

magnetic moment [B]

m exp

0.5

0 2.8 2.85 lattice parameter [] 2.9

Figure 4.6: Magnetic Moment of AFM Cr at

nk = 48

EAFM-ENM [mHartree]

E-E0 [mHartree]

28

CHAPTER 4. CALCULATIONS Volume dependence of the magnetic moment

Below

a = 2.85 , a small magnetic moment appears in the AFM calculation

The evaluated moment at the equilibrium

due to numerical uctuation. of lattice constant is about 0.001 108 Hartree, due to EXC

B , which corresponds to an exchange energy 2 2 I M2 = 0.5 M2 eV [38]. This can be assumed 2

B B

zero as it is just at the edge of accuracy. In principle, the states we obtain below from

a = 2.85 , are the same in both AFM and NM calculations. Starting a = 2.86 the solution splits into two branches when larger moments

evolve. The magnetic moments in Cr show considerable dependence on the volume. From Fig. 4.6 it is apparent that Cr at its LSDA equilibrium volume lies marginal to magnetism. Having a nonmagnetic ground state at the equilibrium LSDA volume, it becomes magnetic when increasing the volume by about

2 %. 0.924 B
at the experimental lattice constant. We

We nd a moment of

give literature values, which cannot quite be compared to our results, since the absolute value of an antiferromagnetic moment depends on the volume of integration. Dierent cuto radii may result in dierent evaluated moments. Vanhoof (2006) [36] obtained gave

0.45 B

(LSDA), Cottenier

et al.

(2002) [34]

0.60 B

(LSDA).

Band structure and DOS

The reason for the AFM conguration being favourable becomes clear when we look at the band structure. In comparison to Fig. 4.7, Fig. 4.8 shows two splittings at the Fermi level in directions

and

M.

These splits

lower the energy of the occupied states and raise it for the unoccupied states. There is further insight into this splittings when we take a look at the DOS (Fig. 4.10). At the Fermi level, a considerable amount of states is shifted by 1 about th eV towards lower energies. For higher resolution of the DOS, we 20 have used nk = 96 points. Fig. 4.9 shows a comparison of the DOS of NM Cr in bcc NM and CsCl AFM congurations. Both densities should be the same, but the small deviation near the Fermi level points to high sensitivity of the DOS regarding

k -point

sampling. Obviously even a value of

96

was not enough here. and

From the DOS we can also probe for instability against ferromagnetic polarisation by checking the Stoner criterion:

IN = 0.25 < 1 at 2.791

0.28 < 1 (NM) at 2.884 14 mHartree [2]. We see

, where we have taken the value by Kbler, that in no case it is fullled.

I =

4.2 Results and Discussion

29

2.0

1.0 Energy n(k) [eV]

0.0

1.0

2.0

Figure 4.7: Bands of NM Cr in CsCl geometry at

a = 2.884

2.0

1.0 Energy n(k) [eV]

0.0

1.0

2.0

Figure 4.8: Bands of AFM Cr at

a = 2.884

30

CHAPTER 4. CALCULATIONS

NM AFM
3

DOS [states/eV]

-4

-2

Energy [eV]

Figure 4.9: DOS at

a = 2.791

AFM NM
3

DOS [states/eV]

-4

-2

Energy [eV]

Figure 4.10: DOS at

a = 2.884

4.2 Results and Discussion

4.2.2 SDW

31

The calculation of truly incommensurate SDW states is beyond band structure calculation, as there is no translational symmetry along the direction of the SDW propagation. So we have set up commensurate states with a period close to the experimental wave vector, which is approximately 21 dl. For comparison with the energies of the NM and AFM states, we have repeated the NM and AFM calculations in the supercell geometry. It could be possible that the values deviate in a supercell geometry from their values in the primitive cells. We have found that the values remained satisfactorily constant, so we give only the values for the primitive cells. It is assumed that the SDW shows similar energy over volume behaviour to the AFM as they both lie energetically close. We did not perform another energy over volume test and we have chosen the experimental lattice constant in order to force a magnetic ground state.

SDW of dierent periods

We have been able to perform calculations for dierent supercell sizes up to 23 dl. The energy decreases with increasing wavelength, but it never The AFM state is still the ground reaches the energy of the AFM state.

state solution, with an energy dierence of Fermi surface nesting seems to be intact.

ESDW EAFM = +40 Hartree

for 21 dl (Fig. 4.11). We nd a local energy minimum for the 21 dl state, so Puzzling is the glance at the band structure plot in Fig. 4.12. numerous gaps opening at the Fermi level in directions and We see

X, M

This picture is conrmed by the DOS in Fig. 4.13, where the 1 th of an shift towards lower energies is even greater in the SDW case, over 10 eV. Nevertheless, this does not give us the necessary energy gain, so we have to assume that this gain in band energy is overcompensated by Coulomb or exchange contributions.

Z R.

Analysis of SDW moment distribution

The following section is dedicated to compare the shape of our SDW states with experimental and theoretical values from the literature. This is a good test for the accuracy of our calculations. We try to answer the question which role higher harmonics play. For the analysis, the distributions of moments of SDWs with dierent wave vectors have been tted according to (3.2). 2 Fig. 4.14(a) shows the results. Our value of P3 /P1 = 7.1 10 (21 dl) 2 is in the region of Tsunodas measurement of 2.1 10 (see 3.1.1). Hirai 2 2 (1996) [30] obtained 3.7 10 , Cottenier (2002) [34] gave 20 10 ,

et al.

32

CHAPTER 4. CALCULATIONS

double layers
-300 15 17 19 21 23
AFM SDW with n/2 N

[ Hartree] E - E0
SDW

-320

-340

-360

-380 0.93

0.94

0.95

0.97 0.96 * q / (a /2)

0.98

0.99

Figure 4.11: energy per atom for varying supercell sizes, q in units of

a 2

2.0

1.0 Energy n(k) [eV]

0.0

1.0

2.0

Figure 4.12: Bands of 21 dl SDW

4.2 Results and Discussion

33

AFM NM SDW

DOS [states/eV]

0 -1

-0.5

0 Energy [eV]

0.5

Figure 4.13: DOS of 21 dl SDW determined at

ntotal = 48 48 2 k

both for the 20 dl SDW. It is hard to tell if our calculations reproduce Fig. 3.4. From 15 to 21 dl, it follows quite well, but the 23 dl deviates. Our calculations deliver a quite sinusoidal shape, without much inuence of higher harmonics. We can state that the amplitude of the SDW is well enough determined by the coecient

P1

up to an accuracy of a few

%.

The coecients

P1

have the

tendency to raise in magnitude towards larger wavelengths, except for one drop at 23 dl (Fig. 4.14(b)). In the AFM case, we observe a high moment of

0.972 B .

This value is somewhat dierent from the value given in section

4.2.1, which was

0.924 B ,

obtained from the primitive cell.

Nevertheless,

the energies in both cases only dier by

1 Hartree.

CDW
Deviations from a normal distributed density, which allocates the same charge around each atom, are present in the SDW case, a sinusoidal modulation of the charge density (CDW) emerges. Motivated by the CDW, we have analysed the behaviour of the occupation numbers, and found small 3 sinusoidal variations. Our value for the SDW without SW is N2 2 10 , 3 this compares quite well with Cotteniers (2002) [34] of N2 2.6 10 ,

et al.

and furthermore with the experimental value, given in section 3.1.2. Hirai

34

CHAPTER 4. CALCULATIONS
double layers 19 17

23 0.07

21

15

0.06

|P3 / P1|

0.05

0.04

0.03 0.04 0.045 0.05

(a)

0.055
over

0.06

0.065

0.07

|P3 /P1 |

double layers
15 1 17 19 21 23

0.9

P1 [B]

0.8

0.7

0.94

0.95

0.96

0.97 * q / (a /2)
over

0.98

0.99

(b)

P1

Figure 4.14: (a) shows the ratio (absolute value) of the 3rd harmonic over the fundamental SDW, of uncertainty:

|P3 /P1 | P1

over

The error bars are from the tting

process, and have further been derived under consideration of propagation orthogonal, so the relative error is are uncorrelated as their referring functions are (P3 /P1 ) = P3 P1 . (b) displays the P3 /P1 P3 P1 amplitudes of the fundamental SDW P1 over q. The moment appears to be constant from 15 to 21 dl, but then drops at 23 dl. result from tting. Again, the error bars

P3

and

4.2 Results and Discussion

(1997) [39] obtained

35
The variations seem to be compensated

N2 0.6 104 .

in the SW case, as in Fig. 4.15.

-0.001

-0.002

N
-0.003 -0.004 -0.005

0.1

1 [10

10
-3

100

Figure 4.15: Occupation number wave in 21 dl supercell geometry. Shown is the coecient

N2

over dierent strain wave amplitudes.

In the AFM

supercell, we have also observed a small

N2 .

We perceived this as numerical

uctuation and included it into the error. Further the error from the tting process enters the total error. The red data point has been calculated at zero distortion, this value has been denoted as

on the logarithmic scale.

SDW with SW
We were hopeful that the application of a lattice distortion would stabilise the SDW and provide additional energy gain. Unfortunately there is no such energy gain in a large area around the experimental value (Fig. 4.16(a)). Even the reversal of the sign of the amplitude, meaning small lattice spacing at a SDW anti-node has no big inuence. It was expected that this should raise the energy. We rather see a symmetric shape. The DOS picture in Fig. 4.16(b) does not help out either, as the shifts are marginal.

36

CHAPTER 4. CALCULATIONS
A2 exp

-100 -150
SW + 21 dl SW - 21 dl

Energy [Hartree]

-200 -250 -300 -350 -400

10 100 -4 SW amplitude [10 ]

(a) Energies of SW

1000

SW 10.5 SW 0.5 SDW

DOS [states/eV]

0 -1

-0.5

0 Energy [eV]
(b) SW DOS

0.5

Figure 4.16: (a) shows the energies for dierent SW amplitudes, for both positive (black) and negative (red) as

A2 .

The experimental SW value is denoted The error bars

Aexp .

SW have only been considered in the 21 dl case.

are due to DOS

amplitude of

10.5 103

sampling. (b) compares the DOS for 2 SW cases, one with an 3 , the other one at 0.5 10 , with the undisturbed

Chapter 5 Summary and Outlook

We are left with the conclusion that the LSDA, and methods beyond, as the literature points out [34], fails to describe the magnetic ground state of chromium correctly. be addressed to. sucient. with respect to There are three main points, where this error could The rst point is that the resolution of the BZ was not number was able to rule that possibility out.

But the careful consideration of energy convergence behaviour

k -point

The second point, as earlier mentioned by [29], is the supporting mechanism of the SW, which would be able to deliver an additional energy gain. Nevertheless, the calculations performed over a wide range of SW amplitudes do not give any hint on such a mechanism. The last point is the missing spin-orbit coupling in our calculations. The justication was a little bit unrm. Additionally, the magnitude of the split is comparable to the energy shift at the Fermi level. These calculations require a high amount of computing time, and the results have not yet been obtained. They are left open for future discussions. It cannot be ruled out at the moment, that even full relativistic LSDA may fail to yield the correct magnetic ground state of Cr. However, the local energy minimum for 21 double layers shown in Fig. 4.11 indicates that Fermi surface nesting seems to be operative.

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Acknowledgement
I am grateful to Prof. Dr. H. Eschrig, director at the Leibniz Institute for Solid State and Materials Research Dresden for oering me the possibility to write my diploma thesis under his guidance, for the scientic management and support. I am deeply indebted to my supervisor Dr. M. Richter, head of the group Numerical Solid State Physics and Simulation, for always being open to discussion, proposing ideas, and encouraging me. I would like to thank all members of our working group, especially Dr. K. Koepernik for opening my mind to technical details, and U. Nitzsche who gave me Linux skills where there haven't been any before. Finally I should mention my parents and friends who supported me throughout the years.

Eidesstattliche Erklrung
Ich versichere, dass ich die vorliegende Arbeit ohne unzulssige Hilfe Dritter und ohne Benutzung anderer als der angegebenen Hilfsmittel angefertigt habe. Aus fremden Quellen bernommene Gedanken und Passagen sind als solche kenntlich gemacht. Diese Arbeit wurde in gleicher oder hnlicher Form noch keiner anderen Prfungsbehrde vorgelegt.

Mathias Bayer