Lecture 3 continuation from Wednesday

Dynamical Matrix Conduction electrons

Importance of el-ph Matrix elements

NiAl

50-50 compound

Confirmed by
H. Chou and S.M.Shapiro Phys. Rev. B48, 16088 (1993)

Exp.
G. L. Zhao and B. N. Harmon, Phys. Rev. B45, 2818 (1991)

Thy

b- phase Ni0.625 Al0.375 T=0K Theory

(using rigid band approximation)

G. L. Zhao and B. N. Harmon, Phys. Rev. B45, 2818 (1992)

Ni0.625 Al0.375

Solid lines are theory, with a fictitious temperature of 1000 K to account for thermal and alloy disorder. Symbols are experiment at RT, and dashed line is experiment at 85 K.
S.M. Shapiro, Mat.Sci. Forum 56-58, 33 (1990) and S.M. Shapiro, B.X. Yand, G. Shirane, Y. Noda, and L.E. Tanner, Phys. Rev. Lett. 62, 1298 (1989)

Many Phonon is Bzone are imaginary!!!

(all first principlesnot a surprise perhaps, at this is for T=0)

NiTi B2 T=0K
Electronic structure force constants

Unstable phonons
Xiangyang Huang, Claudia Bungaro, Vitaliy Godlevsky, and Karin M. Rabe Phys. Rev. 65, 014108 (2001).

Problem with first principles (T=0) calculation of the bcc structure: It is unstable if the temperature effect is not included, as we saw Can be stabilized by non-linear phonon couplings: 3 & 4 order (T=0 OK) Ye, Chen, Ho, Harmon and Lindgrd, PRL, 58, 1769 (1987) A new way is presented above: By allowing atoms to be displaced from the (average) bcc positions Self-consistently calculate forces and mean-square displacements in a 4x4x4 times larger super cell than the uinit one until convergence. Frozen glassy-like structure? This nicely illustrates the bcc problem by a direct FP calculation

Takes into account the temperature!

Compare to T=0 calculations.

Calculated phonon spectra

Imaginary

T>TM

!N

T=0

!N

Energy paths through the landscape The Na story Total energy calculation for structural phase transformations
Y.Y. Ye, C.-T. Chan, K.-M. Ho and B. N. Harmon The International Journal of Supercomputer Applications, Volume 4, No. 3 Fall 1990, pp. 111-121.

Na - precise total energy calculations

bcc hcp 9R

The bcc-hcp transition requires

1. A shuffle of atomic planes corresponding to a T1 Npoint phonon, and 2. A shear (Bain strain) that changes the basal plane angle from 109.47o to 120o.

The minimum energy path displays some interesting physics.

bcc

hcp

9R has slightly lower barrier and slightly lower total energy compared to the hcp phase.

bcc

X-Ray Magnetic Circular Dichroism (XMCD) For Rare Earth Magnetic Materials Toward a Quantitative Analysis Bruce Harmon

TMS March 10, 2008

First, a big thanks! To Karl Gschneidner

TMS March 10, 2008

XRES and XMCD

EF
XRES
5d

XMCD

LCP

RCP L3 L2
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2p3/2 2p1/2

Good Features of XMCD

for magnetism studies
1. Element specific (tune beam to core energy) 2. ~ Orbital specific (dipole selection rule) 3. No nuclear absorption (sometimes problem for neutrons)

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History
Magnetic x-ray dichroism in gadolinium metal P. Carra, B. N. Harmon, B. T. Thole, M. Altarelli, and G. A. Sawatzky EXPERIMENT Phys. Rev. Lett. 66, 2495-2498 (1991) L2 L2 THEORY L3

L3

G. Schtz, et. al., Z. Phys. B 73, 67 (1988).

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TMS March 10, 2008

XMCD SUM RULES

Orbital
X-ray circular dichroism as a probe of orbital magnetization B. T. Thole, P. Carra, F. Sette, and G. van der Laan Phys. Rev. Lett. 68, 1943-1946 (1992)

Spin

where

X-ray circular dichroism and local magnetic fields P. Carra, B. T. Thole, M. Altarelli, and X. Wang Phys. Rev. Lett. 70, 694-697 (1993)

Limitation of the Magnetic-Circular-Dichroism Spin Sum Rule for Transition Metals and Importance of the Magnetic Dipole Term R. Wu and A. J. Freeman Phys. Rev. Lett. 73, 1994-1997 (1994)

TMS March 10, 2008

The Sum Rules work wonderfully for 3dtransition metals! But they do not work for Rare Earth materials!

Why?
(Atomic model assumptions breakdown!)

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4pr2R2(r)

5d

2p position
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TMS March 10, 2008

Solid State Effects

4f

5d spin up wave function is contracted by 4f-5d exchange interaction Spin up Radial Matrix Elements (ME) are larger than spin down

2p
down

up

Energy dependent ME
EF Top of d-bands
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Trend of Exchange and S-O Energy of Heavy Rare-Earth 5d States

TMS March 10, 2008

Branching Ratio L3/L2 Experiment vs. Theory

10 8

RNi2Ge2 Experiment RNi2Ge2

Theory - HCP

Theory - hcp

BRANCHING RATIO

III II L /L

6 4 2

No-Spin Orbit
0

Gd

Tb

Dy

Ho

Er

Tm

J. W. Kim, Y. Lee, D. Wermeille, B. Sieve, L. Tan, S. L. Budko, S. Law, P. C. Canfield, B. N. Harmon, and A. I. Goldman Phys. Rev. B 72, 064403 (2005) TMS March 10, 2008

Gd5Si2Ge2
(Low T) Orthorhombic Monoclinic (High T)

The breaking of Ge(Si) bonds is responsible for loss of magnetism

TMS March 10, 2008

Gd5Si2Ge2 : XMCD
D. Haskel et al. PRL 98 247205 (2007)

* XMCD data at the Ge K and Gd L3 edges. * XMCD signal of Ge K-edge indicates that the Ge 4p states carry magnetic polarization.

TMS March 10, 2008

Gd5Si2Ge2:spin density contours

Orthorhombic Monoclinic

Ge2 Gd Si
b a

Ge1
TMS March 10, 2008

The Er2Fe17 Story

J. Chaboy, H. Maruyama, N. Kawamura, and M. Suzuki Phys. Rev. B 69, 014427 (2004)

Er L3 edge

The Er2Fe17N2.4 XMCD spectra were taken at room temperature and at 50K. Large spectral changes, and quadrupole features observed.
TMS March 10, 2008

The Er2Fe17 Story

J. Chaboy, H. Maruyama, N. Kawamura, and M. Suzuki Phys. Rev. B 69, 014427 (2004)

The Er L2 spectra changes sign with temperature!

TMS March 10, 2008

Calculated L3 for Er2Fe17

Yongbin Lee

with E2 contribution added

TMS March 10, 2008

Calculated L2 for Er2Fe17

with E2 contribution added

TMS March 10, 2008

Experiment
Er L3 edge normalized to peak
0.04
Normalized Dichroism (to peak)

Experiment

Theory

0.02 0 -0.02 -0.04 -0.06 -0.08 -15 -10 -5 0 5 10 15 20 Energy (eV) T=300K T=200K T=125K T=75K

Goldman et. al. L3

Yongbin

TMS March 10, 2008

Experiment

Er L2 edge peak normalized

0.025
Normalized Dichroism (to Peak)

T=300K T=200K T=125K T=75K

0.02 0.015 0.01 0.005 0 -0.005 -0.01 -0.015 -10 -5 0 5 Energy (eV) 10 15

20

Goldman et. al. L2

Yongbin

TMS March 10, 2008

The qualitative agreement leaves little doubt the physics is correct, but the quantitative agreement is poor! New results indicate enhanced orbital polarization on Er and also possibly on Fe can account for all the differences.

TMS March 10, 2008

Thank You

TMS March 10, 2008

K. Takeda et al., J. Alloys Compd. 281, 50 (1998)

TMS March 10, 2008