Neutron scattering as a tool to study

quantum magnetism
Radu Coldea
Oxford
Outline
- principles of (magnetic) neutron scattering
- spin waves in a Heisenberg ferromagnet
- spin waves in square-lattice AFM La2CuO4

- quantum renormalization, spinons and method to determine

Hamiltonian – triangular AFM S = 1/2 Cs2CuCl4

- quantum phase transition in the Ising chain CoNb2O6 in

transverse field
 Neutron reactors Three-axis neutron spectrometer

(Institute Laue Langevin)

- nuclear fission of Uranium

ki

kf
Q

ki – kf = Q
Ei – Ef = E

neutron
guide
spectrometers Clifford Bertram
Shull Brockhouse
 Spallation neutron sources (ISIS, SNS …)
- “evaporation” when fast protons
hit a heavy nucleus (Ta)

proton synchrotron p+
accelerator ~800MeV

neutron
guide
time-of-flight
spectrometer

~40,000 detector elements

count simultaneously (time-
LET@ISIS stamp each arriving neutron
Magnetic neutron diffraction kf

Neutrons have ki
- no charge
- spin-1/2 moment dipole moment M

Periodic magnetic order

t magnetic
=> magnetic Bragg peaks
at Q = t ± q unit cell

- Intensity ~ q

Fourier transform of magnetic

moment density (perp to structural
magnetic
Bragg peak t
scattering wavevector Q)
Inelastic magnetic neutron scattering
kf excited
ki state

sample ground state

matrix element for transition

Fourier transform of magnetic
moment density M a

Fourier transform of
magnetic e- density polarization factor
 Single crystals for inelastic neutron scattering
La2CuO4 Cs2CuCl4 CoNb2O6
(solution growth) (mirror furnace growth)

4 cm

2.5 cm

7 single-crystal mount ~50 g

(flux growth)
floating-zone mirror furnace
 Spin waves in a Heisenberg ferromagnet
H = -  Jij Si·Sj if all Jij > 0 T=0 ground state is ↑↑↑↑↑↑
ij
- neutrons flip over one spin S- =
magnon (q) = -J(q) exact
B (0) +- J(0) + h result
energy
1
J(q) = _ ijJij e
iqrij
Zeeman
2
energy
H =  - Jij Si·Sj - h  Siz Fourier transform
ij i of magnetic couplings
Wavevector (q)
-
= _Jij (Si- Sj+ + Si+Sj- ) +-  Jij SizSjz - h  Siz
ij 2 ij i
hopping One spin flip
manifold
(q)

Energy
coherent propagation of spin-flip states S-
(if Hamiltonian conservs Sz)
Gap 
magnon 0

Dispersion images exchange Hamiltonian

|q> =
1
e iqr |
N i
i
i>
Neutron scattering by ferromagnetic magnons

scattered
incident
neutron kf
S z = + 1/2
ki

S z = -1/2 Magnon
k
Sz = -1

ki - kf = k
Ei - Ef = ħ w(k)
Wavevector k
L (rlu)
Spin waves in the square-lattice anti-ferromagnet
Ground state has Neel order
(<S> reduced by quantum fluctuations)

J antiferromagnetic Spin wave excitations

(approximate eigenstates)
La2CuO4

Magnetic Bragg peak (1/2,1/2,0)

- insulating parent of
high-TC cuprates

- square-lattice of CuO2
planes, Cu2+ S=1/2

Keimer at al, PRB (1992)

 Neutron scattering experiments on La2CuO4

ki
S=1
magnon

kf

7 single crystal mount, ~50 g

RC et al, PRL 86, 5377 (2001)
 Magnetic excitations in La2CuO4
Collect maps of magnetic scattering in the whole
2D Brillouin zone (h,k) at increasing energies E

Energy
325 meV

275 meV

75 meV

Spin-wave dispersion surface

RC et al, PRL 86, 5377 (2001)
Dispersion relations
La2CuO4, T=293 K

Antiferromagnetic
Bragg peak
position

RC et al, PRL 86, 5377 (2001)

Dispersion relation and interactions
- dispersion shape is a direct fingerprint of the magnetic interactions

- “wiggle” in high-energy dispersion is evidence

for a cyclic-exchange between the 4 spins on a
plaquette in addition to the main exchange J

RC et al, PRL 86, 5377 (2001)

Ring exchange in the Hubbard model

Expand up to 4
electron hops
A.H. MacDonald (1990),
Takahashi (1977)
Hubbard model parameters for La2CuO4
- dispersions and intensities
well described by linear spin-
wave theory
t = 0.30(2) eV, U = 2.2 (4) eV
U/t = 7.3 ± 1.3 (10 K)

Intensity renormalization factor

Zc = 0.51 +/- 0.13 (predicted 0.61)

RC et al, PRL 86, 5377 (2001)

Magnetic excitations in S =1/2 triangular lattice AFM Cs2CuCl4
J' - sharp spin-wave mode only very small
J weight
- dominant scattering continuum with
strongly-dispersive boundaries
=> Quantum fluctuations very strong, spin-
wave theory inadequate

1.5 (0,0.5,l) 1.25 1

6

Intensity (a.u.)
Intensity (arb. units)
1

0.1
0.2 0.8
E (meV)
2

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
RC et al, PRB 68, 134424 (2003) Energy (meV)
 Experimental method to determine Hamiltonian
via spin waves in the fully-polarized state in high field
RC et al, PRL 88,137203 (2002)

B=0 B >> J

J antiferromagnetic gapped
ω magnons

State with AF Fully-polarized Δ

correlations state
↑↑↑↑↑ k
Applied
Dispersion is the Fourier
Field
BC transform of exchange
couplings
Magnetically Exact eigenstate if
(k) = J (k) - J (0) + h
ordered, spin Hamiltonian
liquid etc. Bose condensation conserves Sz J (k) = 1 S Jd exp( i k · d)
of magnons at Bc 2 d
 Excitations in the saturated ferromagnetic phase at B=12 T
T=60 mK T=60 mK Lineshapes show sharp

Susceptibility dM/dB (/T)

0.4
1.0 magnon excitations
Magnetization ()

0.8 0.3
Bc = 8.42 T 30 (0,1.447,0)
0.6 0.2

0.4 0.1 20

0.2
0.0 10
0.0 0 2 4 6 8 10
0 2 4 6 8 10 Field // a (Tesla) 0
0.4 0.5 0.6
Field // a (Tesla) Energy (meV)

(021) (010) (020) (021) Fourier transform of

2.0 1.5 1.0 0.0 0.5 1.0
[0,,-1] [0,2,l] couplings J(q)
1.5 J=0.374(5) meV
Energy (meV)

J’=0.128(5) meV J'

J
1.0 _J’ ~ _1
c
J 3

0.5
2D Hamiltonian b
B = 12 T || a D
T < 0.2 K
0.0
1.0 1.5 2.0 J’’= 0.017(2) meV interlayer coupling
[0,k,0] Da = 0.020(0) meV DM anisotropy _| bc plane
RC et al, PRL 88,137203 (2002)
 Magnon condensation below critical field induces transverse order
B<Bc B=Bc B>Bc magnon
dispersion

Gap 

Q
B (T) || a
0 2 4 6 8 10 12
1.50 (a) 20) 1.5
(0
Energy (meV)

1.25
0)

Energy (meV)
1.00 1 1.0
(0 +
0.75 1)
47, Bragg peaks appear
.4 -
(0,
0.50 0.5
1) where the gap closes
0.25 47, D
.4
0.00
(0, 0.0
150 B > Bc
B < Bc
(b) CONE FERRO
1.00 1.25 1.50 1.75 2.00
[0,k,0]
0.04

Intensity a.u.)
Peak intensity
(arb. units)

100
0.03

0.02
50
0.01

0.00 0
0 2 4 6 8 10 12 1.40 1.45 1.50
B (T) || a K (rlu)
RC et al, PRL 88,137203 (2002)
 Link magnetic order with magnon wavefunctions
(000)
+D Alternating layers
1.0
Energy (meV)

counter-rotate
0.5
-D
Sense
-Q +Q selected by
0.0
-0.5 0.0 0.5 DM couplings
[0 k 0]
2 condensates at
D·(Si x Sj)
+Q and -Q
1.5

Asymmetry <Sb>/<Sc>
1.6

Energy (meV)
1.0
1.4

1.2 0.5

1.0
0.0
1.00 1.25 1.50 1.75 2.00
0 1 2 6 8 [0,k,0]
B (T) || a
predicted asymmetry using
magnon wavefunctions
RC et al, PRL 88,137203 (2002)
 Quantum renormalization of incommensurate ordering wavevector
mean-field

Incommensuration
B=Bc 0.05 result

 (2/b)
Q Bc= 8.44(1)T
0.04
c=0.0536(5)
B<Bc
0.03 (0,1.5-,0)
(0,0.5-,1)
0.02
0 2 4 6 8 10 12
Strong quantum B (T) || a

renormalization
20° e0/ecl=0.56
10°

Energy
Wave
vector k

Collinear Quantum Classical

spins Spin-1/2 instability
large-S

RC et al, PRL 88,137203 (2002)

Magnetic excitations at zero field: spin-waves fractionalize
into pairs of S=1/2 spinons
J'
J Si+ Sj- + S-j Si+

S=1/2
J’/J ~ 1/3, J=0.37 meV Spinons

Kohno, Starykh, Balents, Nat. Phys. (07)

 Summary on anisotropic triangular AFM Cs2CuCl4
J'
J

La2CuO4
- anisotropic triangular lattice S=1/2 AFM Cs2CuCl4 has
spiral order coexisting with strong quantum fluctuations
- renormalization of Q-vector and zone-boundary energy
measured by quenching quantum fluctuations via field and
revealing “classical” behaviour
- dominant continuum scattering (spin-waves fractionalize
into pairs of spinons) Headings, Hayden, RC …, PRL (2010)
 Ising magnets and phase transitions
Classical
- classical Ising model thermally-driven
z
H = -  J Si z S j + <Sz>
continuous phase
i,j transition
- 2D model Onsager exact solution (1944)
0 TC Temperature

Quantum fluctuations
<Sz> driven continuous
phase transition
quantum fluctuations
add transverse field
- B Sx 0
quantum tunneling BC B field
- B (S++S-) / 2
T=0 “quantum melting of order”
 An Ising ferromagnet in transverse field
z z
H = -  J Si Si+1 +- B S ix
i
T - transverse field
- B Sx = - B (S++S-) / 2
TC Quantum generates quantum fluctuations
Ferromagnet paramagnet that “melt” the spontaneous
magnetic order at BC ~ J/2
0 BC Field
z
↑↑↑↑ →→→→ x

Ordered
moment Magnetization

continuous quantum phase transition

Quantum criticality: experimental challenges
and opportunities
Temperature
Critical
Phase 1 Phase 2 Tuning
0 parameter
BC

-what is microscopic mechanism of transition, can one observe the

quantum fluctuations that drive transition ?

- how quasiparticles evolve near critical point ?

- what are the fundamental symmetries that govern physics of QCP ?

- what are finite-T properties (interplay of thermal and quantum

fluctuations, under what conditions universal scaling ?
 1D Ising chain in transverse field
z z
H = -  J Si Si+1 + 2 ground states: ↑↑↑↑↑↑ or ↑↑↑↑↑↑
i
↑↑↑↓↑↑↑↑↑↑↑
…
↑↑↑↓↓↓↓↓↓↑↑
• •
J
domain walls (solitons)
↑↑↑↑↑↑ z
- transverse field B Sx ~ - B (S++S-)
flips spins ↑↑↑↓↓↓↓↓↓↑↑ Gap D
• • Bx
=> propagating solitons
(Jordan Wigner fermions) Quantum
Ferro-
magnet BC paramagnet
spin-flip
classical soliton solitons
quasiparticle
(large-S limit) ↑↑↑↓↓↓↓↓↓↑↑
• • →→←→→
 Ising chain at criticality

gapless linear (Dirac) spectrum

w = c|k|

for critical solitons

- w/T scaling expected, special “conformal” symmetry

- different universality class from Luttinger liquids (1D Heisenberg and XY
AFM chains)
 Experimental requirements
1) good 1D character to see solitons
2) low-exchange J ~ 1 meV to access critical field BC ~ J/2 < 10 T
3) strong uniaxial anisotropy (Ising character) but not perfect to still
have transverse g-factor l L•S
Strong Crystal field + Spin Orbit

- best Ising magnets are based on Co2+ 3d7

lowest Kramers doublet effective spin-1/2 Ising-like

2D Ising AF K2CoF4 (Birgeneau ‘73, Cowley ‘84)

1D Ising AF CsCoCl3 (Goff ’95) also CsCoBr3 (Nagler)
J ~ 12 meV BC > 50 T not accessible
Quasi-1D Ising ferromagnet CoNb2O6
Oxygen
zig-zag Co2+ spin chain along c
Ferromagnetic
superexchange Co2+
~ 90° bond Co-O-Co
~ 20K ~ 2meV

Single crystal
of CoNb2O6
4 cm
Ferromagnetic order along chain (Oxford
Strong easy-axis (Ising) in ac plane image
furnace)
 Magnetic excitations in 1D phase seen by
T= 5 K, 1D phase above TN neutron scattering

k1
k2

incident ↓ ↑ scattered
↑↑↑↑↑↑↑↑↑↑↑
↑↑↑↑↑↓↑↑↑↑↑
••
- gapped continua characteristic of ↑↑↑↑↓↓↓↑↑↑↑
• •
2-soliton excitations

RC et al, Science 327, 177 (2010) k1 k2

 Magnetic excitations in zero field TC

ordered
z ↑↑↑↑
0
BC
T= 5 K, 1D phase above TN T= 0.04 K, deep in 3D phase

1D phase 3D phase

- rich structure : continuum as characteristic of 2-soliton excitations

+ sharp modes (bound states)

RC et al, Science 327, 177 (2010)

 Excitations have 1D character –
no measurable dispersion ┴ chains
|| chain direction

0.4 H=-2.5
H=-2.0

Intensity (arb, units)

H=-1.5
0.3

0.2

0.1

0
1.1 1.2 1.3 1.4 1.5
Energy (meV)

┴ chain direction
 Zeeman ladder of bound states in 3D ordered phase
T=5K T =40 mK Zeeman ladder of bound states
0.04 K
1 5K
0.3

Intensity (arb units)

L = 0.00(5)

2
0.2

3
0.1 4
5

0.0
1.0 1.2 1.4 1.6
Energy (meV)
Continuum of Bound states in
free 2-soliton confining potential Soliton separation
states costs energy
E ↑↑↑↑↑↑↑↑↑
J’
V(x) = l x
…

x x x x
↑↑↓↓↓↓↑↑↑
2 l ~ J’ Sz
1
Longitudinal mean-field -hSz , l=2 h Sz
 Zeeman ladder of bound states in 3D ordered phase
T=5K T =40 mK Zeeman ladder of bound states
0.04 K
1 5K
0.3

Intensity (arb units)

L = 0.00(5)

2
0.2

3
0.1 4
5

0.0
1.0 1.2 1.4 1.6
Energy (meV)
Continuum of Bound states in
free 2-soliton confining potential Soliton separation
states costs energy
E ↑↑↑↑↑↑↑↑↑
J’
V(x) = l x
…

x x x x x
↑↑↓↓↓↓↓↑↑
2 l ~ J’ Sz
1
Longitudinal mean-field -hSz , l=2 h Sz
 Zeeman ladder of bound states in 3D ordered phase
T=5K T =40 mK Zeeman ladder of bound states
0.04 K
1 5K
0.3

Intensity (arb units)

L = 0.00(5)

2
0.2

3
0.1 4
5

0.0
1.0 1.2 1.4 1.6
Energy (meV)
Continuum of Bound states in
free 2-soliton confining potential Soliton separation
states costs energy
E ↑↑↑↑↑↑↑↑↑
J’
V(x) = l x
…

x x x x x x
↑↑↓↓↓↓↓↓↑
2 l ~ J’ Sz
1
Longitudinal mean-field -hSz , l=2 h Sz
 Soliton confinement 0.04 K
1 5K
0.3
McCoy&Wu (‘78)

Intensity (arb units)

L = 0.00(5)

Schrödinger’s equation m m 0.2

2

3
0.1 4
5

0.0
1.0 1.2 1.4 1.6
kinetic energy string tension Energy (meV)

=> bound states

0.5
Ai(z)

-0.5
Airy function
-10 -5 z 0 5 zn = 2.33, 4.08, 5.52, 6.78…
Phenomenological model of soliton gas
- work perturbatively around the Ising limit
(spin clusters)
J ↑↑↑↓↓↓↑↑
• • 2-soliton states

↑↑↑↑↑↑

H ↑↑↑↓↓↓↓↓↓↑↑ a 2 soliton state

=J ↑↑↑↓↓↓↓↓↓↑↑ from Ising J Siz Si+1

z gap

-a ↑↑↑↓↓↓↓↓↓↓↑ +… soliton hopping

-b d n,1 ↑↑↓↑↑ + ↑↑↓↑↑ from XY term kinetic bound state

i+1 i-1

RC et al, Science 327, 177 (2010)

- Jxy ( Six Si+1
x + Sy Sy
i i+1
) ~ S + S- + S - S+
i i+1 i i+1
 Phenomenological model of soliton gas describes full spectrum

T = 40 mK

Gap: J ~ 1.94 meV from Ising zz exchange

Bandwidth a = 0.12 J domain-wall hopping term ↑↑↑↓↓↓↓↓↓↑↑

[ microscopic origin SzSx … ?]

Kinetic bound state : transverse couplings for nn bond SxSx + SySy , J ┴/ J z = 0.24
and 2-nd neighbour AFM along chain J z' = - 0.15 J z
Weak confinement term: hz ~ 0.02 J longitudinal field includes interchain mean-field
numerical calculation agrees with exact analytic solution of effective Hamiltonian
S.B. Rutkevich, J. Stat. Phys (2010)
 Experiments in applied transverse field
0T 3.25 T 4T

Energy
Gap decreases wavevector
with field
B - field tunes quasiparticle dispersion
z
t CoNb2O6
Field ~ kinetic energy
torque crystal

↑↑↑↓↓↓↓↓↓↑↑
• • BxSx = (S++S-)/2
Place crystal in metallic cage to
prevent movement under high torque
Excitations as a function of transverse field
4T Magnetic 3D LRO 6T 7T
Bragg peak

Two-soliton states Single sharp

Ordered Paramagnetic
mode
1000

↑↑↑↓↓↓↓↓↓↑↑ →→←→→ 800

Intensity (a.u.)
600

Excitations change 400

character above 200

critical field 0

0.5 1.0 1.5 2.0

Energy(meV)
 Excitations in
transverse field

2-soliton continuum
RC et al, Science 327, 177 (2010)
 Summary
- realized experimentally field-tuned quantum phase transition in
quasi 1D Ising magnet CoNb2O6

- observed transmutation of quasiparticles at critical point

ordered paramagnet
2-soliton
states spin-flip
→←→
 Conclusions
- neutron scattering is a very versatile probe of magnetic ordering and
dynamics (meV->eV, magnetic field (15 T->25 T), low T (mK)
- quantitative: probe dispersions of excitations through well-
understood matrix element (quantitative comparison with theories)
- sample size limited, large crystals needed (advanced crystal growth)
- new neutron sources (ISIS 2nd target station, USA + JAPAN, ESS) will
bring new opportunities: higher flux, higher resolution, wider coverage

50 detectors, 40,000 detectors,

2D data set 4D data set, 4
energies measured
simultaneously,

- complementary to resonant x-ray diffraction and inelastic (RIXS)

(samples 10’s of mm, resolution >30 meV, T > few K – beam heating)
 Collaborators
La2CuO4
S.M. Hayden (Bristol),
G. Aeppli (UCL)
T.G. Perring(ISIS)
C.D. Frost (ISIS)
T.E. Mason (Oak Ridge)
S.W. Cheong (Rutgers)
Z. Fisk (Florida)
Cs2CuCl4
D. A. Tennant (HZB)
A.M. Tsvelik (Brookhaven)
K. Habicht, P. Smeibidl (HZB)
Z. Tylczynski (Poland)
Y. Tokiwa, F. Steglich (Dresden)
CoNb2O6
D.A. Tennant, (HZB Berlin)
Elisa Wheeler (Oxford)
Ewa Wawrzynska (Bristol)
M. Telling (ISIS)
K. Habicht, P. Smeibidl, K.Kieffer (HZB)
D. Prabhakaran (Oxford)
Ivelisse Cabrera (Oxford)
Jordan Thompson (Oxford)
R. Bewley, T. Guidi (ISIS)
C. Stock, J. Rodriguez-Rivera (NIST)
F. H.L. Essler, N. Robinson (Oxford)