Volborthite Cu3 V2 O7 (OH)2 2H2 O: Orbital ordering on a distorted kagome geometry

O. Janson1 , J. Richter2 , P Sindzingre3 and H. Rosner1 .

fur Chemische Physik fester Stoffe, Dresden fur Theoretische Physik, Universitat Magdeburg 3 Laboratoire de Physique Theorique de la Matiere Condensee, Universite ` Pierre et Marie Curie, Paris
2 Institut
J1 Jic J2
b a

1 Max-Planck-Institut

Jic J1 J2

27.10.2009
O. Janson, J. Richter, P Sindzingre, H. Rosner . volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Motivation

or magnetic frustration

spin-liquid ground state

S (S + 1)
low dimensional geometry

quantum uctuations

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Motivation
Geometrical frustration Frustration due to competing interactions

triangular lattice honeycomb lattice pyrochlore lattice kagome lattice J1 J2 chain frustrated square lattice anisotropic (triangular,

pyrochlore etc.) lattices

Quantum uctuations Cations with localized spin-1/2: Cu2+ , V4+ , Cr5+ ...
O. Janson, J. Richter, P Sindzingre, H. Rosner . volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Motivation

herbertsmithite Cu3 Zn(OH)6 Cl2

ideal geometry Cu/Zn disorder

Cu2+ kagome systems

volborthite Cu3 [V2 O7 ](OH)2 2H2 O

distorted

kapellasite Cu3 Zn(OH)6 Cl2 haydeeite Cu3 Mg(OH)6 Cl2

ideal geometry additional coupling Jd

vs.

geometry
clean samples

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Volborthite Cu2+ [V2 O7 ](OH)2 2H2 O 3

a candidate for the realization of

a spin-1/2 kagome Heisenberg AFM

experiments ((T ), cp (T ), M(H),
51 V

NMR, SR)
no long-range magnetic ordering frustration (Tmax =21 K, CW =115 K) partial spin freezing below 2 K mysterious magnetization steps

theory: pure and slightly distorted

kagome models
no clear physical picture

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Crystal structure

At a rst glance looks like a slightly distorted kagome layer...

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Crystal structure

Cu(1) 2+4

Cu(2) 4+2

...but crystal chemistry is different from our expectations:

different types of distortion for Cu(1) and Cu(2)

orbital physics? dimensionality?

coupled edge-sharing chains

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Crystal structure

Cu(OH)2

V2 O7 CuO2 (OH)2

H2 O

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Method

DFT calculations (fplo8.00-31) LDA calculations DOS, band structure Tight-binding model (tting the LDA band structure) extended Hubbard model Heisenberg model (J AFM ) Total energy LSDA + U calculations (supercells) = orbital patterns orbital GS = spin patterns J = J AFM + J FM Exact diagonalization full, N=18, 24 (T ) sparse, N=18, 24, 36 Si Sj , M(H)

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

LDA: band structure

Strong hybridization of Cu 3dx 2 y 2 and 3d3z 2 r 2

6 bands at F instead of 3 = 2 orbitals per Cu atom

2D (tiny dispersion along Z, to kagome planes)

O. Janson, J. Richter, P Sindzingre, H. Rosner . volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

LDA: orbitals
Cu(1) (2+4):
8 Cu(1) total Cu(1) 3dxy Cu(1) 3dxz Cu(1) 3d3z2-r2 Cu(1) 3dyz Cu(1) 3dx2-y2 4 8

Cu(2) (4+2):
Cu(2) total Cu(2) 3dxy Cu(2) 3dx Cu(2) 3d3z2-r2 Cu(2) 3dyz Cu(2) 3dx2-y2 4

DOS (states / eV / cell)

DOS (states / eV / cell) 0

-2

-1 energy (eV)

-2

-1 energy (eV)

strong hybridization of Cu 3dx 2 y 2 3d3z 2 r 2 close to half-lling

and 3d3z 2 r 2 orbitals

considerable hybridization of Cu 3dx 2 y 2 close to half-lling

3dx 2 y 2 and 3d3z 2 r 2 orbitals

What do correlations change?

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

LSDA+U: magnetic orbitals

Cu(1) Cu(2)

energy (eV)

1
standard cuprate scenario

Energy cost per Cu atom: Cu(1) 0.7 eV Cu(2) 1.2 eV Orbital order
Exchange integrals?

0
Cu(1) Cu(2)

GS

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

LSDA+U: exchange integrals

J1 Jic

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

LSDA+U: exchange integrals

J1 Jic

AFM FM AFM Where is the frustration?

O. Janson, J. Richter, P Sindzingre, H. Rosner . volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Possible origin for frustration

FM AFM

volborthite

LiCu2 O2 Li2 ZrCuO4 CuCl2

frustrated chains with FM J1 and AFM J2

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

LSDA+U: exchange integrals

J1 Jic J2

|J1 | 0.5Jic J2 |J1 |

2D network with NNN frustration (FMAFM chains)

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Phase diagram of the J1 J2 Jic model (ground state)

2.25 2.0 1.75 1.5 1.25 1 0.75 0.5 1 2 3 4 Jic/|J1| 5 6 7
0.5 0 0.5 0.5

0
0.5

S0 SR
S0 SR
quantum classical

singlet GS

J2/|J1|

0.5

0.5 0.5

S0 SR
0

0.5

GS with S > 0

AMF

FLL

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Ground state of the J1 J2 Jic model

thermodynamics (N=18) is strongly affected by nite size effects (NNN couplings), work for larger clusters (N=24) is in progress classical GS:

singlet GS

quantum GS: LSDA + U results are close to the phase transition crystal structure data are crucial accurate choice of parameters for LSDA + U calculations is necessary short range order for the spin-spin correlation functions does not contradict to experiments

O. Janson, J. Richter, P Sindzingre, H. Rosner .

volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Summary and outlook

geometrical distortion unique orbital ordering new microscopic model frustration originates not from the NN, but from the

NNN couplings
volborthite is far from the original kagome model

Outlook:
results sensitive to OH distance

better structural data (neutron diffraction)

pressure NMR in high magnetic eld

We acknowledge fruitful discussions with Z. Hiroi, O. Cepas, G. Nielsen, S.-L. Drechsler, D. Kasinathan and A. Tsirlin.

Thank you for your attention!

O. Janson, J. Richter, P Sindzingre, H. Rosner . volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome

Picture to take home

b a
O. Janson, J. Richter, P Sindzingre, H. Rosner .

Jic J1 J2
volborthite Cu3 V2 O7 (OH)2 2H2 O distorted spin-1/2 kagome