Polaronic transport in solids:

Some recent results using the

Dynamical Mean Field Theory
S. Fratini, S. Ciuchi
experimental framework and overview of standard theories
DMFT results (almost analytical)
a few tentative applications: titanates and vanadates

Landau (1933): phenomenological model, electron-phonon interaction

the electron polarizes the medium, that deforms and traps it

Frhlich (1954): microscopic model, long range e-ph interaction

with LO modes
=> large polarons (hydrogenic states, Rp>>a)

A (very) brief History of polarons

What if the polaron size Rp~a ?

experimental problem: resistivity of NiO, CoO, MnO
(Yamashita et Kurosawa 1954, Heikes et Johnston 1957)
thermally activated behavior, but fixed number of carriers

Activated Conductivity
=ne/m=A exp (-/kT)
1) semiconducting gap:
carrier density is activated

2) interactions:
carrier mobility is activated

Ep
polaron trapped on a site:
hopping transport
untrapping energy Ep

Morin (1954)

Small polaron transport has since been reported in:

almost every transition metal oxide:
NiO, MnO, CoO, CuO, ZnO, LaCoO3 ...
Fe3TiO4, TiO2, SrLaTiO3, SrLaVO3 ... (titanates, vanadates)
LaCaMnO3, Tl2Mn2O7... (manganites, pyrochlores)
atomic and molecular solids:
Ne, Ar, Kr, Xe...
N2,O2,CO...
biological and organic compounds:
DNA, TCNQ, oligoacenes (pentacene, anthracene, etc.) ...
other
NiCuS2, NiSSe ...

Holstein model (1959)

Solid = lattice of deformable molecules,

(electronic level if occupied)

E0

E1

tight binding electrons : - t c+icj

optical bosons (phonons, excitons...): 0 a+iai
local interaction: g (a+i+ai) c+ici
2 dimensionless parameters
=0/t

adiabaticity :
<<1 fast electrons, slow phonons
(ordinary solids)
>>1 fast phonons, slow electrons
(narrow band solids)

=g/0t or =(g/0)
interaction strength:
polarons if

>1 (<<1)
>1 ( >>1)
+ density (take n independent polarons)
+ temperature...

we are left with:

2 (adiabatic/nonadiabatic)
x 2 (strong/weak coupling)
x 3 (low, room, high temperature)
-----------------------------------------------------= 12 different regimes !
i.e. basically 12 different theoretical approaches...

but:
people are mainly interested in the strong coupling regime, at RT
=> 2 formulas are sufficient (adiabatic/nonadiabatic)
=> both appear in the original paper by Holstein (1959)

1) adiabatic regime 0<<t

(low energy phonons)
transport is dominated by
the slow d.o.f. (phonons)

p/2

0
site i

2) nonadiabatic regime 0>>t

(extremely narrow bands,
or AF phases)
transport is dominated by
the slow d.o.f. (electrons)

long and involved calculation

+ divergent result,
to be regularized ad hoc

site i+1

Landau- Zener WKB theory:

Arrhenius law : w~0 exp (p/2kT)
Einstein relation ad=AT exp (p/2kT)
derived in a two- site model, who knows
what happens in an infinite lattice?

anti=AT3/2 exp (p/2kT)

inconsistent regularization: assumes strong
phonon dispersion, but initial model has
Einstein phonons (local)

Open questions (an arbitrary selection)



many polaron theory -> individual single polarons

transport, 2 main experimental problems:

1) simple Arrhenius law always fails at low T
2) Holstein's theory fails to explain self- consistently
d.c. transport and optical absorption data:
microscopic parameters extracted from d.c.
resistivity are inconsistent with ()

examples: 1) failure of pure Arrhenius behaviour

the data fit nicely to eq. (1)
LaSrMn2O7, Chatterjee PRB2003

can be fitted according to eq. (2)

LaTiO3.41, Kuntscher PRB2003

some easier transport channel appears at low T

VRH ? exp (T-)
coherent (band) motion of small polarons?
often, magnetic transitions at low T

Coherent band motion at low T

Instead of hopping incoherently, the electron can tunnel coherently
to any quantum state of equivalent energy, and form a band
(need quantum phonons)

no phonon scattering up to 0 , exp (- 0/kT)

in principle dominates at low temperature


BUT t* is exponentially reduced, very sensitive to disorder

There are only a few reports of this low T regime in the

small polaron literature (but very common for large polarons):
-

LaTiO3.41, Kuntscher PRB2003 (could be LP)

LaCaMnO3, Zhao PRL2000 (within FM phase, t enhanced)
naphthalene, Schein PR78 (+ Schn...)
NiS2-xSex, Kwizera PRB80

1/T

more examples:
Pr2CuO4, Homes PRB 2002

LaTiO3, Lunkenheimer PRB 2003

more examples:
La0.66Ca0.33MnO3 films, Jaime PRB 96
Tc=238K

La1.2Sr1.8Mn2O7, Chen PRB2003

Tc=125K

examples: 2) inconsistency with optics

BaTiO3, Iguchi PRB91

BaTiO3, Berglund PR67

d.c.=68meV

opt=450- 600 meV

(d.c.)=Ep/2
(opt)=2Ep

(d.c.)
Standard theory predicts:
=4
(opt)

here ~ 8

Dynamical mean field theory (DMFT)

mean field (ordinary):
isolate a particle, the rest of the system is described by an effective
field h to be determined self- consistently
(average on space AND time)
h
mean field (dynamical):
idem, but h(t) is time dependent (average on space only)
- becomes exact infinite dimensions
- excellent approximation d=2,3 systems
for local phenomena
(Holstein polaron: OK)
- analytical solution
if n independent polarons
(Ciuchi, Feinberg, Fratini, De Pasquale 1996)

h(t)

G()

The DMFT loop



Numerical (QMC,ED, NRG)

Analytical

impurity propagator

lattice propagator

Single polaron DOS & damping

Weak coupling
weakly renormalized DOS distribution
low energy coherent part
high energy weakly incoherent part

Single polaron DOS & damping

Strong coupling
low energy coherent peaks (the first is the "polaron" band)
low- intermediate energy resonances
high energy broad incoherent continuum

Calculation of resistivity (Kubo formula)

Boltzmann statistics

units: ohm cm

2 approximations:
- dynamical mean field
- independent polarons

spectral function (cf. ARPES)

BUT

no small parameter :
- valid for any t, 0, g
- at all temperatures T

Pros:
one can treat both
- phonon quantum fluctuations (00): access low T regime
- electronic dispersion (t0): no need for ad hoc regularization
(+ 1 theory instead of 12 different approximations)

Cons:
Analytical method but final integral is numeric,
no direct formula for (T)
(still searching a general formula, found one in nonadiabatic regime...)

DMFT results: 3 regimes

I

II

III

=10
increasing

I. coherent motion T<0

III. residual scattering T>Ep

tunneling with large eff. mass

T/

A exp (- 0/kT)

II. activated behavior 0<T<Ep

= exp (/kT)

Analytical formula in nonadiabatic regime

At large =0/t the resistivity obeys:
The DMFT data are well described by:

y=T/0

Activation gap:
sensibly reduced: d.c=1/2 Ep
temperature dependent !

3/8 Ep (solve mismatch with optics ?)

(downturn of Arrhenius plots at low T)

Onset of phonon quantum fluctuations:

a ROBUST precursor to the low T coherent motion (not destroyed by disorder).

Tentative application: titanates

fit yields
Ep=200meV

polaron absorption should be

at 2Ep = 400meV = 3200cm
+ independent estimate of 0=130cm

Tentative application: vanadates

Tokura, PRB95

peak position according to DMFT fit

peak position according to Arrhenius fit

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Concluding remarks
0

Small polarons are quite common in oxides (but not only)

Standard theory by Holstein often fails to describe self- consistently

d.c. transport and optical absorption experiments
2

The mismatch is due to inconsistencies in the standard

approximations (ad- hoc regularization, two-site model)
3

DMFT seems to go in the right direction:

- enhancement of conductivity at low T, deviations from Arrhenius
related to phonon quantum fluctuations
- reduction of polaron energy extracted from experimental data
related to weak dispersion of optical phonons (local)
restore agreement with ()

work in progress (long term): systematic reanalysis of experiments

(contact with experimentalists needed...)

Note:
The theoretical inconsistencies pointed out here were clearly stated
in Holstein's original work in 1959.
The scientific community does not seem to be aware of such
inconsistencies.
Holstein's paper has been cited 1496 times to date.