Molecular Electronics

The advances in nanofabrication techniques have made possible to study the electronic transport through single atoms and molecules, which has given rise to the field of Molecular Electronics. Electronics

1950

1980

1990

2000

Fundamental issues: issues

New physical phenomena Potential applications

Molecular Electronics: Electronics: Experimental techniques

1 Scanning tunneling 1. l microscope 2. BreakB Break kjunctions

3 Electrochemical methods 3.

4 Electromigration 4.

Molecular Electronics: Electronics: Functional structures

1. Diode: Diode: Au-SAM-Ti-Au (Nanopore)
4-thioacetatebiphenyl, M. Reed, APL (1997)

2. Swicht Swicht: h : Nanopore N (60 K) )

M. Reed et al., Science (1999)

3. Reconfigurable Swicht: Swicht: Catanane

J.R. Heath et al., Science (2000)

4. SingleSingle-electron transistor:
Park et al., Nature (2002).

Molecular Electronics: Electronics: Scaling and integration

HP P invent: nanoscale l molecular-swicht l l h crossbar b circuits (2003) ( )

SAM between metallic nanowires

[2]rotaxenes

Crossbar (Pt/Ti) Imprinting lithography

Molecular electronics: Goals for the theory

Understanding of the transport mechanisms at the molecular scale. Quantitative description of the transport properties. properties

Outline of this lecture

1) Coherent transport through single-molecule junctions. 1.1 Landauer approach: relation conductance-transmission. 12S 1.2 Some e le lessons from f toy t models. del 1.3 Greens functions. 1.4 Ab initio methods: density y functional theory. y 1.5 Validity of the coherent picture. 2) Single-molecule Single molecule transistors: Coulomb blockade. blockade 2.1 Experimental motivation. 2.2 Coulomb blockade regime: rate equations. 3) Inelastic current: role of the vibration modes. 3 1 Experimental motivation. 3.1 motivation 3.2 Simple theoretical model: Different transport regimes. 3.3 First-principle calculations. 4) Other topics, challenges and open problems.

References
A. Nitzan, Ann. Rev. Phys. Chem. 52, 681 (2001). Quantum Transport: Atom to Transistor, S. Datta, Cambridge University Press (2005). (2005) Introducing Molecular Electronics, Lectures Notes in Physics, Vol. 80, Eds. G. Cuniberti et al., Springer Verlag (2005).

MolecularElectronics: AnIntroductiontoTheoryandExperiment, J.C.CuevasandE.Scheer, tobepublishedinWorldScientific(2010).

1 Coherenttransportthroughsingle 1. moleculejunctions
Reference
M l l El Molecular Electronics: t i An A Introduction I t d ti t toTheory Th and dE Experiment i t, J.C.CuevasandE.Scheer, tobepublishedinWorldScientific(2010).

1.1 Landauer approach to electron transport

[R.Landauer,IBMJ.Res.Dev.1,223(1957)]

real system

electron reservoirs scattering region

EF+eV

EF

L d Landauer f formula l
incoming incoming

NL
outgoing

NR
outgoing

2e 2 G T ( EF ) h

G =conductance;T(EF) =transmission atthe Fermienergy.

1.1 Understanding the Landauer formula

Electronic transport as scattering problem

e J * * evk T (k ) 2mi
Inaso solid d s state a ede device: ce

Current density:

2e I dE T ( E ) f L f R h
G0
Conductance quantum

Li Linear response: I = GV; G = Conductance. C d At A low l temperatures:

G G0T ( EF )
T = Total transmission

2e 2 1 G0 12.9 k h

1.2 Resonant tunneling model

2e I (V ) dET ( E , V ) f L f R h
1 0 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1

Currentformula

4L R 11 00 T ( E ,V ) 00 11 2 2 00 11 [ E ( V )] [ ] L R 0 00 11 00 11 00 11 00 11 R 00 11 [BreitWigner formula] 00 11 00 11 00 11 00 11 0 level position 00 11 00 11 00 11 00 R 11 L R level l l width idth 00 11 00 11 00 11 00 11 00 11

Metal Molecule Metal

1.2 Resonant tunneling model

1.2 Off Off-resonant tunneling: molecules as t tunnel l j junctions ti

Lo bias region : | eV Low V || 0 |

Lowbias expansion: I (V ) AV BV G (V ) A 3BV

3

1.2 Single g molecules as tunnel j junctions

Cui et al. (Lindsays group), Science 294, , 571 ( (2001) )

1.2 Temperature dependence of the current

Wang, Lee and Reed, PRB 68, 035416 (2003)
Voltagedependence: Againatunneljunction!

Currentindependentofthetemperature

CH 3 (CH 2 ) n 1 SH

1.2 Temperature dependence of the current

0 1 eV; L R 2 meV

Offresonanttransport p Tindependent p Onresonanttransport Tdependent (aslongasT>)

1.2 Symmetry of the IVs: Rectification

Molecularrectifiers AriehAviramandMarkA.Ratner ( h (Chem. Phys. h Lett.,1974) )
The construction of a very simple electronic device, a rectifier, based on the used of a single organic molecule is discussed. discussed The molecular rectifier consists of a donor pi system and a acceptor pi system, separated by a sigma-bonded (methylene) tunneling bridge. The response of such a molecule to an applied field is calculated and rectifier properties indeed appear calculated, appear.

(23 yearslater)

R.Metzgeretal.,JACS1997

1.2 Symmetry of the IVs: Rectification

Single-level model: asymmetric coupling

L R eV 0 (V ) 0 2 R L
0 1 eV V
R 20 meV

1.2 Does this toy model work in practice?

Linda A. Zotti, T. Kirchner, J.C. Cuevas, F. Pauly, T. Huhn, E. Scheer, A. Erbe, Small (2010)

1.3 Calculation of the transmission: Greens functions

h c c H ij i j
ij

Atoms

Orbitals

Gi , j (t ,0) i ci (t )c j ( 0 )
Equation of motion?

Greens function

dci (t ) i ci (t ), H dt

r , a ( E ) E i H G
r

H H H V V h.c. H L R C LC RC
Threesubsystems:left(L),right(R)andcenter(C)

(G ) ] relation: [G
a

1.3 Calculation of the transmission: Greens functions

0 HL V LC V H H V CL C CR 0 VRC H R
1 r ,a where ( E ) VC E i H V C

r ,a r ,a r , a ( E ) E i H G C C L R

( L, R) are the self - energies

Im a - - - - scattering rates

Totaltransmission

r ( E ) a (E) ( E )G ( E )G T ( E ) 4Tr T L C R C

T (E) Tr t t Tn n

r 1/ 2 G 1/ 2 2 t L C R
=transmission matrix t

Tn =transmission coefficients

Exercice 1
Derivethe BreitWigner formulafor the transmission through asingle electronic level starting from the generalexpression ofthe transmission.
1 0 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 1 0 0 1 0 1 0 1 0 1 0 1 0 1 R 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 R 0 1 0 1 0 1 0 1 0 1

Hamiltonian: H C 0
a r * Selfenergies: L , R iL , R ( L , R )
Im( a ) Scattering rates: L,R L,R
r , a ( E ) ( E i ) H r ,a r ,a Greens functions: G C C L R

Metal Molecule Metal

Transmission (BreitWigner formula)

r ( E ) a (E) L ( E )G T ( E ) 4Tr E G ( ) C R C

4L R ( E 0 ) 2 (L R ) 2

1.3 Conductance of a hydrogen molecule

R H M Smit R.H.M. Smit, Y. Y Noat Noat, C. C Untiedt Untiedt, N.D. N D Lang, Lang M.C. M C van Hemert, Hemert J.M. van Ruitenbeek, Nature 419, 906 (2002)

The hydrogen molecule forms a stable

b id between bridge b t Pt electrodes. l t d

The conductance is G ~ G0 and it is largely d min t d by dominated b a single sin l conduction nd ti n channel. h nn l

Exercice 2
Derivethe expression ofthe transmission through ahydrogen molecule.

Hamiltonian: H C t H

tH 0
0 a 0 0 ; R 0 0 iR

iL a Selfenergies: L 0

Im( a ) Scattering rates: L,R L,R

,a r , a ( E ) ( E i ) H r r ,a Greens functions: G C C L R

Transmission
2 2 4 tH T ( E ) 4Tr L ( E )G ( E )R ( E )G ( E ) [( E ) 2 2 ][( E ) 2 2 ] r C a C

where

0 tH

(bonding andantibonding states)

1.3 TwoTwo-level model

Bondingandantibondingstates

0 tH

Transmission:
2 4 2t H T (E) [( E ) 2 2 ][( E ) 2 2 ]

1.3 Length dependence of conductance

Wang, Lee and Reed, PRB 68, 035416 (2003) The conductance decays exponentially with the length of the molecule

G G0 e

1.3 NN-level bridge: attenuation factor

2e dET ( E , V ) f L f R I (V ) h

2e 2 G T ( EF ) h
T ( E ) 4L R G1N ( E )
2

Off - resonant tunneling : max(ti ,i 1 ) min(| E i |) G1N

1 E N

E
i 1

N 1

ti ,i 1

homogeneous bridge : ti ,i 1 t and i 4L R t T (E) | t |2 E

2N

e ( E ) L

2 E ( E ) ln a t

a = lattice constant; Na = L

1.3 Role of the conjugation in molecular wires

Influence of the conjugation (two two-ring molecules)

1.3 Role of the conjugation in molecular wires wires: i : origin i i of f cos2

2e 2 G T ( EF ) h
T ( E ) 4L R G1N ( E )
2

Off - resonant tunneling : max(ti ,i 1 ) min(| E i |) G1N

1 E N

E
i 1

N 1

ti ,i 1

In a conjugated molecule, the coupling between different segments is mediated by a hopping element

t t0 cos T cos 2

1.4 Ab initio methods: Density functional theory

HohenbergKohn Theorems: PierreHohenberg The energy of the ground state can be determined from the electron density KohnSham K h h Approach h: Functional: E[] = TS[] + J[] + Eext[] + EXC[] Electron density TS[] exact kinetic energy of a non-interacting system with the same density as the interacting one. J[] classical Coulomb part. Eext (nuclei ). ) t[] external part (nuclei, EXC[] exchange correlation part. BP86: exchange part Becke 1988 and correlation part Perdew 1986

WalterKohn

1.4 Density functional theory

Variational approach leads to KohnSham Equations: FKSji = iji (integro differential equations) (integro-differential

FKS

1 2 (r2 ) ZA dr2 VXC (r1 ) 2 r12 A r 1A

LuJeuSham

Linear combination of local orbitals: ji = n cni n Linear set of equations: FKSC = SC Kohn Sham matrix:

( FKS ) ij i (r ) f KS (r ) j (r )dr

Coefficient C ffi i t matrix: t i (C)ij=cij Overlap matrix:

( S ) ijj i (r ) j (r )dr

Diagonal matrix of the orbital energies

1.4 An example example: : Highly conductive benzene junctions

M. Kiguchi, O. Tal, S. Wohlthat, F. Pauly, M. Krieger, D. Djukic, J.C. Cuevas, and J.M. van Ruitenbeek, Phys. Rev. Lett. 101, 046801 (2008).
Vibration spectroscopy

Shot noise measurements

Exercice 3
Computethe transmission through benzene using asimplenearestneighbors tightbinding model to describethe electrons inthis molecule.

0 2t

L t t t R
1

0 t
4

0 t
0 t

t t t

0 t

(a)Model for the metalbenzenemetaljunction. Hamiltonian:

0 2t
(b)Energy spectrum ofthe molecule Selfenergies:

0 t 0 H C 0 0 t

0 t

0 0

0 0 0 t

0
t 0 0 0

0
t 0 0

0
t 0

0
t

t 0 0 0 t 0

iL if i j 1 ( ) 0 otherwise
a L ij

iR if i j 4 ( ) 0 otherwise
a R ij

Exercice 3
Im( a ) Scattering rates: L,R L,R
,a r , a ( E ) ( E i ) H r r ,a Greens functions: G C C L R

r ( E ) a ( E ) 4 G a (E) L ( E )G R ( E )G Transmission: T ( E ) 4Tr 1, 4 C C L R

Examples: Examples :
T Transmiss ission

0.8

Symmetric junction
0.6
=t = 0.5t = 0.1t

L R

0.4

0.2

0 -3

-2

-1

(E-0)/t

1.4 Electronic structure of benzene: benzene: -orbital system

(LUMO)

(HOMO)

1.4 Possible contact formation of a PtPtbenzenebenzene -Pt junction

1.4 The vibration modes in the relevant energy region

Pt carbon bond stretch mode transverse benzene mode:
4.91 : 405 cm-1 = 50 meV 5.31 : 376 cm-1 = 47 meV 5.71 : 332 cm-1 = 41 meV 6 11 : 278 cm-1 = 34 meV 6.11

Pt carbon bond rotation mode rotation of f the h benzene: b

4.91 : 423 cm-1 = 52 meV 5.31 : 419 cm-1 = 52 meV 5 71 : 414 cm-1 = 51 meV 5.71 6.11 : 408 cm-1 = 51 meV

Distance:5.71

1.4 Conductance and transmission coefficients

1.4 Chemical nature of the conduction through benzene

HOMO1 HOMO2 LUMO1 LUMO2

4.9 A

1.5 1 0.5 0

Ttot T1 1.2 1 T2 T3 0.8 0.6 0.4 0.2 0

0.4 0.2

6.5 A

LDOS (1/eV /eV)

Trans ansmission

0.4 0.2 0 -10 -8

HOMO1 HOMO2 LUMO1 LUMO2

-6

-4

-2

0 0 -10

-8

-6

-4

-2

E (eV)

E (eV)

1.5 Validity y of the coherent p picture

E | 0 EF | injection energy L R level width
Traversal time:

1 0 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1

11 00 00 11 00 11 00 11 00 11 00 11 00 11 00 11 R 00 11 00 11 00 11 00 11 00 11 00 11 00 11 00 11 R 00 11 00 11 00 11 00 11 00 11

/ E 2 2
Energy scales:

e - e : U ; e - ph :
Coherent transport: transport:

min( / U , / )
Incoherent transport transport: :

Metal Molecule Metal

min( ( / U , / )

2 Singlemoleculetransistors: 2. Coulombblockade
REFERENCES
1) Singlemolecule electrical junctions,Y.Selzer andD.L.Allara,Annu.Rev.Phys.Chem.57,593 (2006). 2) Coulombblockade oscillations insemiconductornanostructures,H.vanHouten,C.W.J. Beenakker,andA.A.M.Staring inSingleCharge Tunneling,edited by H.Grabert andM.H. Devoret,NATOASISeriesB294(Plenum,NewYork,1992). 3) Electron transport inquantumdots,L.P.Kouwenhoven etal.inMesoscopic Electron Transport, edited by L.L.Sohn,L.P.Kouwenhoven,G.Schoen (Kluwer 1997).

2.1 Experimental motivation: Three Three-terminal d i devices

2.1 Experimental motivation: Transport characteristics h t i ti of f singlesingle in l -molecule m l l transistors t n i t

Park et al., Nature 407, 57 (2000)

2.1 Experimental motivation: Transport characteristics h t i ti of f singlesingle in l -molecule m l l transistors t n i t

Park et al., Nature 417, 722 (2002)

2.1 Experimental motivation: Transport characteristics h t i ti of f singlesingle in l -molecule m l l transistors t n i t

S. Kubatkin et al., Nature 425, 698 (2003).

2.1 Coulomb blockade: a wellwell-known ph n m n n in mesoscopic phenomenon m pi physics ph i

Metallic islands

2.1 Coulomb blockade: a wellwell-known ph n m n n in mesoscopic phenomenon m pi physics ph i

Nanoparticles

2.1 Coulomb blockade: a wellwell-known ph n m n n in mesoscopic phenomenon m pi physics ph i

Semiconductorquantumdots

2.1 Experimental motivation: Coulomb bl k d ph blockade phenomenology n m n l in carbon b n n nanotubes n t b

S.J. Tans et al., Nature 386, 474 (1997)
(i)Coulomboscillations
(a) (b)

(c)

(ii) ii)Coulombstaircase

(d)

(iii) iii)Caracteristic temperature temperat re dependence

2.2 Basic Coulomb blockade theory theory: : ch charging in effects ff cts

How small and how cold should a conductor be so that adding or subtracting a single electron has a measurable effect?

1) The capacitance C ofthe island (or dot)hasto be such that the charging energy (e2/C)be smaller than the thermal energy (kBT):

e2 / C kBT
2) ) The barriers have to be sufficiently y opaque p q such that the electron arelocated inthe dot:

Et (e2 / C)(Rt C) h Rt h / e2

Inmoleculartransistors these two requirements equ e e s ca canbe eas easily y met!!! e

2.2 Basic Coulomb blockade theory y

Edot ( N ) U ( N ) E p
p 1

E p ( p 1,2, ,...) ) single g - electron energy gy levels

l r p , p tunnel rates

U ( N ) ( Ne) 2 / 2C NeVext

C C S C D CG
Vext CSVS CGVG C DVD / C

k BT , E h( l r )

2.2 Basic Coulomb blockade theory

Periodicity ofthe oscillations oscillations: :
P(N)=Probability to find Nelectrons inthe quantumdot. dot
1 [ ( ) ] F N NE Equilibrium P ( N ) constant exp F ; F ( N ) free energy k T B Anecessary condition to have afinite conductance is:

P( N 1) P ( N ) F ( N 1) F ( N ) EF
AtT=0the freeenergy F(N)equals the ground state energy ofthe dot:

F ( N ) U ( N ) E p ; where U ( N ) is the electrostatic energy

p 1

Therefore,

E N U ( N ) U ( N 1) E F

2.2 Basic Coulomb blockade theory

Constant interaction model:the electrostatic energy is taking into account macroscopically: Ne U ( N ) (Q)dQ, where (Q) Q/C ext
0

Assuming that the capacitance C is independent ofN anddefining Qext =Cext:

U ( N ) ( Ne) 2 / 2C Neext U ( N ) ( Ne Qext ) 2 / 2C constant

Thus,the condition for afinite conductance is:

e2 E N ( N 1 / 2) EF eext C
So,finally the periodicity ofthe oscillations (fixing ext andchanging EF)is given by:

e2 EF E C

(E level spacing) p g)

2.2 Basic Coulomb blockade theory y

Amplitude andlineshape ofthe oscillations oscillations: :
Different tunneling processes (energy conservation):
state p in the dot (N electrons) - - left lead at energy E f ,l ( N ) : E f ,l ( N ) E p U ( N ) U ( N 1) (1 )eV left lead at energy E i ,l ( N ) - - state p in the dot (N electrons) : E i ,l ( N ) E p U ( N 1) U ( N ) (1 )eV state p in the dot (N electrons) - -- right lead at energy E f ,r ( N ) : E f ,r ( N ) E p U ( N ) U ( N 1) eV right lead at energy E i ,r ( N ) - -- state p in the dot (N electrons) : E i ,r ( N ) E p U ( N 1) U ( N ) eV

Stationary current through the left barrier:

l I e p P({ni }) n p ,0 f ( E i ,l ( N ) EF ) n p ,1[1 f ( E f ,l ( N ) EF )] p 1 {ni }

2.2 Basic Coulomb blockade theory y

Inequilibrium the probability distribution P({ni}) is given by the Gibbs distribution inthe grand canonicalensemble:
1 1 Peq ({ni }) exp Ei ni U ( N ) NE F ; Z partition function Z k T B i 1

The nonequilibrium probability distribution P is astationary solution ofthe kinetic equation: q

r l P ({ni }) 0 P ({ni }) n p ,0 [p f ( E i ,l ( N ) EF ) p f ( E i ,r ( N ) EF )] t p
l r P({ni }) n p ,1[p (1 f ( E f ,l ( N ) EF )) p (1 f ( E f ,r ( N ) E F ))] p l r P(n1 , , n p 1 ,1, n p 1 , ) n p ,0 [p (1 f ( E f ,l ( N 1) EF )) p (1 f ( E f ,r ( N 1) EF ))] p l r P(n1 , , n p 1 ,0, n p 1 , ) n p ,1[p f ( E i ,l ( N 1) EF ) p f ( E i ,r ( N 1) E F )] p

2.2 Basic Coulomb blockade theory

eV ({ni }) k BT The joint probability that the quantumdot contains Nelectrons andthat the level is occupied is: Peq q ( N , n p 1) P eq q ({ni }) N , ni n p ,1 i {n }

Linearresponsetheory theory: : P({ni }) Peq ({ni }) 1

Interms ofthis probability the conductance is given by:

e2 G k BT
Limit:

p 1 N 1

l r p p l p

r p

Peq ( N , n p 1) 1 f ( E p U ( N ) U ( N 1) EF )

G / Gmax Gmax

k BT e 2 / C , E

min / k BT 2 min cosh h sinh( min / k BT ) 2.5k BT

e2 l r 2E l r

2.2 An example example: : Coulomb oscillations and d staircase t i

E1 EF 50 meV; E2 EF 80 meV E 30 meV; e 2 / C 100 meV T 30 K; K 1 meV; V 0.6

2.2 An example example: : Stability diagrams and Coulomb C l b diamonds di d

3.Inelasticcurrent:roleofthevibration modes
Reference
M l l El Molecular Electronics: t i An A Introduction I t d ti t toTheory Th and dE Experiment i t, J.C.CuevasandE.Scheer, tobepublishedinWorldScientific(2010).

3.0 Molecular vibrational modes: a reminder

Molecularspectra:electronic states +vibrational modes +rotational levels.

3.1 Experimental motivation: Inelastic electron tunneling spectroscopy (IETS)

B.C. Stipe, M.A. Rezaei, and W. Ho, Science 280, 1732 (1998).

Example:STMstudy ofacetylene (C2H2)on Cu(100).

3.1 Experimental motivation: Point contact spectroscopy (PCS) of gold atomic chains
N. Agrat, C. Untiedt, G. Rubio-Bollinger, S. Vieira, Phys. Rev. Lett. 88, 216803 (2002).

3.1 Experimental motivation: Point contact spectroscopy (PCS) of Pt Pt-H2-Pt junctions

R.H.M. Smit, Y. Noat, C. Untiedt, N.D. Lang, M.C. van Hemert, J.M. van Ruitenbeek, Nature 419, 906 (2002)
2 dG/dV (a a.u.) Diff ferential c conductance /h

0,95

0,94

0,93

Pt H H
0,92 0,04 0,03 0,02 0,01 0,00 -0,01 -0,02 -0,03 -0,04 -0,05 -100 -50 0

Pt

63.5 mV

- 63.5 mV

50

100

Bias voltage (mV)

Measurement of the conductance of a hydrogen molecule between Pt leads with the break-junction technique

3.1 Experimental motivation: motivation: Pt Pt-benzene benzene-Pt junctions

M. Kiguchi, O. Tal, S. Wohlthat, F. Pauly, M. Krieger, D. Djukic, J.C. Cuevas, and J J.M. van R Ruitenbeek k, Phys. y R Rev. Lett. 101, , 046801 ( (2008) )

Signature ofthe vibration modes: step upinthe conductance.

3.1 Experimental motivation: Resonant inelastic electron tunneling (RIETS) in singlesingle-molecule transistor

Nature 407, 407 57 (2000). (2000)

3.1 Signatures of vibrational modes modes: : a summary

3.2 Inelastic current: singlesingle-phonon model

eV
H e ph c c (b b)

electron-phonon coupling constant energyofthevibrationmode

Metal Molecule Metal

I I elastic I inelastic
Need of approximations: Weak ee-ph interaction lowest lowest-order perturbation theory p y( (LOE) )

[Keldysh formalism]

2 2 2e 2e r r I el dE 4L R G ( E ) ( f L f R ); I in (2iL ) dE G ( E ) f L (1 f L ) h h

(0)

( E 2 2 )

(0)

3.2 Weak ee-ph interaction: tunneling processes

(a) Elastic process eV (b) Phonon absorption h eV

L 0 R

L 0 R

Metal Molecule Metal

Metal Molecule Metal

(c) Phonon emission h eV

(d) Elastic correction h eV

L 0 R

L 0 R

Metal Molecule Metal

Metal Molecule Metal

3.2 Simple model: high high-transparency limit

0 EF 0.0; 2 ; L R 10

3.2 Simple model: low low-transparency limit

0 EF 80 ; 2; L R 10; k BT 0.05

3.2 Simple model: model: PCS PCS-IETS crossover

2 ; L R 10 ; k BT 0.05

3.2 Simple model: arbitrary transparency

M. Paulsson, M P l T Frederiksen, T. F d ik and d M. M Brandbyge, B db Ph Rev. Phys. R B 72, 72 201101 (2005). (2005) L. de la Vega, A. Martin-Rodero, N. Agrat, and A. Levy Yeyati, Phys. Rev. B 73,075428 (2006) . Neglect g the energy gy dependence p of the elastic transmission.

Symmetric contact : L R
Transmission : T 2 G
2

The inelastic correction to the conductance step at low temperatures is given by

Gstep
G

2 T (1 2T ) 2

G Step up

T 1/ 2

Step down

T 1/ 2

eV

eV

3.2 Confirmation of the simple p model: model: transport through water molecules
O. Tal, , M. K Krieger, g , B. Leerink,and k, J.M. van R J Ruitenbeek, k, Phys. y R Rev. Lett. 100, , 196804 ( (2008) )

Pt-water-Pt junctions: Conductance histogram

Inelastic electron tunneling spectroscopy

3.2 Intermediate ee-ph interaction: resonant phonon emission p

See for instance M. Galperin, A. Nitzan, M.A. Ratner, Phys. Rev. B 73, 045314 (2006) Theoretical method: Equation ofmotion

( E 2 2 )
Resonant phonon emission

0.01 eV; L R 0.02 eV; 0 2 eV; T 10 K; 0.2 eV

3.2 Strong ee-ph interaction: phonon sidebands

See for instance S. Braig and K. Flensberg, PRB 68, 205324 (2003)
Rateequations:

( E 2 2 )

3.3 Inelastic transport in gold atomic wires

T. Frederiksen, M. Brandbyge, N. Lorente, A.P. Juaho, PRL 93, 256601 (2004)
L = 12.22 2.89 2.86 2.73 2.89 2.89 2.74 2.86 2.73 2.89

(a)

ABL mode:

L = 12.68 2.89 2.92 2.84 2.89 2.83 2.92 2.84 2.89 2.89

(b)

L = 12.22 L = 12.68

-20

Primary ABL: Secondary ABL:

= 10.0 meV G/G(0V) = 0.4% = 8.2 meV G/G(0V) = 0.2%

Bias voltage [mV]

-10

10

20

30

Method: DFT + Self-consistent Born approximation

dG/dV dV [(G0V) ) ]

= 13.4 meV G/G(0V) = 0.4%

1 0.99 0.98 0.97 2 1 0 -1 -2 -30

G [G0]

-1

3.3 Inelastic transport in gold wires

J.K. Viljas, J.C. Cuevas, F. Pauly, M. Hfner, Phys.Rev. B 72 ,245415 (2005)
L

T
a /2
(a) L (b) L (c) L (d) T (e) T (f) T (g) L (h) T

L T

T T
Ginel Gec

L
(a)

a /2
16.4 meV 13.1 meV 11.8 meV 7.1 meV 6.8 meV

(h)
0

Gine /G and Gec/G0 inel 0

-0.01
G(V (V)/G0

1
2

0.98

(2e /h)T0 (g) (b) (a)

-0.02

0.96

T = 0.01 K
0.94 0 10 20 30

4.9 meV 4.2 meV 2.6 meV

-0.03 0

Voltage (mV)

10

15

Voltage (mV)

Method:TB + LOE

3.3 IETS in organic molecules

Experiment: J.G. Kushmerick et al. Nano Lett. (2004).

C osswires Cross es tunnel junctions

Theory: T. Frederiksen et al., Nano Lett. (2006) PRB (2007). (2006); (2007)

Method: DFT + LOE

4.Othertopics, topics challengesandopen problems

4.1 Missing g in this lecture

Electronic correlation effects:Kondophysics. Other transport properties: i)shot noise,etc. Thermal transport: i)thermal conducance ii)heating iii)thermopower Optical properties ofcurrentcarrying molecularjunctions: i)Raman scattering ii)lightinduced currents iii)electroluminiscence iv)optoelectronic devices Electronic transport inlong molecules (like DNA):hopping regime.

4.2 Challenges g and open p problems p

Quantitative agreement with experimental results in the different transport p regimes. g Development of new methods to describe the transport through molecular junctions with strong electronic correlations. Development of transport theories able to describe the chemical and conformational changes induced by a finite bias voltage. More extensive work on gating on molecular junctions. Understanding U d t di heating, h ti heat h t conduction d ti and d thermoelectric th l t i properties. ti Characterizing transport junctions behavior in the presence of radiation. Transition between coherent and incoherent transport in long molecules. Elucidating the change in behavior from a single molecule conductance through junctions comprising a few molecules to molecular film conductors.

Collaborators
Universidad Autnoma Madrid Linda Li d A A. Zotti Z tti Stefan Bilan Universitt Karlsruhe Janne J K. K Viljas Vilj ( (now i in TKK) Fabian Pauly Sren Wohlthat (now in Sidney) Michael Hfner Rice University y Dan Ward Douglas Natelson

University y of Leiden Universitt Konstanz Manu Kiguchi Thomas Kirchner Oren Tal Artur Erbe Darko Djukic Elke Scheer Michael Krieger Jan M. M van Ruitenbeek