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Application of Electron Propagator Theory

To Simulation of Electron Transport

Through Molecules
Aleksey Kletsov and Yuri Dahnovsky
University of Wyoming
Electron Transport Through Channel
(Single Level) in Nanoscale Device
Steady-state electron
transport through channel:
q 1 2
I= [ f 1( ) - f 2( )]
h 1+ 2

1/h , 2/h - rates of electron escaping from the level into

the source and drain contacts respectively
f1 , f2 - Fermi functions of the source and drain contacts
q charge of electron, energy of the level
Level Broadening = Coupling
Coupling to the
electrodes (determined
by couplings, )
broadens the energy
level spreading it
outside the energy
range between 1 and
2 where current flows
1 and 2 - chemical
Electron Propagator Theory
Ab initio many-body formalism for calculations of
electronic structure of molecules that accounts for
electron-electron correlations in molecules
Propagator, GPQ (t,t ) P(t); Q(t ) double-time
Greens Function (solution of Schrdinger's equation)
defining a systems response (such as binding
energies) to a perturbation
P(t), Q(t) operators in Heisenbergs representation
Propagator in energy domain (matrix representation):
G (E) (u | ( EI H ) u)
E energy, H Hamiltonian of system, u vector of
field operator
Electron Propagator
(One-) Electron Propagator propagator GPS(E) with
operator P = a+(creation) and Q = a (annihilation), and
the initial and final states differing by only one electron:
0 N | ar | n N 1 n N 1 | as | 0 N 0 N | as | m N 1 m N 1 | ar | 0 N
Grs (E)
n E En (N 1) E0 (N) n E Em (N 1) E0 (N)

Poles of electron propagator: Ionization Energies, En(N-

1) E0(N), and Electron Affinities, E0(N) + Em(N+1)
Residues (Feynman-Dyson Amplitudes) for poles:
U iIE,n n N 1 | as | 0 N
N 1
,m m | a r | 0 N
Hamiltonian of Molecular Junction
H = H M H LM +H RM +H L +H R
HM Hamiltonian of the molecule
H(L,R)M Hamiltonian of the left (right) contact
HL,R Hamiltonian of the left (right) electrode
Current: From Single Level To Molecule

q 1 2
I= [ f 1( ) - f 2( )]
h 1+ 2

f L (w) f R (w)Tr G G
e dw
J= R r L a

h 2
Single energy level, Hamiltonian of system, H
fL,R Fermi function of the left (right) electrode
L, R coupling matrix of the left (right) electrode
Gr,a retarded (advanced) Green's function
Greens Function for Molecule
G(w) = + (|l l |)
l w l

l l-th Dyson orbital

l Dyson pole energy (electron binding energy:
electron affinity or ionization energy) of l-th Dyson
al Dyson pole strength (sum of squared coefficients
in l-th Dyson orbitals expansion, |l = d k |k atomic )
Dyson Orbital Expansion
Dyson orbital - correlated molecular orbital (linear
combination of Hartree-Fock canonical
molecular/atomic orbitals)

|l = d k |k atomic
|k atomic k-th atomic orbital

dk expansion coefficient of k-th atomic orbital

Electric Current: Working Formula
e (l ) (l )al
J L [ f ( ) f ( )]
l (l ) (l )
R L l R l

l and al pole energy and pole strength of the l-th

Dyson orbital
fL,R(l ) - Fermi-functions of the left (right) electrodes

L,R - coupling matrices for the left (right) electrodes

Single Terminal Orbital Approximation
sulfur atomic

gold terminal atomic orbitals

Terminal orbitals electrode's atomic orbitals having

maximum overlap with molecules atomic orbitals
Single terminal orbital approximation only a single gold
atomic orbital in each electrode couples to molecule
Matrices L,R numbers c2L,R(l)L,R(l)
Orbitals Contributions to Current
cL , R (l ) d k (l ) S ( L , R ) k
k 1
cL,R(l) lth Dyson orbitals partial contribution to

dk(l) a coefficient with which the kth atomic

orbital is included into the lth Dyson orbitals
expansion over n atomic orbitals
S overlap matrix element representing coupling
between terminal orbital and kth atomic orbital
Gaussian 03: Computational Output
Computational software Gaussian 03 calculated
electronic structure of molecular junction (1,4-
benzene dithiol molecule attached to gold electrodes):
Dyson pole energies, l
Dyson pole strengths, al
expansion coefficients of Dyson orbitals, dk
overlap matrix elements, S
This output was used to calculate the electric current
through molecular junction by means of derived
working formula
I-V Characteristics of C6H6S2
Negative Differential Resistance
Calculated I-V characteristics exhibit negative
differential resistance
Its mechanism is explained by
voltage dependence of Dyson pole energies and
atomic orbitals contributions to overall current through
molecular junction
Summary and Conclusions
Using ab initio electron propagator theory, formula for
electron transport through molecular junction is
derived in terms of standard output of Gaussian 03
Derived formula is applied for calculations of
electric current through benzene dithiol molecule
coupled to gold electrodes
Proposed method may be used for predicting useful
effects in molecular junctions