March202014,DueonApril32014(printandemail)

526:Problemset5

(1)Thepicturebelowrepresentsanelectrontransferbetweenamoleculeacharacterizedbythedonor
level a of energy E
a
and an molecule b with an acceptor level b of energy E
b
. These energies are
eigenstates of the Hamiltonian in the absence of the couplings shown in the figure. Molecule b is
adsorbedonametal,representedbyacontinuumofstates
{ }
m .Itisgiventhatthemetallevelsare
unoccupiedintheenergyrangeshown,soanelectroninbwillbetransferredtothemetal.Keepingthe
couplingV
ab
constant,thecouplingV
bm
canbechangedbychangingthemetalmoleculedistance.
|b>
{|m >}
V
bm
V
ab
a

The rate of electron transfer from a to the metal was measured as a function of distance between
molecule b and the metal distance (i.e. of V
bm
) and it was found that it is zero for 0
bm
V = and goes
throughamaximumwhen
bm
V increases.Explainthismaximum.

(2)Doindetailstheproblemdiscussedinclass:TheHamiltonianis

0

H H V = + (1.1)

0 0 1

0 0 1 1
l r
l r
H E E E l l E r r = + + +

(1.2)
( ) ( )
0,1 1,0 ,1 1, ,1 1,

0 1 1 0 1 1 1 1
l l r r
l r
V V V V l V l V r V r = + + + + +

(1.3)
Level 0 drives the system (it can corresponds to the ground state plus one photon in a mode of
frequency , so
0 g
E E e = + where g is the molecular ground state, see picture below). Show that
theratetogofrom0tomanifoldK(K=LorR)isgivenby
|g>
|1>
{|r>}
{|l>}
V
1,r
V
1,l
R L

( ) ( )
2
1,0
1 0
0
2
2
0 1 1 0
| |
( )
; ,
( ) / 2
K
K
V
E
k K L R
E E E

I
= =
+ I

where
1 1 1 L R
I = I + I and
1 1 1 0 1 0
( ) ( )
L R
E E E E = + A + A

whereforK=R
2
1
1 1 1
2
1 1
2
1
1
| |
( ) ( ) (1/ 2) ( )
/ 2
( ) 2 ( )
( )
( )
r
r
R R R
r r
R r R r
E E
r R r
R r
r
V
B E E i E
E E i
E V E
V E
E PP dE
E E
q
t

= A I
+
| |
I =
|
\ .
A =

andsimilarexpressionsfork=L.

(3)(a)Inthecasewhere|0>isthemoleculargroundstateplusonephotoninaradiationfieldmodeof
frequency , and 1 is a molecular excited state with no photons, write an explicit expression for the
coupling
01
V .
(b) For this case, with
0 g
E E e = + and assuming that R is the radiative continuum (one photon
states dressing the ground molecular state) and L is a non radiative continuum (representing, e.g.,
energy loss to a solvent, discuss the strength of absorption (that can be monitored by the intensity of
lightcomingout,
0 R
k

,asafunctionofthestrengthofcouplingtothenonradiativecontinuumL.