The dynamics of electron transfer (ET)

Apply TST and quantum theory to the study of electron transfer

22.9 ET in homogeneous system


 D +

 
 A−

+
D+ A → D =+A−
v kobs [=
D ][ A] , K
[ D ][ A]
+ − + −
D + A  k  DA  k   → +
ka ket
      D A kd
D A
−a − et

ka ket kd 1 1 k  k − et 
kobs = → =+ − a 1 + 
k − a k − et + k − a kd + kd ket kobs ka ka ket  k d 

1 1  k− a 
If kd >> k − et , = 1 + 
kobs ka  ket 
(i ) ket >> k − a kobs ≈ ka Diffusion-controlled
ka
(ii ) ket << k − a kobs ≈ ket = K DAket where ket = κν e − ∆ G RT
#

k− a
controlled by the activation energy of ET

(2015) Chemical Kinetics by M Lim 1

 + − + −
D + A  k  DA  k   → +
ka ket
      D A kd
D A
−a − et

=v k=
obs [ D ][ A] k 
d  D A 
+ −

Steady state approximation

d  D + A− 
ket [ DA] − ( k − et + kd )  D A  =
( k − et + kd ) + −
= + −
0 → [ DA] = D A 
 
dt ket
d [ DA]
= ka [ D ][ A] − ( k − a + ket ) [ DA] + k − et  D + =
A−  0
dt
( k + kd )  D + A−  + k  D + A−  =
ka [ D ][ A] − ( k − a + ket ) r 0
ket   − et  
ka [ D ][ A] ka ket
 D A  =
+ −
= [ D ][ A]
( − a et ) ( r d ) − k
k + k k + k k − a k − et + k − a kd + ket k − et + ket kd − k − et ket
− et
ket
ka ket kd
∴v [ ][ ] d 
kobs=D A k 
= D + −
A  k k + k k + k k [ D ][ A]

− a − et −a d et d

(2015) Chemical Kinetics by M Lim 2

 22.9(a) The role of electron tunneling
• Electrons are transferred by tunneling through a potential barrier
→ influence κν
• DA and surrounding solvent molecules undergo structural
rearrangements prior to ET → ΔrGo and λ determine ΔǂG
(∆ G)
#

λ: the reorganization energy

The energy needed for the molecular
rearrangement that must take place for DA
to attain the equilibrium geometry of D+A-.

2
tunneling rate ∝ = H DA0 e− β r
2
H DA
where H DA ≡ ∫ Ψ D Hˆ DAΨ Adτ
Ψ D : wavefunction for electronic level of D
Ψ A : wavefunction for electronic level of A
H DA: the coupling H of the electronic wavefunction
β : a parameter that measures the sensitivity of H DA to r
(2015) Chemical Kinetics by M Lim 3
22.9(b) The expression for the rate of ET

For weak electronic coupling and only at high T where

thermal fluctuations alone can bring R to AC
2
2 H DA π 3 − ∆ G RT
k et = ∝ e − β r e − ∆ G RT
# #
e
h 4λ RT
( + λ)
2
∆G o

∆G≡
r
#
← (Next slide)
4λ

A large number of ET reactions including those between proteins during

metabolism are weak coupling (wavefunctions do not overlap extensively).
cf, strongly-coupled system: mixed-valence, binuclear d-metal ions,
ex, LmMn+-B-Mp+Lm (r < 1 nm)

(2015) Chemical Kinetics by M Lim 4

 Gibbs energy of activation
When the surfaces for DA and D+A− are described by classical HOs with identical µ and ω.

N A µω 2 ( q − q0R ) + Gm ,R ( q0R )
1
,R ( q )
2
Gm=
2
Gm=,P ( q )
1
2
N A µω 2
( q − q 0 ) + Gm , P ( q0 )
P 2 P

∆ rG o ≡ Gm ,P ( q0P ) − Gm ,R ( q0R ) , q* =q0R + α ( q0P − q0R )

λ ≡ Gm ,R ( q0P ) − Gm ,R ( q0R=
) N A µω 2 ( q0P − q0R )
1 2

2
∆ #G Gm ,R ( q* ) − Gm ,R ( q0R )
=
1
N A µω ( q −=
q0 )
1
N A µω α ( q0 −=
q0 ) { }
2
R 2
Harmonic potential = 2 * 2 P R
α 2λ
2 2
1
E = kx 2
2 1  ∆ rG o + λ 
α=   (next slide)
k 2 λ 
ω= → k= µω 2
µ ( + λ)
2
∆G o

∆G=
# r

E=
1
µω 2 x 2 4λ
2
(2015) Chemical Kinetics by M Lim 5
 Gm ,R ( q* )
1
{ }
N A µω 2 α ( q0P − q0R ) + Gm ,R ( q0R )
2
=
N A µω ( q − q0 ) + Gm ,R ( q0 )
1
,R ( q )
R 2
Gm= 2 R
2
2
m ,P ( ) 1
{ ( 0 ) }
+ Gm ,P ( q0P )
2
= µω − + α −
( 0 ) m,P ( 0 )
* 2 R P P R
1 G q N q q q q
,P ( )
2
Gm= q N A µω 2
q − q P
+ G q P
2
A 0 0 0
2
∆ rG o ≡ Gm ,P ( q0P ) − Gm ,R ( q0R )
1
{ }
N A µω 2 (α − 1) ( q0P − q0R ) + Gm ,P ( q0P )
2
=
2
q = q0 + α ( q0 − q0 )
{
Using N A µω 2 ( q0P − q0R ) = }
* R P R
1 2
λ
2
λ ≡ N A µω 2 ( q0P − q0R )
1 2

2 Gm ,R (=q* ) λα 2 + Gm ,R ( q0R ) ------ (1)

Gm ,P ( q* ) = λ (α − 1) + Gm ,P ( q0P )
2
------ (2)

(1) − (2), and since Gm ,R ( q* ) =

Gm ,P ( q* )

( ) {
0= λ α 2 − (α − 1) + Gm ,R ( q0R ) − Gm ,P ( q0P )
2
}
λ ( 2α − 1) − ∆ rG o =0
1  ∆ rG o  1  ∆ rG o + λ 
∴α
= = + 1
2  λ  2
 λ 


(2015) Chemical Kinetics by M Lim 6

22.9(c) Experimental results-1 k =
2 H DA
2
π 3 − ∆ G RT
e
#

4λ RT
et
h
2
When e − ∆ #G RT
ket − β r + constant
is constant, ln= 2 H DA0 e− β r π 3 − ∆ G RT
=
#
e
h 4λ RT
( + λ)
2
∆
( ∆ rG o + λ )
o
2 G
∆G=
r
∆ #G
#

When r is constant, ln ket ∝ − = − 4λ

RT 4λ RT
When D and A are positioned by covalent
attachment to molecular linkers

The value of β depends on the medium which the

electron must travel from donor to acceptor

Vacuum: 28 nm-1 < β < 35 nm-1

A molecular link, β ~ 9 nm-1
In protein up to β ~ 2 nm-1

(2015) Chemical Kinetics by M Lim 7

 22.9(c) Experimental results-2
∆ #G 1
( ∆ rG + λ )
2
When r is constant, ln ket ∝ − =− o

RT 4λ RT
The distance r and λ are kept constant
Inverted region

ket is maximum
λ = –ΔrG

1
( ∆ rG o + λ )
2
−
4λ RT

=
−
(∆ G ) r
o 2

−
2∆ rG oλ
−
λ2
4λ RT 4λ RT 4λ RT
2
RT  ∆ rG o  1  ∆ rG o  λ
=
−   −   −
4λ  RT  2  RT  4 RT (2015) Chemical Kinetics by M Lim 8
22.10 ET processes at electrodes
• As for homogeneous systems, ET at the surface of an
electrode involves electron tunneling.
- The electrode possesses a nearly infinite # of closely spaced
electronic energy levels.
- Specific interactions with the electrode surface give the solute
and solvent special properties that can be very different from
those observed in the bulk of solution.

• Let’s begin with a description of the electrode-solution

interface.
• Then, describe the kinetics of electrode processes by
using a largely phenomenological approach that draws
on the thermodynamic language inspired by TST.

(2015) Chemical Kinetics by M Lim 9

 22.10(a) The electrode-solution interface
• Electric double layer (most primitive model): a sheet of positive charge at the
surface of the electrode + a sheet of negative charge next to it in the solution
(creates an electrical potential difference: Galvanic potential difference)
• Helmholtz layer mode: the gradual changes in the structure of the solution
between two extremes. Solvated ions. Outer Helmholtz plane (OHP)
• Gouy-Chapman model (diffuse double layer): the disordering effect of thermal
motion is taken account
• Stern model: an inner rigid Helmholtz model + an outer Gouy-Chapman model
• Grahame model: adds an inner Helmholtz model to the Stern model
Galvani potential difference, between points in the bulk metal and the bulk
solution

(2015) Chemical Kinetics by M Lim 10

 22.10 (b) The Butler-Volmer equation
The Butler-Volmer equation: The effect of the Galvani potential difference at the
electrode on the current density, j

= {
j j0 e(1−α ) f η − e −α f η }
f = F RT
overpotential: η= E '− E
E ' : the electrode potential when a current is being drawn from cell
E : the electrode potential at equilibrium (when there is no net flow of current)
α : transfer coefficient
(an indication of whether the transition state between the reduced
and oxidized forms of the electroactive species in solution is
reactant-like (α 0=
= ) or product-like (α 1) )
j0 : exchange-current density (the magnitude of the equal but opposite current
densities when the elctrode is at equilibrium)
(2015) Chemical Kinetics by M Lim 11
 22.10 (b) The Butler-Volmer equation
When the overpotential is so small (η < 0.01 V)

j {
j0 e(1
−α ) f η
− e −α f η }
{ }
RTj
= j0 (1 + (1 − α ) f η + ⋅⋅⋅) − (1 − α f η + ⋅⋅⋅) ≈ j0 f η for f η  1 η=
Fj0
j > 0 when η > 0: the current is anodic
j < 0 when η < 0: the current is cathodic

When the overpotential is large and positive (η > 0.12 V)

=j j0 e( −α ) { 1 fη
− e −α f η }
= j0e( ln j= ln j0 + (1 − α ) f η
1−α ) f η

When the overpotential is large and negative (η < −0.12 V)

= {
j j0 e(1−α ) f η − e −α f η }
=− j0e −α f η ln ( − j ) =ln j0 − α f η
(2015) Chemical Kinetics by M Lim 12
 22.10 (b) The Butler-Volmer equation

Exchange currents are generally large when the redox involves no bond
breaking or if only weal bonds are broken

Exchange currents are generally small when more than one electron
needs to be transferred or strong bonds are broken and in redox
reactions of organic compounds

(2015) Chemical Kinetics by M Lim 13