Theory of electron transfer

Winterschool for Theoretical Chemistry and Spectroscopy

Han-sur-Lesse, Belgium, 12-16 December 2011

Friday, December 16, 2011

 Electron transfer
Electrolyse Battery

Anode (oxidation): 2 H2O(l) → O2(g) + 4 H+(aq) + 4e

Cathode (reduction): 2 H+(aq) + 2e− → H2(g)

Redox reactions Electron transfer system Photoactive proteins

4 Fe2+ + O2 → 4 Fe3+ + 2 O2−

Friday, December 16, 2011

 Electron transfer
D+A D+ + A-
electron transfer

chemical reaction electronic excitation

A+B C+D A A*

transition
ΔG state E
ΔG* λ
absorption
fluorescence
ΔG0

reactants products

reaction coordinate re

Friday, December 16, 2011

 Chemical reaction

D+A D+ + A-
Svante Arrhenius Henry Eyring
1859-1927 1901-1981
1903 Nobel prize
Arrhenius equation
−β∆G∗
kRS→PS = k0 e
ΔG transition
state Final equilibrium
[D+ ][A− ] kRS→PS
ΔG* K = =
[D][A] kPS→RS
ΔG0 k0 e−β(GTS −GRS )
=
k0 e−β(GTS −GPS )
reactants products = e−β∆G0
reaction coordinate
Friday, December 16, 2011
 Franck Condon principle
E1
ω=6
ω=5
ω=4
James Franck Edward Condon
1882-1964 ω=3
1902-1974
1925 Nobel prize ω=2
ω=1
ω=0
The probability (or amplitude) of a simultaneous
electronic and vibrational transition to a new
E0
“vibronic” state depends on the overlap between ω=6
the wavefunctions of the ground and excited
ω=5
states.
ω=4
Or: ω=3
Electrons move much faster than nuclei. For an ω=2
electronic excitation to occur, the nucleic
ω=1
configuration should be optimal (the same).
ω=0

Friday, December 16, 2011

 Marcus theory of electron transfer

Not quite as the Chemical Reaction picture

• The transfer of the electron is not a good reaction coordinate; it is
not the slow variable.

Not quite as the Franck-Condon picture

• Vertical excitation does not conserve energy; electron transfer
reactions also occur in the dark.

G D– + A D + A–

ΔE
λ

reaction coordinate

Friday, December 16, 2011

 Contents

Marcus theory of electron transfer

Friday, December 16, 2011

 Marcus theory of electron transfer
G D– + A D + A–

ΔG*

Rudolph A. Marcus (1923) ΔG0

1992 Nobel prize
reaction coordinate

The reaction coordinate is a

measure of the amount of charge
that is transfered.
It is also a measure of the response D– A D A–
(polarization) of the dielectric
environment (solvent).

Friday, December 16, 2011

 Marcus idea
Classical electrostatic model
Δe to vacuum
initial
Take a charged and neutral sphere in a –
state
dielectric medium.

Step 1: move half an electron to reach a

symmetric system. ΔW1
The work ΔW1 is due to the electric field
on the solvent which creates an electronic
and configurational polarization, Pe + Pc
Δe from vacuum
1
–– 1
––
Step 2: move half an electron back, but
2 2
maintain the atom configuration fixed.
Δe to vacuum
Only the electronic polarization adapts.

The Gibbs free energy to reach this (non-

equilibrium) transition state is ΔW1 + ΔW2 fixed solvent ΔW2

transition –
state Δe from vacuum

Friday, December 16, 2011

 Marcus idea
Classical electrostatic model
Δe to vacuum
initial
The complicated reaction coordinate –
state
involving all solvent atom coordinates is
replaced by a single coordinate: the
solvent polarization.
ΔW1
The gibbs free energy can this way be
calculated for any arbitrary charge
transfer.
Δe from vacuum
! 1 1 1 " ! 1 1"
1
–– 1
––
∆G = + − · − · (∆e)2 2 2
2r1 2r2 R12 !op !s Δe to vacuum
r1, r2 : sphere radii
R12 : distance between spheres
εop : optical dielectric constant fixed solvent ΔW2
εs : static dielectric constant
Δe : amount of charge transfered

The free energy profile is a parabola. transition –

state Δe from vacuum

Friday, December 16, 2011

 Gaussian potentials
To move to a microscopic, atomistic, picture, the spheres could Classical electrostatic model
represent a ligated metal ion, such as in:

[FeII(H2O)6]2+ + [FeIII(H2O)6]3+ [FeIII(H2O)6]3+ + [FeII(H2O)6]2+

diabatic
G D– + A D + A–

Although, we cannot transfer a partial electron charge, the

previous theory still holds, if we consider the reaction coordinate to ΔE
be the polarization due to a hypothetical Δe. (Outer sphere ET) λ

The polarization response of a charged species by an environment

continuously fluctuates. The fluctuations can be assumed
Gaussian statistics, as they are the sum of many uncorrelated
reaction coordinate
solvent interactions (central limit theorem).

If the two states |D–+A> and |D+A–> are very weakly coupled, we
can treat them as separate states along the reaction coordinate. Reactant state
The activation energy is governed by that rare polarization event
as if half an electron was transfered. The electron can then
instantaneously jump.

Note that the transition state is not a single configuration. D– A

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 Central Limit Theorem

Friday, December 16, 2011

 Density fluctuations

An information theory model of hydrophobic interactions.

G Hummer, S Garde, A E García, A Pohorille, and L R Pratt
Proc. Natl. Acad. Sci. USA 93, 8951 (1996)

Friday, December 16, 2011

 Gaussian potentials
Classical electrostatic model diabatic

G D– + A D + A–
In the microscopic picture the free energy curve is a similar
parabola as with the conducting spheres (a is a microscopic
length). ΔE
λ
1 ! 1 1"
∆G ∼ · − · (∆e)2
a !op !s
When moving one electron charge, ∆G = λ − ∆G0 reaction coordinate
so that
1 ! 1 1" 2
λ∼ · − ·e
a "op "s
Reactant state
For water the static dielectric constant is about 80 and the optical
constant about 2. This gives for the reorganization free energy a
number close to 2 eV.
D– A
The reorganization free energy is not completely a universal
property of the solvent. Also inner sphere reorganization (ligand
fluctuation) plays a small part. Therefore, also in non-polar solvents
λ is not zero. (Benzene gives 0.2-0.6 eV).

Friday, December 16, 2011

 Inner sphere
Classical electrostatic model diabatic
The reorganization free energy is not completely a universal
property of the solvent. Also inner sphere reorganization (ligand
fluctuation) plays a small part. G D– + A D + A–

Inner sphere reorganization refers to vibrational changes inside the

redox species (molecule or complex). ΔE
λ
For the Fe2+/Fe3+ redox couple, the breathing modes of the 6 water
molecules in the first coordination shell (ligands) change.

Assuming harmonic conditions and frequencies νD and νA, the reaction coordinate
force constants, fD and fA are: f=4π2ν2μ and the energies are:

ED = ED (q0 , D) + 3fD (∆qD )2

EA = EA (q0 , A) + 3fA (∆qA )2

Also in the inner sphere reorganization the potential energy curve

is quadratic, but here it is due to the vibrations.

q0,D fD + q0,A fA 3fD fA

q =
∗
λin = ∆E =∗
(q0,D − q0,A )2
fD + fA fD + fA

Friday, December 16, 2011

 Energy barrier
Gaussian potential curves
1 D– + A D + A–
GR = G0R + k(q − qR )2
2 G

1
GP = G0P + k(q − qP )2 GR GP
2

Where do they cross?

k 2 qR q* qP q
G0P − G0R = [q − 2qP q + qP2 − q 2 + 2qR q − qR
2
]
2
(G0P − G0R )
2 = 2(qR − qP )q + qP2 − qR
2
k
1 2 ∆G0 1 !1 ∆G "2
q∗ = (q − qP ) +
2
∆G∗ = k (qR
2
− qP2 ) +
0
2 R k(qR − qP ) 2 2 k(qR − qP )
With reorganization free energy, λ

1 (λ + ∆G0 )2
λ = k(qP − qR )2 ∆G =
∗
2 4λ

Friday, December 16, 2011

 Fermiʼs golden rule
The transfer barrier
D– + A D + A– (λ + ∆G0 )2 1
G ∆G =∗ λ = k(qP − qR )2
4λ 2

GR GP The rate
The electron transfer rate is the obtained using the
Arrhenius equation:

qR q* qP q !(λ + ∆G0 )2 "

k = k0 exp −
4λkB T
2π
pi→j = | < ψi |V |ψj > |2 ρj
!
Total non-adiabatic solution
The probability of a transition from an eigenstate |
ψi> to a final state |ψj> depends on the overlap
2π 2 (λ + ∆G 0 )2
between the states and the degeneracy (density, ρ) ket = |HAB |2 √ exp −
of the final state. ! 4πλkB T 4λkB T

Fermiʼs golden rule was first derived by Dirac, using

time-dependent perturbation theory to first order,
using a (time-dependent) perturbation interaction, V.

Friday, December 16, 2011

 Marcus inverted region
The transfer barrier The electron transfer rate is the obtained using the
Arrhenius equation:
(λ + ∆G0 )2 1 !(λ + ∆G0 )2 "
∆G = ∗ λ = k(qP − qR )2 k = k0 exp −
4λ 2 4λkB T

∆G0 = ∆E + λ
Increasing of the “driving force” ΔG0 No barrier; ΔG*=0, Inverted region: barrier increases
increases the rate (as expected) ΔG0 = λ with ΔG0 (rate decreases)

G G G

ΔG*
ΔG*
ΔE
ΔG0
λ

reaction coordinate reaction coordinate reaction coordinate

Friday, December 16, 2011

 Marcus inverted region
normal region inverted region

• Marcus pubished his theory in JCP 1956

• Experiments with reactions of increasing ΔG0 show increasing rate
(up to diffusion limit)
• Until Miller, Calcaterra, Closs, JACS 106, 3047 (1984), inverted
region in intermolecular ET, with donor and acceptor at fixed distance
Friday, December 16, 2011
 Duttonʼs ruler
Comparison of different ΔG0 in photosynthetic reaction center by
• regarding different electron transfer processes (different D-A distance)
• replacing donor or acceptor amino acids (environment remains unchanged)

log10 ket = 13 − 0.6(R − 3.6) − 3.1(∆G0 + λ)2 /λ

Friday, December 16, 2011

 Summary

• Marcus theory builds on Arrhenius equation

• Formula for the rate
• Dependence of activation energy on driving force ΔG0 and
reorganization free energy
• Environment response by inner and outer sphere reorganization
• Gaussian potential functions (linear response of environment)
• Inverted region when λ < ΔG0

Friday, December 16, 2011

 Electron transfer
quantum mechanical picture
Consider two identical ions, A and B,
separated by a distance R and an extra
electron. V(z)
zA zB
For very large R, the electron sits either on A
or B, and the degenerate states |A> and |B>
do not mix.

For a typical ion-contact pair distance (~5 Å),

E1
the two states are coupled, resulting into two
mixed states, E = E∞ ± K, with a gap of 2K. 2K
E∞ E∞
E0
< A|H0 |B >= −K
! "
0 −K
H0 =
−K 0
R
• K decays exponentially with distance
• The coupling is small but not zero
(otherwise there would be no transfer)
• An asymmetric redox pair tilts the picture
• Adding a solvent will increase the gap and
the asymmetry.
Friday, December 16, 2011
 Electron transfer
quantum mechanical picture V(z)
zA zB
Adding ligands and solvent changes the Hamiltonian.

If the electron is mainly localized on one of the two

ions, the gap is increased by the solvent reaction field
that interacts with the redox pair dipole. The solvation E1
energy is:
e2 1
Esolv ≈ − (1 − ) E∞
a !s
ΔE
If the electron is delocalized over the two ions, the
E∞
dipole fluctuations are to fast to couple to the solvent
configuration; only the electronic polarizability couples. E0
The solvation energy is:
e2 1
Esolv ≈ − (1 − )
a !opt
R
Thus:

e2 ! 1 1" e2
∆E ∼ · − ≈
a !opt !s a!opt

Friday, December 16, 2011

 Electron transfer
quantum mechanical picture
The total Hamiltonian is:
! " ! " ! " ! "
0 −K −1 0 1 0 HA −K
H= −E + Hbath (x1 , x2 , . . . , xN ) =
−K −∆e 0 −1 0 1 −K HB

E is the local electric field on the redox dipole. F(ε)

It shows Gaussian statistics. (inner shell / outer shell)
D+A D+ + A-
The environment contributes 2E to the gap:

∆E = HB − HA = −∆! − 2E

HX is total Hamiltonian when electron is on site X. 2K

Fb (E) =
1 2
E
-α α ε
2α Δε

< E >b = 0 < E 2 >b = kB T α

adiabatic
1 2 1 2
FA (E) = E +E FB (E) = E − E − ∆" spin boson model
2α 2α

Friday, December 16, 2011

 Marcus inverted region

normal region inverted region

quantum tunneling

Friday, December 16, 2011

 Quantum effects
Spectral density of gap correlation

quantum nature of water for Fe3+/Fe2+

classical
kET /kET ≈ 60, H2 O

≈ 25, D2 O

Friday, December 16, 2011

 Summary Part 1
F(ε)

D+A D+ + A-

Marcus theory of Electron transfer

2K
-α α ε
2π 2 (λ + ∆G0 )2
ket = 2
|HAB | √ exp − Δε
! 4πλkB T 4λkB T

1. reaction rate theory (Eyring) or vibronic excitation (Franck-Condon)

2. Gaussian potentials when polarization is the reaction coordinate
3. λ = inner sphere (harmonic vibrations) plus outer sphere (central limit
theory) reorganization
4. dependence of activation energy on driving force ΔG0 and reorganization
free energy
5. inverted region when λ < ΔG0
6. adiabatic vs diabatic picture (energy gap versus Fermiʼs golden rule)
7. quantum tunneling

Friday, December 16, 2011

 Bibliography and further reading

• R. A. Marcus, J. Chem. Phys. 24, 966 (1956)

• R. A. Marcus, Discuss Faraday Soc. 29, 21 (1960)
• R. A. Marcus, J. Chem. Phys 43, 679 (1965)
• R. A. Marcus, Rev. Mod. Phys. 65, 599 (1993)
• A. Washel J. Phys. Chem. 86, 2218 (1982)
• R.A. Kuharski, J.S. Bader, D. Chandler, M. Sprik, M.L. Klein, R.W. Impey, J. Chem. Phys. 89, 3248 (1988)
• D. Chandler Chapter in Classical and Quantum Dynamics in Condensed Phase Simulations, edited by B.
J. Berne, G. Ciccotti and D. F. Coker (World Scientific, Singapore, 1998), pgs. 25-49.
• A. Tokmakoff, MIT Department of Chemistry, Lecture notes 12-6, 2008
• A. Crofts, University of Illinois at Urbana-Champaign, Lecture notes, 1996
• N. Sutin, J. Phys. Chem. 1986, 90, 3465
• J. Jortner and K.F. Freed J. Chem. Phys. 52, 6272 (1970)
• L. Bernasconi, J. Blumberger, M. Sprik and R. Vuilleumier, J. Chem. Phys.121,11885 (2004)
• J Blumberger and M. Sprik, J. Phys. Chem. B 108, 6529 (2004)
• J Blumberger and M. Sprik, J. Phys. Chem. B 109, 6793 (2005)
• J Blumberger and M. Sprik,Theor. Chem. Acc. 115, 113 (2006)
• S. Bhattacharyya, M. Stankovich, D. G. Truhlar, J Gao, J. Phys. Chem. A 111, 5729 (2007)
• J. Blumberger, J. Am. Chem. Soc. 130, 16065 (2008)
• J. Blumberger, Phys. Chem. Chem. Phys. 10, 5651 (2008)

Friday, December 16, 2011