Perspective
Cite This: J. Am. Chem. Soc. 2019, 141, 708−722 pubs.acs.org/JACS
From Fundamental Theories to Quantum Coherences in Electron
Transfer
Shahnawaz Rafiq and Gregory D. Scholes*
Frick Chemistry Laboratory, Princeton University, Princeton, New Jersey 08544, United States
ABSTRACT: Photoinduced electron transfer (ET) is a
cornerstone of energy transduction from light to
chemistry. The past decade has seen tremendous advances
in the possible role of quantum coherent effects in the
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light-initiated energy and ET processes in chemical,
biological, and materials systems. The prevalence of
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such coherence effects holds a promise to increase the
efficiency and robustness of transport even in the face of
energetic or structural disorder. A primary motive of this
Perspective is to work out how to think about “coherence”
in ET reactions. We will discuss how the interplay of basic
parameters governing ET reactionslike electronic
coupling, interactions with the environment, and intra-
molecular high-frequency quantum vibrationsimpact
coherences. This includes revisiting the insights from
the seminal work on the theory of ET and time-resolved
measurements on coherent dynamics to explore the role
of coherences in ET reactions. We conclude by suggesting
that in addition to optical spectroscopies, validating the
functional role of coherences would require simultaneous
mapping of correlated electron motion and atomically
resolved nuclear structure.
■ INTRODUCTION
Recent work has suggested that effects collectively called
coherencelong thought to be irrelevant for robust function
owing to their fleeting presencemight be harnessed
efficiently even when electronic coupling is not such a
dominant participant.1−7 Coherence refers to phase relations
among the constituents of the superposition of quantum states
that carries extra correlations beyond those predicted by the
classical probability theory.8,9 When such phase relationships
among quantitieslike quantum amplitudeare retained long
enough to have a mechanistic and functional relevance to the
underlying process, the dynamics are rendered coherent. In
relation to practical systems, when electronic states are
localized, transport of energy or charge is incoherentit
hops randomly from site to site. Similarly, stochastic
incoherent transport is prevalent when the electronic states
are strongly delocalized over multiple sites to form extended
eigenstatesthat is, population relaxes incoherently owing to
minimal interactions with the surroundings. These two
extremes are prevalent when the electronic coupling between
the sites is either much smaller or much larger than the
reorganization energy of the surroundings. In these limits,
optimization of the transport becomes very challenging.10−12
In the middle of the two extremeslocalization and
delocalizationthe interplay of energy fluctuations and
© 2018 American Chemical Society
transport leads to a competition between the delocalization
and localization, and that is where coherences seem to matter
(Figure 1). The resulting dynamics are complex and could
sometimes translate to robust and disorder-resistant trans-
port.13,14 In this regime, due to competition of the time scales,
the system exhibits coherent dynamics at short times, and at
later times incoherent transport dominates. From the coupling
perspective, the three regimes are analogous to the valence
electron localization or delocalization in the Creutz−Taube
ions.15,16 Exploration of electron transfer (ET) systems capable
of retaining phase information for a practical time scale could
help to direct or control charge separation and recombination.
Electron transfer is a ubiquitous process whose mechanism
and dynamics are relevant to applications like solar cells,
molecular electronic devices, biosensing techniques, and
various photoactivated processes.17−24 Its importance is
emphasized every time an organic chemist draws a reaction
mechanism. Chemistry is about coercing electrons to move.
The advent of ultrafast broadband electronic spectroscopy has
provided new insights into the microscopic mechanisms of
such a fundamental process.22,25−28 In this Perspective, we will
start with a quantum/semiclassical description of ET reactions,
to lay a groundwork for introducing coherences in photo-
induced ET reactions.
Coherences will be discussed in chemical, biological, and
material systems with examples cited in each section. We will
explore what is meant by coherences in ET. Specifically, we
will ask how to assess adiabaticity and friction (coupling of a
reaction coordinate to solvent and/or nuclear modes) in
experimental studies of ET reactions. The role of high-
frequency vibrations in ET reactions, while not a new subject,
has been highlighted by recent work using coherent spectros-
copies. We will examine the mechanistic role of high-frequency
vibrations using wavepacket spectroscopies. We present a
perspective for new experimental strategies which could impart
functional validation to the coherences beyond the skepticism
emerging from pure optical spectroscopies. This is a review of
early steps toward working out how to design systems that uses
coherence to assist in ET and inhibit back-reactions.
■
QUANTUM AND SEMICLASSICAL DESCRIPTION
OF ELECTRON TRANSFER
The pioneering work by Marcus assumes the well-known
thermally activated form of transition-state theory, wherein
nuclear motions of the reactant molecules and the solvent are
in thermal equilibrium before the reaction.29−31 Equilibrium
fluctuations of the solvent dielectric polarization enables the
Received: August 22, 2018
Published: November 9, 2018
708 DOI: 10.1021/jacs.8b09059
J. Am. Chem. Soc. 2019, 141, 708−722
Journal of the American Chemical Society
Figure 1. Limiting cases of transport as a function of electronic coupling. (a) Weak electronic coupling: incoherent transport from one curve to
other. (b) Strong electronic coupling: incoherent relaxation among highly delocalized states. (c) Intermediate electronic coupling: competition
between the energetic disorder and the coupling could give rise to a unique transport mechanism at short times of the dynamics.
reactant and product energies to occasionally become quasi-
degenerate, so that an ET event can occur, leaving the product
in an energetically rich state. The classical Marcus theory of ET
kET = Kelνn exp((λ + ΔG°)2/4λkBT) generally works well for
reactions where transition probability of ET is close to unity
most adiabatic ET reactionswhere Kel is the electronic
transmission coefficient and νn is the frequency of passage
(nuclear motion) through the transition state. However, to
explain ET reactions where transition probability is much less
than unitymost non-adiabatic ET reactionsa quantum
mechanical description to the nuclear motion is required. The
transition probability in such cases was formulated in a Golden
Rule description, originally by Levich and Dogonadze.32 The
concept of the electron tunneling from donor to acceptor as
well as the nuclear tunneling from reactant to product were
introduced. The nuclear tunneling is required particularly in
the inverted regime of ET to move from the energy minimum
of the donor surface to the acceptor surface due to the avoided
crossing between the two surfaces. Hopfield was the first to
study how nuclear tunneling explained low-temperature
biological ET kinetics by using a semiclassical treatment.33
The Golden Rule treatment was also applied by Jortner and
co-workers,34,35 as well as Marcus and co-workers,36 who
showed the role of high-frequency quantum vibrations of the
product as energy accepting modes. The Golden Rule
expression for the ET rate constant is
2π 2
kET = V FCWD
ℏ (1)
where V is the matrix element for the electronic coupling
between the initial and final states and FCWD is the Franck−
Condon weighted density of states. In a full quantum
treatment of ET, the FCWD contains a summation over all
the vibronic states of the reactant, the product, and the solvent
vibrational modes. Knowing that solvent stochastic fluctuations
occur mainly at low frequencies and can therefore be treated
classically, the quantum treatment could only be applied to the
high-frequency intramolecular vibrational modes.
An assumption was further made to reduce the number of
high-frequency vibrations to only one averaged mode of
frequency ν by Jortner,37 Miller et al.,38 and Brunschwig and
Sutin,39 which resulted in the following semiclassical Marcus
ij −(λs + ΔG°0 → n)2 yz
equation for a non-adiabatic limit:
expjjj zz
j zz
2π (V 0 → n)2
k {
0→n
kNA =
ℏ 4πλskBT 4λskBT (2)
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Perspective
The overall ET rate is
0→n
kET = ∑ kNA
n (3)
k0→n
NA is the non-adiabatic rate constant for each vibronic
channel.
ΔG°0 → n = ΔG° + nhν (4)
(V 0 → n)2 = V 2 |⟨0|n⟩|2 (5)
|⟨0|n⟩|2 = (Sn/n! ) exp( −S) (6)
S, being the electron-vibrational coupling strength, or
Huang−Rhys factor, is defined as a ratio of the reorganization
energy and frequency of the high-frequency mode (λvib/
(hνvib)), n is the vibrational quantum number, and λs and λvib
are the solvent and vibrational reorganization energies.
In the high-temperature limit, this semiclassical Marcus
equation (eqs 2 and 3) reduces to a simpler and more familiar
ij −(λ + ΔG°)2 yz
equation:
expjjj zz
j zz
2πV 2
k {
kET =
ℏ 4πλkBT 4λkBT (7)
where λ = λs + λvib is the total reorganization energy. Equation
7 is more like a classical Marcus equation. The 1950s Marcus
theory assumed a nuclear frequency factor characteristic of the
potential energy surface curvature. Whereas, the later theories
of solvent-limited rates assumed overdamped or diffusive
motion along the reaction coordinate, leading to different pre-
factors of the classical and semiclassical Marcus rate equations.
The dependence of the ET rate on the energy gap leads to
three distinct regimes based on the ratio of standard free
energy change between the reactant and product species and
the solvent reorganization energy: normal, barrierless, and
inverted regimes.40 The classical and semiclassical Marcus
equations both predict a symmetric quadratic logarithmic rate
constant as a function of free energy gap on either side of the
barrierless regime because ET occurs only at the intersection
point of the two single free energy curves. However, in the
quantum description (eq 2), a more effective route is nuclear
tunneling through vibrational overlaps, which can open extra
channels for ET. This condition is particularly important in the
inverted region, where vibrational wave functions of the
reactant and the product states are embedded, so Franck−
Condon factors are much larger than the normal region. Siders
and Marcus36 confirmed that the inclusion of nuclear tunneling
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Figure 2. Semiclassical electron transfer models: (a) Sumi−Marcus model, (b) Jortner−Bixon model, and (c) Walker−Barbara model. These
models were built on the Fermi’s Golden Rule description of ET to accommodate the roles of solvation dynamics, adiabaticity, and high-frequency
quantum vibrations in the inverted region toward ET.

predicts an asymmetric fall off in the logarithmic rate constant the non-adiabatic and the adiabatic limits through a parameter
in the inverted region. for adiabaticity.56
The existence of the inverted region and the asymmetric kNA
shape of the ln(kET) vs ΔG° curve were experimentally verified kET =
by Miller et al. in intermolecular charge transfer (CT) between 1 + HA (8)
the biphenyl radical anion and various acceptors in a rigid low- HA is the adiabaticity parameter to entertain the transition
temperature glass as well as in biphenyl radical anion from the non-adiabatic to the solvent-controlled adiabatic ET
connected to various acceptors by a hydrocarbon bridge.38,40 and implicates the delocalization of the vibronic wave function
Later, researchers in the groups of Farid41 and Gray42,43 in the intersection region, given by
verified a Marcus inverted region with a symmetric ln(kET) vs
ΔG° curve, which was an indicative of nuclear tunneling 4πV 2τs
HA =
through vibrational overlaps of low-frequency modes. More ℏλs (9)
recent advances in photoinduced ET are highlighted in the
work by Vauthey and co-workers.22,44−47 where τs is the longitudinal dielectric relaxation time in the
The semiclassical treatment works well in the weak-coupling reaction coordinate. Equation 8 represents a continuous
non-adiabatic limit, where the ET process is treated within the change from the non-adiabatic limit (HA ≪ 1) to the adiabatic
equilibrium transition-state framework. However, in the limit (HA ≫ 1). In the solvent-controlled adiabatic limit, the
strong-coupling limit, the ET reaction proceeds adiabatically rate constant can be recast into the Kramer’s-like expression

ij −(λs + ΔG°)2 yz
on the lower energy surface, so that the probability of ET does for adiabatic ET rate:

not directly depend on the electronic coupling, but rather on
the probability of the reaction coordinate to reach the barrier
crossing. Therefore, instead of equilibrium contributions, the
response of the solvent polarization contributes to the reaction
coordinate, and ET dynamics is discussed in the framework of
Kramer’s theory.48−51 Kramer’s theory treats a reaction as a
potential barrier crossing by stochastic motion on the potential
energy surface, where in the reaction rate is inversely
proportional to the dielectric relaxation time. The reaction
can thus be identified as a solvent-controlled adiabatic
reaction.51
The transition from non-adiabatic ET to solvent-controlled
ET, was originally studied by Zusman using stochastic motion
along the reaction coordinate with transition probability
proportional to V2.52 Friedman and Newton53 and Sumi and
Marcus54 used the first-passage approach, while Rips and
Jortner adopted the real-time path integral formalism.55 Garg,
Onuchic, and Ambegaokar introduced a block-summation
technique to derive an expression for the rate, which bridges
710
expjjj zz
zz
j
1 λs
k {
kA =
τs 16πkBT 4 λ s k BT (10)
The above approaches connect the non-adiabatic limit,
where the probability of ET is determined by the electronic
tunneling and tunneling fluctuations, and the adiabatic limit,
where it is determined by the reaction coordinate dynamics. In
other words, the two limits differ in the nature of nuclear
motion through the curve crossing region, which is considered
to be overdamped for non-adiabatic and ballistic or diffusive
for adiabatic transfer.
In the adiabatic case of strong coupling, an electron is
transferred ballistically by nuclear motion through the
transition state, while in the solvent-controlled adiabatic
limit, the electronic coupling may still be weak; however, the
rate is affected by frictional couplingcoupling of the nuclear
reaction coordinate to other nuclear coordinates and the
solvent relaxation coordinate. Frictional coupling ensures that
the time spent in the curve crossing region is long enough that
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every time an electron approaches the crossing region, the
donor−acceptor encounter is effective, even though electronic
coupling is weak. Hence, the reaction appears adiabatic owing
to the nuclear control rather than electronic tunneling.
In the solvent-controlled adiabatic limit or in the adiabatic
limit of strong coupling, the nuclear motions and the solvent
relaxation rates thus decide the ET probability. Therefore,
many theories were put forward to address the role of
vibrational motion and solvation dynamics in ET.
Sumi and Marcus, in 1986, used a low-frequency (classical)
vibrational degree of freedom and a classical solvent degree of
freedom to address the role of vibrational motion and solvation
dynamics in ET (Figure 2a).54 In this two-dimensional model,
the ET occurs along the classical vibrational coordinate (q),
and the free energy barrier in the vibrational direction is
circumvented by energy fluctuations via reorganization along
the solvent coordinate (X). This model, however, predicts a
vanishing ET rate constant as temperature approaches zero
and also propounds that the barrier must be crossed for ET to
occur, implying that there is no scope for possible quantum
tunneling through the barrier.57
Jortner and Bixon, in 1988, while retaining the classical
solvent degree of freedom to account for dielectric relaxation,
incorporated high-frequency quantum vibrations of the donor
and acceptor centers as the intramolecular vibrational
coordinate coupled to the ET process (Figure 2b).58 High-
frequency vibrations were shown to influence ET dynamics in
three ways: providing a multitude of parallel kinetic channels.
A “polaron dressing” effect (dressing electronic coupling by the
nuclear Franck−Condon factor) reduces both the non-
adiabatic rate constant (eq 1) and the adiabaticity parameter
(eq 8). Vibrational excitation reduces the effective energy gap,
lowering the activation barrier in the inverted region. The
overall ET rate is a summation over all the high-frequency
vibronic channels,
∞ 0→n
kNA
kET = ∑ can be treated as an event occurring between a localized initial
n=0
1 + HAn (11)
where k0→nNA is given by eq 6, and the Franck−Condon
dressed adiabaticity parameter is HnA = HA|⟨0|n⟩|2. The solvent-
controlled adiabatic limit can be realized for some of the n = 0
→ n channels; i.e., the polaron dressed adiabaticity parameter
should be greater than unity for some values of n, which are
denoted by {n̅}. The ET rate is written as
∞ 0→n ∞ 0→n
kNA kNA
kET = ∑ + ∑
n ∈{n ̅ }
HAn n ≠{n ̅ }
1 + HAn (12)
This model thus introduces nuclear tunneling, and the
extent of tunneling is decided by the vibrational mixing
between the reactant and product states. Only those
intramolecular modes which involve large displacements
from the reactant to the product potentials need to be
considered.
Photoinduced ET reactions much faster than solvation
dynamics have been observed experimentally.59−61 Walker et
al. studied ultrafast photoinduced back-electron transfer in
betaines.57 Tominaga et al. found intervalence CT in mixed-
valence compounds faster than the solvation dynamics.62
Kobayashi et al. studied ultrafast intermolecular ET in the
electron-donating solvents as fast as 100 fs though fluorescence
quenching.63 Similar observations were found with oxazines
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Perspective
and coumarins.59 The Sumi−Marcus model predicts a slow
rate of ET reaction in these systemsall these ET reactions
fall in Marcus inverted regime. The Bixon−Jortner treatment
reproduces these experimental ET rates in fast relaxing solvents
only, but overestimates the rate in slow-relaxing solvents,
where it does not scale with solvation dynamics. Walker et al.
discussed how the Jortner−Bixon treatment was unable to
reproduce the switch from the solvation dynamical control to
the vibrational control.57,61,64,65
Walker and Barbara, in 1992, thus came up with a hybrid
model by extending the Sumi−Marcus model to incorporate
the effect of high-frequency vibrations in a manner similar to
that developed in the Jortner−Bixon model (Figure 2c).57 The
solvent dependent rate constant was expressed as
0→n
k(X ) = ∑ kNA (X )
n (13)
ij −(λi + ΔG°0 → n(X ))2 yz
expjjj zz
j zz
4π 2(V 0 → n)2
k {
0→n
kNA (X ) =
h 4πλikBT 4λ i k BT
(14)
ΔG°0 → n(X ) = ΔG° + λs − 2λsX + nhv (15)
The classical reorganization was split into two parts: one
corresponding to the classical vibration (λi) and second to the
solvent reorganization (λs). ΔG°0→n(X) is the solvent-
coordinate dependent effective free energy gap between the
ground state of the reactant and the nth vibrational level of the
product state. The issues of the time scale for solvent
polarization that contributes to the ET reorganization energy
have been much discussed by Matyushov and others.66−69
The ET models described above established the role of
vibrations in ET reactions, which can be understood more
comprehensibly in the context of the proton-coupled electron
transfer (PCET) reactions. In PCET reactions, while the ET
and a localized final state, the proton transfer occurs between
manifold of localized proton states on the initial state and a
corresponding manifold of vibrational states on the final
state.70 The initial state of the proton may not be thermally
accessible (as the proton potential well may have a frequency
of ∼2000 cm−1), but with a simultaneous ET event, the solvent
reorganization can provide near-degenerate multiple proton
accepting levels on the final statenested energy surfaces. For
more details, Hammes-Schiffer group has developed a general
theory for PCET reactions.71−77
Now it is established that ET reactions in the intermediate
or strong coupling limits depend significantly on the vibronic
interactions in addition to the solvent bath polarization.
Therefore, frictional coupling as explained above, plays an
essential role in ET reactions. When friction is strong
compared to other competing energy-scales, the reactant
executes a random walk along the reaction coordinate to the
barrier crossing (non-adiabatic ET).56 This is the incoherent
limit. A contrary situation where there is no frictiona
complete separation of the nuclear reaction coordinate from
other nuclear and/or solvent degreesshould manifest as a
coherent transfer (ballistic) with fastest rates of ET. However,
the findings of Garg et al. showed that fastest rate does not
come from a frictionless limit.56 Instead, the rate increases as
fiction is introduced. This is resonant with Wolynes’s work,
which suggested that quantum mechanical effects, for example
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Journal of the American Chemical Society
Figure 3. Wavepacket dynamics and its spectroscopy. (a) Generation of a coherent wavepacket on electronic potentials by a broadband laser pulse.
(b) Motion of the wavepacket in the phase space of the electronic potential modulates the signal amplitude of Cresyl Violet (in methanol), and that
modulation appears as ripples in the time-domain spectroscopic signals. (c) Fourier transform of the Cresyl Violet residual ripples produces
frequency of the wavepacket generated along Franck−Condon active nuclear vibrations. Panels b and c are reprinted with permission from ref 103.
Copyright 2016 American Chemical Society.
curve crossing, conspire with dissipation in an interesting way.
He argued that friction generally increases the adiabaticity of a
barrier crossing because of the increased time spent by the
electron in the crossing region and multiple chances to move
back and forth.78 In the regime where friction and adiabaticity
corroborate, the dynamics becomes complex, and coherent
interactions enabled by the reaction coordinate may matter.
■
COHERENCE IN PHOTOINDUCED ELECTRON
TRANSFER
The Non-adiabatic Limit. In the non-adiabatic limit of
Marcus’s classical theory,29 the jump of electron from the
reactant free energy curve to the product curve follows a
Franck−Condon principle in the same way as it is obeyed in
photoexcitation. In the normal regime of ET, this instanta-
neous transfer of the electron requires the reactant and product
energies to be degeneratedriven by solvent energy
fluctuations. In the inverted regime, that instantaneous transfer
is achieved by invoking nuclear tunneling to accomplish the
energy matching, and the phase coherence is equivalently
maintained during the ET reaction. However, it is a very
simplistic aspect of coherent transfer, as the coherence is
maintained only for a few femtosecondsthe time scale
during which the actual ET occurs. In this non-adiabatic limit,
the solvent coordinate and the nuclear coordinate are
completely orthogonal to each other, and the reaction is
promoted by the solvent dielectric relaxation.
Elegant examples of such quantum coherence can be found
abundantly at the molecule scale, when the relevant energy
scales are very large compared to thermal energy. For example,
in superexchange-mediated ET in donor−bridge−acceptor
complexes, the different electronic coupling pathways across
the bridge interfere quantum mechanically at the amplitude
level, leading to an utterly different outcome than predicted by
the classical probability laws.79−86
The Adiabatic Limit. Quantum coherence involving
electronic coupling trajectoriesas described in the non-
adiabatic limitcannot be considered as a powerful tuning
element, even though it is omnipresent, because it is strongly
subjected to dephasing.87 One may imagine that since ET is
strongly slaved to stochastic polarization fluctuations of the
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Perspective
environment, then quantum coherences should always be
subjected to strong dephasing.
Some recent research suggests that quantum coherence
could be facilitated by resonance with vibrational coher-
encesidentified as vibronic coherences.6,9,88−91 Reimers and
Hush92,93 have studied ET involving a single vibrational mode,
providing insights into vibronic coupling. In the adiabatic limit,
the reactant and product are coupled together to make Born−
Oppenheimer adiabatic ground and excited states. Theoretical
treatments by Reimers and Hush suggest that on the reactant
and product sides of the reaction coordinate, the electrons are
localized and vibrations are localized, but in the vicinity of the
transition state the electronic wave function and vibrations are
delocalized.94,95 Recent work has shown that ET in the
inverted regime in a photosynthetic reaction center (photo-
system II) is expedited when vibrational levels bridge
reactant−product electronic gaps.96−99 This work highlights
the importance of elucidating how molecular vibrations aid ET
reactions. That issue is salient because these vibrational
frequencies and the nature of those modes can be tuned by
chemical structurethus giving the chemist control over this
apparently powerful and exotic design ingredient.
Vibrational Coherences. The interest in the role of
coherences in ET reactions was triggered by the short-pulse
pump−probe experiments of Vos and co-workers in the early
1990s, in the bacterial photosynthetic reaction centers.100−102
An implicit manifestation of using short pump pulses is the
generation of superpositions of vibrational wave functions
wavepackets comprising Franck−Condon active modes
(Figure 3).103 These wavepackets modulate the signal
amplitude of the electronic surfaces. The modulations when
probed by another laser pulse, appear as oscillations on top of a
smooth population decay in the time-domain signal.
Oscillations are Fourier transformed to show the vibrational
frequency of the Franck−Condon active modes accessed by
the bandwidth of the pump pulse (Figure 3). In the
photosynthetic reaction center, the vibrational coherences
along the low frequency nuclear modes surprisingly survived
the primary ET event.100−102 This work implicated a possible
functional role of vibrational coherences for ET. An outcome
of that period was a better understanding of vibrational
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coherences in ET, succinctly pre-empted by Jortner and Bixon
(discussed above).58
The Bixon−Jortner description of the role of vibrations in
ET formed the basis of interpreting vibrational coherences in
ET.104 More direct questions pertain to the role of vibrations:
Are there particular vibrations that promote or attenuate the
ET? Is the bath polarization coordinate orthogonal to the
vibrational coordinate, or is there a collective additive effect of
bath polarization and intramolecular vibrations that affects the
ET reaction? To answer these questions, many ET systems
have been studied using ultrafast coherent pump−probe-type
spectroscopies in parallel with theoretical treatments to
speculate the role of vibrational coherences toward the ET
reactions.
Coherent vibrational wavepackets generated on the reactant
state are uniquely suited to report on the coupling of nuclear
motions to the ET reactions, especially outside the Franck−
Condon region. On one hand, vibrational coherence that is
weakly coupled to the reaction coordinate does not affect the
reaction and will have no bearing on the ET dynamicshence
superpositions (wavepackets) involving such modes will not be
affected by ET (Figure 4a). The free energy curves in such
Figure 4. Free energy curves and intramolecular modes. The effect of
coupling a vibrational mode to the ET on the wavepacket dynamics.
Due to nested free energy crossings enabled by coupling a nuclear
mode to the ET reaction, the wavepacket dispersion is enhanced, and
that translates into faster dephasing of the reactive mode wavepacket.
This dephasing time could correspond to the mean first passage time
to the transition state of the ET reaction.
cases cross like pure diabats. On the other hand, ET aided by a
nuclear mode modifies that picture. The coupled vibrational
mode “nests” the free energy curves much like the way proton
vibrations nest the energy curves of a proton-coupled ET
reaction. Thereby, the vibration increases the number of ET
channels (Figure 4b) as well as the range of the activation
barriers and effective reorganization energies by the
permutation of offsets (Bixon−Jortner theory). This peculiar
case is common to non-adiabatic and adiabatic ET reactions,
though the picture gets more complicated in the adiabatic
regime.
The nesting of the free energy curves dephases the
vibrational wavepackets during the ET reaction. To elaborate,
when a superposition is generated along a coupled vibration on
the reactant state, coefficients of individual vibrational levels
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Perspective
have a set of values which define the contribution of each
vibrational level to the superposition (i.e., wavepacket).
Multiple crossings due to the nesting of the free energy
surfaces will modify the value of the coefficients of each
vibrational level as the reactant passes into the product, leading
to dispersion of the wavepacket (Figure 4b). Thus, the
dephasing time of the reactive mode wavepacket should
correspond to the mean first passage time to the transition
state, which is defined as the time needed to reach the
transition state or the mixed region by a statistical ensemble of
initial states. Mean first passage time is expected to be shorter
than the actual ET time, as the overall ET time includes the
time during which the transition state evolves into the
equilibrated final state.
A Note on Basis. We wish to point out that understanding
the experimental signatures of coherence demands a general
understanding of basis, because without knowing the basis of
the initial state, it is challenging to identify coherence.
Experiments such as two-dimensional electronic spectroscopy
(2DES) detect coherence in the adiabatic basis in the Franck−
Condon region. For example, in CdSe nanoplatelets, where the
basis is clearly delocalized, the oscillating off-diagonal cross-
peaks were assigned to an excitonic coherence (see Figure 7d−
f, below).87 That oscillating cross-peak indicates that the two
excitonic states are coupled and share excitation. The
modulation of the electronic wavepacket between the two
excitonic states lives for the time scale of the optical coherence
between the ground and the excitonic states. So, experiments
measure coherence in the adiabatic basis, because it probes
coupling between the electronic states through wave function
delocalization. In other words, oscillations in the cross peak of
2D maps can definitively assess state coherences. However,
when the dephasing is strong/rapid, the experiment will detect
localized states, more like the theorist exploring a localized
basis.
In the case of ET reactions, the reaction coordinate follows a
basis rotation, as epitomized by the method Larrson used to
calculate ET matrix elements.105 Calculations find that the
electron is localized on the donor in the Franck−Condon
region, but an external electric field can be changed, mimicking
solvent reorganization, until the calculation predicts a perfectly
delocalized state where the electron is shared between the
donor and acceptor. Similarly, when we think about most ET
reactions, an initial state is prepared in a localized reactant
basis, which evolves into the transition state that is a quantum-
mechanical superposition of the reactant and product statesa
state best described in the delocalized basis. The transition
state finally collapses into the product localized basis. In such a
situation, 2DES cannot assess coherence definitively at the off-
diagonal cross peaks because basis changes during ET.
However, if the reactant and product states are coupled in
the Franck−Condon region, then 2DES can provide definitive
insights in the coherent ET dynamics.
Coherences in Chemical Systems. The first and foremost
constraint to experimentally exploring the role of coherences in
ET is to focus on systems with ET rate is faster than vibrational
dephasing. Barbara and co-workers used ca. 20 fs time-
resolution pump−probe spectroscopy to measure an ca. 85 fs
ET time-constant corresponding to the photoinduced back-ET
reaction in the mixed-valence metal dimers.106−108 Analysis of
the oscillations demonstrated that the average vibrational
dephasing for the observed modes is ca. 300 fs. The longer
dephasing time of the vibrational coherences relative to the ET
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Figure 5. Wavepacket dynamics during electron transfer. (a) Wavepacket branching at the branching space of the conical intersection along the
tuning and the coupling modes that define the CI between CT states and neutral ground state in the π-stacked dimer. (b) Integrated Fourier
transform of Betaine-30. Multiple frequency components are separated by using super-Gaussian windows of different widths followed by inverse
Fourier transformation of the frequency domain signal into the time domain to calculate dephasing times. Point to note is that certain high-
frequency modes dephase much faster in acetonitrile solvent than methanol, which is in correspondence with the solvent-dependent ET rate. (c)
Reactant−product coupling enabled by displaced high-frequency quantum vibration. The effective coupling is shown to be reduced by dressing of
Franck−Condon factors to the electronic coupling. Panel a is adapted with permission from ref 116. Copyright 2016 American Chemical Society.
Panels b and c are reprinted with permission from ref 121. Copyright 2017 Elsevier.

time (85 fs) indicated that coherence is maintained for some
degrees of freedom during the back-ET reaction. Scherer and
co-workers demonstrated that the wavepacket motion in
Prussian blue intervalence CT complex originated from the
ground state and the excited CT state.109 Further, it was
proposed that several low-frequency vibrational modes are
coupled to the CT coordinate.109 The longer lifetime of the
vibrational coherences than ET could implicate that wave-
packet survives the ET event and is transferred to the product
surface.
Wynne et al. in 1996 used a 40 fs, 810 nm pump pulse to
create vibrational coherences in the CT state of an electron
donor−acceptor π-stacked complex between tetracyanoethy-
lene (TCNE) and pyrene.110 Clear oscillations were observed
in the ground-state bleach and the stimulated emission signals
during the back-ET process in 250 fs−1.5 ps. It was found that
the oscillations due to 160 cm−1 mode in the stimulated
emission signal survived for the time scale of the ET and
modulated the rate of the back-ET from the CT to the ground
state. This vibrational wavepacket was implicated to result in
coherent formation of the product state via stepwise
modulations of the ground-state signal.110,111 However,
identifying a temporal modulation on the basis of visual
distinction between vibrationally modulated recovery of
population and sinusoidal wavepacket oscillations on the
ground state is almost impossible, unless we are dealing with a
diatomic moleculefor example, the familiar dissociation of
sodium iodide studied by Zewail and co-workers.112−114
Bixon and Jortner in 1997 modeled the temporal vibrational
coherence effects in non-adiabatic ET dynamics in the π-
stacked TCNE-pyrene ET complex.104 The calculations
predicted that for a nonradiative decay, the amplitude of
coherences is determined by the off-diagonal matrix element
(vibronic or electronic coupling between the states) and the
reactant−product correlation (a function of FC vibrational
overlaps between the reactant and the product states). It was
proposed that in the TCNE−pyrene ET complex, the most
pronounced modulations originate in the vibrational wave-
packet motion of the initial state and are not due to the
vibrationally coherent product formation.
714
A new question arises then: Does a coherent excitation of a
wavepacket modify the ET dynamics? A coherent excitation
instantaneously prepares a non-Boltzmann distribution of an
initial reactant state as superpositions of vibrational states of
the Franck−Condon active nuclear modes. In the case of weak
electronic coupling, due to the separation of time scales
between the electronic and nuclear motion, ET occurs only
after the relaxation of nuclei to the Boltzmann distribution.103
Therefore, the temporal coherences created by wavepacket
motion dephase in the reactant state. On the other hand, in the
intermediate regime of coupling, an ET reaction may be faster
than the nuclear relaxation that dephases the wavepacket
(often similar to the time scale of intramolecular vibrational
relaxation); thus, an ET reaction occurs from “hot” vibrational
states. This will be interesting to study, but the challenge is
how to analyze the effect of a non-Boltzmann distribution of
initially prepared states on the ET dynamics.
Mathies and co-workers studied a π-stacked CT complex
tetramethylbenzene−tetracyanoquinodimethane, using two-
dimensional Raman spectroscopy and proposed that intra-
molecular CT is equivalent to a conical intersection between
excited and ground states.115,116 The branching space of the
conical intersection is defined by the anharmonically coupled
totally symmetric 323 cm−1 CCN bend (tuning mode) and
non-totally symmetric 1271 cm−1 CC rocking mode
(coupling mode) (Figure 5a). The coherences produced
along the tuning and coupling modes branch at the conical
intersection, and a portion of it crosses over to the ground state
during the back-ET process.117−119
Betaine-30 is another example, in which photoexcitation
accesses a CT state, followed by a solvent-dependent ultrafast
back-ET1.2 ps in acetonitrile and 3.1 ps in methanol.120 The
possible role of coherent vibrational motion was explored by
Scholes and co-workers using a ca. 12 fs broadband pump−
probe spectroscopy.121 It was found that dephasing times of
certain high-frequency vibrations (1356, 1581, 1602 cm−1)
correlate with the solvent-dependent ET rate, which suggests
they are pertinent for the ET (Figure 5b). For example, the
dephasing time constants of 1581 and 1602 cm−1 modes are
0.27 and 0.29 ps in acetonitrile, where the rate of ET is 1.2 ps,
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and the corresponding dephasing time constants in methanol
are 0.57 and 0.84 ps, where the rate of ET is 3.1 ps. Silva and
co-workers reported that these high-frequency modes show
frequency shifts and are anharmonically coupled to the low-
frequency modesprompting them to suggest that these
modes are relevant to the back-ET.122 Back-ET in Betaine-30
represents a radiationless crossing of the excited-state and the
ground-state potentials in the adiabatic limit.121 As per Bixon−
Jortner theory, to bridge the energy gap between the two
potentials, high-frequency quantum vibrations couple to the
ET process. In Betaine-30, the free energy change for the
product formation in acetonitrile is ca. 11 000 cm−1, so for the
high-frequency mode (say 1600 cm−1) to participate in the
back-ET process, it must provide a fourth or fifth vibrational
quantum on the product surface (Figure 5c) to make the
process barrierless (considering a total reorganization energy of
ca. 3500 cm−1 for acetonitrile).121 Note that this large energy
gap relative to the reorganization energy in Betaine-30 makes
this a case of Marcus inverted region.
A vibrational quantum (fourth or fifth) that is high in the
potential will have a very small Franck−Condon factor
associated with it. Thus, the enhancement in the rate due to
the vibronic interactions is an outcome of near resonance
condition between the reactant and product states but not due
to the electronic coupling (ca. 2500 cm−1). The effective
coupling (<5 cm−1) is significantly smaller due to the dressing
by the Franck−Condon factor. With that small effective
coupling, the correlation between the generated superposition
on the reactant surface and the acceptor vibrational states on
the product will be random due to the strong amplitude of
energy gap fluctuations produced by solvent polarization.
Therefore, vibrational coherences generated on the reactant
state thus largely dephase on the reactant surface, with a very
negligible transfer to the product surface. Thereby any
coherence effect is lost due to strong energy gap disorder
induced by the surrounding fluctuations, and hence the back-
ET will be predominantly incoherent.121
The correlation between the back-ET rate and vibrational
wavepacket dephasing of certain high-frequency modes,
mentioned above, can be put in perspective by invoking the
nested free energy crossings, discussed above (Figure 4). Along
all the vibronic channels furnished by the coupled high-
frequency modes, multiple crossings between reactant and
product free energies induce dispersion of the vibrational
coherence involving the coupled modes. That dispersion
causes faster dephasing of the wavepacket in acetonitrile
solvent (1.2 ps) relative to the methanol solvent (3.1 ps). We
therefore suggest that the mean first passage time of the ET to
the transition state is shorter in acetonitrile compared to
methanol solvent, and that these values scale proportionally to
the reaction rates.
In the case of intermolecular or outer-sphere ET systems
with inherently large heterogeneities, the correlations between
reactant and product states are subject to stronger energetic
disorder originating from solvent reorganization; hence,
vibrational coherence dynamics may present differently.
Zinth and co-workers, while studying ET from an electron-
donating solvent (dimethylaniline) to a photoexcited electron-
accepting dye (oxazine)with an ET time constant of ca. 80
fs, identified high-frequency wavepacket motion of 600 cm−1
using a 20 fs pump pulse.123−125 While earlier experiments
probed wavepacket motion in the reactant state only, their
work probed oscillations in the product state also. The
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Perspective
presence of coherent oscillations in the product state indicated
wavepacket transfer during the ET reaction. It was proposed
that vibrational motion along the 600 cm−1 mode plays an
active role in the ultrafast ET from DMA to oxazine. Scholes
and co-workers revisited the same ET systems and concluded
that the wavepacket motion on the product state is not an
outcome of coherence transfer.126 It is merely a spectator that
passes from the reactant to the product state without affecting
the ET reaction. This is consistent with the Born−
Oppenheimer separation of electronic and nuclear degrees of
freedom. The ultrafast rate of the ET may indeed derive from
the coupling of high-frequency quantum vibrations to the ET
reaction as represented in the Bixon−Jortner theory.104
The examples cited above highlight the use of vibrational
wavepacket dynamics as internal clocks in probing the role of
high-frequency quantum vibrations in the ET reactions. To
summarize, the main challenge is to identify the reaction-
promoting vibrations from a sea of spectator vibrations. The
reaction promoting vibrations are part of the ET reaction
coordinate, while the spectator modes, as the name suggests,
do not participate in the ET reaction. Spectator modes are
orthogonal to the reaction coordinate, so their corresponding
wavepackets dephase on a longer time scales than wavepackets
of the reactive modes. In other words, a wavepacket
comprising spectator vibrations can be transmitted through
the crossing region of ET without undergoing any significant
additional dephasing. Contrarily, a wavepacket comprising
reaction-promoting vibrations can undergo rapid dephasing
due to the nesting of free energy curves, as discussed above.
Vibronic coupling may have varying effects on the ET
dynamics depending on the extent of vibronic wave function
delocalization, which strongly depends on the reactant−-
product energy gap. In the presence of a large reactant−-
product energy gap, the bottom acceptor levels are offset from
the donor level leading to highly localized wave functions on
the product potential. The ET along localized channels occur
only when energy fluctuations induce transient degeneracy of
the reactant and product. However, the higher accepting level
of the product state may be in accidental quasi-degeneracy
with the donor level, therefore resulting in vibrational wave
function delocalization between the reactant and product wells.
Such wave function delocalization is a result of mixing
electronic wave functions of the reactant and product states
in the presence of a resonant vibration as well as electronic
coupling. Due to these vibronic mixing effects, ET may be fast
along certain intramolecular coordinates.
In a strong coupling regime, where vibronic mixing is
prominent, photoexcitation will directly access a vibronic CT
state, so the concept of photoexcited ET from reactant to
product is superfluous. However, in an intermediate coupling
regime, the ET dynamics will generally involve interplay of
solvent reorganization and the vibrational reaction coordinate.
Certain solvent fluctuations might, for instance, produce
conditions enabling vibronic resonance, which may provide
coherent contributions to the transfer. In the non-adiabatic
limit, this scenario is precisely that indicated by the nested free
energy curve model.
In the past few years, researchers in the groups of
Rubtsov127,128 and Weinstein129−131 have used infrared
perturbations and demonstrated the effect of vibrational
excitation of bridging modes on the ET reactions. The
measurements on donor−bridge−acceptor CT complexes
revealed that the rate of ET is highly dependent on the
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amount of excess energy localized on the bridge. By applying

an infrared excitation pulse resonant with a bridge vibration, an
ET pathway was selectively turned off or slowed down. One of
the reasons for such a control has recently been proposed to
originate from level matching or mismatching between the
reactant and product states upon vibrational excitation.132
These studies have used vibrations as an active control for the
ET reactions and are potentially promising to shine light on
the vibronic mixing effects, coherent contributions enabled by
vibrations, etc.
Coherences in Biological Systems. Vibronic mixing enables
wave function delocalization in the presence of a disorder
comparable to the electronic coupling and has been
demonstrated for photoinduced ET in photosystem-II reaction
center.98,99 The charge separation process in photosynthesis
converts excitation energy into a stable charge-separated
state.133 In isolated reaction centers that lack quinones, the
absorbed energy relaxes to the lowest state in a few hundred
femtoseconds.134 This lowest energy state evolves into a CT
state characterized by localization of the electron and the hole
on adjacent chlorophyll molecules.135,136
Romero et al.98 and Fuller et al.99 applied 2DES137−139 and
simulations to study the role of coherences during photo-
induced charge separation event in the photosystem II reaction
center. Their measurements revealed coherent oscillations in
the time domain signals like those observed during the energy
transfer in photosynthetic systems.140−143 To determine the
origin of the coherent oscillationselectronic, vibrational, or Figure 6. Effect of resonant vibration on dynamics. The effect of the
mixed electronic−vibrational (vibronic)a comparison was absence or presence of a vibration resonant with the energy gap
made between the experimentally observed pattern of between the exciton and charge-transfer state on electron-vibrational
oscillations and those from Redfield theory-predicted simu- mixing (top panel) and charge-separation dynamics (bottom panel) is
lations. This comparison revealed that the temporal oscillations shown. In the presence of finite electronic coupling (150 cm−1 in this
are predominantly of vibronic origin (mixed electronic− example), under resonant conditions, zero vibrational quanta of the
vibrational), and the coherence is maintained by resonant exciton mixes with higher vibrational quanta of the CT state. This
nonequilibrium vibrational modes between the excitonic states mixing induces delocalization of the vibronic wave functions.
Whereas, under nonresonant conditions, the vibrational wave
and the CT state. The coherences were found to persist on the functions remain localized, so mixing or delocalization is prevented.
time scale of charge separation. These mixed electronic− The mixing of the vibronic wave functions from resonant interaction
vibrational (vibronic) coherences were proposed to enhance results in 3.3-fold increases in the ET rate. This mixing essentially
the rate of charge separation due to vibrational level bridging prevents back-reactions and thus results in directionality and
the electronic gap resulting in wave function delocalization. efficiency of the forward process. Adapted with permission from ref
Such electronic vibrational resonances have been suggested to 5. Copyright 2017 Springer Nature.
be potentially important for enhancing photosynthetic energy
transport.6,88,90,143−147 These types of studies have lead individual wells, but also between the wells over the curve
researchers to propound a quantum design of photosynthesis crossing region. It was further shown that the presence of a
for bioinspired solar-energy conversion.96,148 resonant vibration enables 3.3-fold increase in the population
The effect of the absence and presence of a vibration transfer rate from the exciton state to the CT state.148
resonant with the exciton-CT energy gap on electron- Such interplay between electronic states and coupled
vibrational mixing and the CT dynamics was shown by van vibrational modes has also been predicted in organic
Grondelle and co-workers145,148 and also by Scholes and co- photovoltaic (OPV) material systems. Coercing ET events
workers (on energy transfer dynamics)6 for a two-level one through vibrations make it a particularly attractive design
mode system (Figure 6). In the absence of the resonant principle, which has a potential for preparing more efficient
vibration (vibrational frequency detuned from the energy gap), OPV materials.
the vibrational wave functions of the exciton and the CT state Coherences in Material Systems. A largely accepted
do not overlap; therefore, they are predominantly localized in viewpoint regarding OPVs is that light absorption creates a
their individual potential wells. However, in the presence of the localized exciton that hops randomly and incoherently before
resonant vibration, the vibronic coupling leads to mixing of the dissociating into free charge carriers.149 Achieving efficient
excitonic and CT state potential wells. From the perspective of dissociation of exciton into free carriers has long been
the wavepacket dynamics, under non-resonant conditions the recognized as a vital challenge for molecular-based solar
wavepacket oscillates in the localized potential wells of the cells.149−152 Recent work has indicated that coherence effects
exciton and CT state. However, under resonant conditions, the can be prevalent in OPVs also; therefore, coherence may have
wavepacket oscillates between the potential wells of the exciton an active role in ultrafast charge separation.10 Heeger and co-
and the CT state. Which means that phase coherence of the workers performed transient absorption measurements on
vibronic wave functions is not only maintained in the polymer−fullerene bulk heterojunction solar cells and found
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Figure 7. Coherent dynamics in material systems. (a,b) Two-dimensional electronic spectra of a P3HT/PCBM blend at 35 and 300 fs after
photoexcitation. (c) Time dependence of the amplitude of signal at the hole PIA cross-peak and P3HT bleach. (d) Absorption spectrum of
cadmium selenide (CdSe) nanoplatelets showing HX and LX transitions. Shaded curve is the laser pulse spectrum used to measure 2DES data. (e)
2D spectrum at 52 fs showing clear diagonal and anti-diagonal peaks. (f) Kinetic trace extracted at the lower cross peak showing amplitude
modulations as a function of waiting time. The frequency of the modulation corresponds to the energy difference between the two excitonic
statesreferred to as electronic coherence. Panels a−c are adapted with permission from ref 160. Copyright 2014 Springer Nature. Panels d−f are
adapted with permission from ref 87. Copyright 2015 Springer Nature.

that majority of charge carriers are generated within ca. 100
fs.153 It was proposed that the initial photoexcited state is a
coherently delocalized state instead of a localized exciton, and
excitonic delocalization is responsible for ultrafast charge
separation over long distance.153 Friend and co-workers
studied the time dependence of the separation of photo-
generated electron−hole pairs across the donor−acceptor
heterojunction.154 They found that the Coulombic barrier
between electron and hole is surmounted in ca. 40 fs, which
would be possible only in the presence of rapid charge motion
away from the interface through delocalized band states. The
electronic motion on the acceptor site was modeled to be
coherently coupled to the nearest neighbors, which gave rise to
a band of delocalized eigenstates, and this coherent coupling
causes charge separation over a distance of 3−5 nm within a
few hundred femtoseconds.154
Burghardt and co-workers applied a quantum mechanical
treatment of the combined electronic and nuclear evolution to
study the ultrafast charge separation in the conjugated
oligomer−fullerene complex of P3HT and C60.155 The initial
CT dynamics was shown to be guided by vibronic coherence,
which determines the observed oscillatory features of the
transient dynamics. It was shown that coupled phonon
modesparticularly high-frequency modes of the acceptor
are essential to dissipate energy and induce dephasing, thus
leading to immediate charge separation in ca. 100 fs. The work
predicts that it is the vibronic coupling which directs charge
separation, instead of the thermally induced barrier crossing as
considered previously.156,157
Lienau and co-workers investigated the primary CT process
in a prototypical artificial reaction centera supramolecular
triad of carotene−porphyrin−fullerene.158 Combined exper-
imental and theoretical data provided evidence for a correlated,
717
quantum coherent motion of electrons governing the primary
charge flow, which is coupled to the delocalized nuclear
motion across the porphyrin−fullerene region. The CT was
shown to occur in ca. 70 fs, and on this time scale the launched
electronic wavepacket of 30 fs period oscillates between the
carotenoid−porphyrin group and the fullerene.158 They further
extended the study to a conjugated polymer−fullerene blend
and observed coherent vibrational motion of the fullerene
acceptor after impulsive excitation of the P3HT polymer
donor.159 An electronic oscillation was coherently produced on
the fullerene acceptor after photoexcitation of the polymer
blend, and the period of this oscillation (25 fs) matches with
the vibrational frequency of the blend. It was proposed that
upon optical excitationwhich creates an electron−hole pair
on the P3HT polymerthe strong electronic−vibrational
coupling induces a delocalization of the electronic wave
function across the interface. The correlated motion of the
electron density and the nuclei on the same time scale was
proposed to be responsible for the early time ultrafast charge
separation in this model OPV system.159
Once this coherently driven delocalization of electronic wave
function across the donor−acceptor interface catches up with
the phonon cloudmolecular relaxation that stabilizes the
chargethe localization of electron density occurs. This
localization, however, occurs at some distance from the
interface resulting in reducing the electron−hole attraction.
Further, due to the associated phonon interaction, the electron
must now be transported forward via hopping, thereby
reducing the chance of back-reactions.10
To illustrate the experimental detection of coherent
oscillations in an OPV active layer, 2DES measurements of
the P3HT−PCBM blend are shown in Figure 7.160 Excitation
of a P3HT donor, when blended with fullerene acceptor, the
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Figure 8. Mapping electron and nuclear dynamics. (a) Direct measurement of ultrafast charge transfer in amino acid phenylalanine after a sub-300-
attosecond XUV pump excitation. The charge transfer manifested itself as a sub-4.5 fs-oscillation in the formation of the doubly charged immonium
ion suggestive of periodic electronic wavepacket motion. (b) Theoretically simulated variation of hole density after XUV excitation as a function of
time. Snapshots at time intervals of 4.4 and 3.4 fs show same hole density at the highlighted amino group suggestive of the periodic wavepacket
dynamics. (c) Schematic drawing of the ultrafast electron diffraction experiment which uses an optical pump pulse and an electron probe pulse. The
subsequent real-space analysis of diffraction patterns of CF3I molecule are shown. (d) Detailed wavepacket dynamics over multiple potential energy
surfaces of CF3 I deduced from UED experiments. Panels a and b are reprinted with permission from ref 162. Copyright 2014 AAAS. Panels c and
d are reprinted with permission from ref 170. Copyright 2018 AAAS.

C60 derivative PCBM, results in rapid ET from the P3HT to
the fullerene domain. This is confirmed by a growth of the
P3HT hole transient signalindicated by a photoinduced
absorption that is clearly resolved as a cross peak in the 2DES
maps (Figure 7a−c). Vibrational wavepackets generated in
both the ground and excited states of the P3HT exciton
spectral region are later detected in the product photoinduced
absorption signal of the P3HT hole. Such transfer of a
wavepacket is an indicative of either the spectator nature of the
modes or a more obscured reactive significance. This example
shows how vibrational wavepackets can label excited states and
provide information through amplitude and phase of the
oscillations as the reactant state evolves into the product state
during ET event.
In addition to observing vibrational wavepackets, the
prowess of 2DES in detecting electronic coherences exclusively
was shown by Cassette et al. between two excitonic states,
heavy-hole exciton (HX) and light-hole exciton (LX), of a
semiconductor “nanoplatelet” colloid dispersed in a solution at
ambient temperature (Figure 7d−f).87 The amplitude of the
cross peak, HX-LX and LX-HX, in the 2D signal map oscillate
as a function of waiting time, showing that the quantum
amplitude of HX and LX bands are correlated until the
excitonic superposition dephases. The dephasing time constant
of this ensemble was found to be of 13 fs, while the typical
electronic decoherence time constant is ≤100 fs.
energy disorder.161 Indeed, spectral line widths of the
electronic transitions would imply the dephasing time scale
of <100 fs. A shift in the perspective has, however, been offered
by the developments in the area of photosynthetic energy
transfer where coherence effects are more robust to dephasing
when electronic energy gaps are matched by vibrational energy
gaps. We anticipate that such vibronically enabled coherence is
functionally relevant for a dynamical process like ET at least in
phase space representing a quantum mixture of donor and
acceptor states. Putting it in perspective, the donor and
acceptor potentials may be local at their equilibrium positions,
but the crossing region can be adiabatic, and hence the system
may repeatedly pass from a localized to delocalized basis (or
incoherent to coherent) as a function of vibronically coupled
nuclear coordinate. Therefore, the functional role of
coherences should not rely on the fragile and rapidly dephasing
superposition of states. Instead, it represents the trajectories in
that small phase space through which donor states transport
electrons into the acceptor states.
We can ask, What is needed to shift these pioneering studies
from being notional to incisive? A key question relates to how
we think of “coherences” in ET reactions beyond what we
know. What are the experimental variables, which can provide
decisive information about the coherent or incoherent nature
of the process? How do we establish the role of coherence for

■ PERSPECTIVE ON COHERENCES IN ELECTRON

TRANSFER
The argument against a functional role of coherence in
complex systems is that the phase-locking of the wave
functions is rapidly lost by dephasing in systems having strong
718
function? To this end, we must categorize more definitely the
different ways that coherence contributes to ET reactions. Is
adiabaticity significant in this regard, or obvious? Is the role of
high-frequency intramolecular modes the key? Do we need to
develop new experiments which can distinguish the effects of
local environment and complex electronic and vibrational
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structure of the systems more adequately than current
femtosecond experiments?
Pure optical spectroscopies have so far been pivotal in
revealing time-domain coherent oscillations. We believe that
the functional role of coherences might emerge by exploring
real-time atomic-scale spatial imaging of charge and nuclear
dynamics. That would require time resolution into the
attosecond regimecapable of revealing electron correlations
and non-adiabatic dynamics.162 Emerging X-ray free electron
laser (XFEL) sources capable of producing ultrashort X-ray
pulses at high repetition rates hold the key to capturing the
atomically resolved structures.163−165 X-rays have enough
momentum to provide a complete map of the electronic and
vibrational states. A suite of X-ray-based diffractive, spectro-
scopic, and imaging techniques can be applied to capture the
motion of electron density excited locally and subsequently
moving rapidly across to the acceptor.
A demonstration of the impact of attosecond spectroscopy
was shown by Calegari et al. for the CT dynamics in amino
acid phenylalanine where CT manifested itself as a sub-4.5-fs
oscillation (Figure 8a,b).162 The initial creation of electronic
coherences and coherently driven electronic rearrangement
can be probed by mapping the charge as a function of time.
Electronic coherence would mean that charge oscillates from
reactant to the product potentials before localization, which
can be captured by free electron lasers.162,166,167 Because of the
spatial resolution, this technique can further probe the position
of nuclei as the electronic wave function evolves, and hence the
vibronic effects, which may give rise to coherent dynamics, can
also be probed.
Ultrafast electron diffraction (UED) is another direct probe
of structural dynamics exhibiting high spatial and temporal
resolution.168,169 UED uses electron pulses to probe structural
dynamics from the diffraction pattern created by the electron
pulses, after optical pulses access high-energy states. Recent
work by Yang et al. imaged conical intersection and
photodissociation dynamics of CF3I using UED (Figure
8c,d).170,171 Conical intersections, as described above, play
an important role in controlling excited-state dynamics and
have been proposed to be functional in the coherent back-ET
of π-stacked donor−acceptor complexes, etc. UED has been
shown to image real-space trajectories of coherent nuclear
wavepacket bifurcating at the branching space of the conical
intersection. The beauty of UED like XFELs is that it probes
both electronic and nuclear motions simultaneously, so if a
correlation exists between the electronic and the nuclear
motion, these techniques can resolve such coherent
interactions in both time and space. Therefore, we believe
that validating the functional role of coherences requires to go
beyond the pure optical spectroscopies and move toward time-
resolved dynamical probes.
■ CONCLUSION
In this Perspective we discussed how vibrational coherences
can help characterize some elements of reactant-product
interactions in electron transfer reactions. That character-
ization hinges on watching the evolution of coherences
involving the spectator and reactive vibrational modes.
Coherences comprising spectator modes do not undergo
phase dispersion during ET; therefore, no additional dephasing
of the wavepacket is induced. Contrarily, in the ET reactions
where nested free energy curves provide multiple kinetic
pathways from reactant to product, the phases that make up
719
Perspective
the wavepacket become out of step owing to dispersion of the
transition states for the different pathways. Therefore, the
reactive wavepackets dephase rapidly as the system reaches the
transition state.
The direct participation of coherence in controlling function
is a fascinating idea that might possibly have revolutionary
prospects, as discussed recently.6 To date, the most direct
implication has been envisioned in OPVs, in which coherent
generation of mobile charge carriers has been hypothesized. It
is actually the subsequent decoherence which is important for
inhibiting recombination of the electrons and holes.10
Irrespective of the amount of work done in the field of
coherences, much more is needed to get a better under-
standing of coherences in ET. Often researchers are tempted to
focus solely on measurement of time-domain wavepacket
oscillations. The challenge, though, is to disentangle oscillatory
signals from the actual role played by vibrations or coherence.
In our studies we have found that in most systems, oscillations
result from spectator modes; therefore, they have little
relevance to the process. One must fully explore the large
state-space, identify the reactive vibrations, and then assess
coherences along those reactive modes. Coherence in ET is
firmly connected to adiabaticity, environment fluctuations and
their time scales, and intramolecular vibrations, so exploring
the effect of these parameters on reactive wavepacket dynamics
could help us in first identifying the presence of coherent
effects and then assessing their potential functional relevance.
The key question is whether coherence in ET can provide new
function or whether it simply modifies details of the
mechanism? Exploring these issues in ET may provide new
connections between chemical design at the molecular level
and energy transduction dynamics and efficacy.
■
AUTHOR INFORMATION
Corresponding Author
*gscholes@princeton.edu
ORCID
Shahnawaz Rafiq: 0000-0002-9660-4495
Gregory D. Scholes: 0000-0003-3336-7960
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
S.R. and G.D.S. acknowledge support from the Division of
Chemical Sciences, Geosciences, and Biosciences, Office of
Basic Energy Sciences, of the U.S. Department of Energy
through Grant No. DE-SC0015429.
■
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722 DOI: 10.1021/jacs.8b09059

J. Am. Chem. Soc. 2019, 141, 708−722