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 Journal of Physics B: Atomic, Molecular and Optical Physics

J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003 (12pp) https://doi.org/10.1088/1361-6455/aa93d0

Impact of charge-transfer excitons in

regioregular polythiophene on the charge
separation at polythiophene-fullerene
heterojunctions
M Polkehn1, H Tamura2 and I Burghardt1
1
Institute for Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7,
D-60438 Frankfurt, Germany
2
Department of Chemical System Engineering, School of Engineering, The University of Tokyo, Tokyo
113-8656, Japan

E-mail: burghardt@chemie.uni-frankfurt.de

Received 6 July 2017, revised 1 October 2017

Accepted for publication 16 October 2017
Published 30 November 2017

Abstract
This study addresses the mechanism of ultrafast charge separation in regioregular
oligothiophene-fullerene assemblies representative of poly-3-hexylthiophene
(P3HT)-[6,6]-phenyl-C61 butyric acid methyl ester (PCBM) heterojunctions, with special
emphasis on the inclusion of charge transfer excitons in the oligothiophene phase. The formation
of polaronic inter-chain charge separated species in highly ordered oligothiophene has been
demonstrated in recent experiments and could have a significant impact on the net charge
transfer to the fullerene acceptor. The present approach combines a first-principles parametrized
multi-site Hamiltonian, based on time-dependent density functional theory calculations, with
accurate quantum dynamics simulations using the multi-layer multi-configuration time-
dependent Hartree method. Quantum dynamical studies are carried out for up to 182 electronic
states and 112 phonon modes. The present analysis follows up on our previous study of (Huix-
Rotllant et al 2015 J. Phys. Chem. Lett. 6 1702) and significantly expands the scope of this
analysis by including the dynamical role of charge transfer excitons. Our investigation highlights
the pronounced mixing of photogenerated Frenkel excitons with charge transfer excitons in the
oligothiophene domain, and the opening of new transfer channels due the creation of such
charge-separated species. As a result, it turns out that the interfacial donor/acceptor charge
transfer state can be largely circumvented due to the presence of charge transfer excitons.
However, the latter states in turn act as a trap, such that the free carrier yield observed on
ultrafast time scales is tangibly reduced. The present analysis underscores the complexity of the
transfer pathways at P3HT-PCBM type junctions.
Keywords: quantum dynamics, organic photovoltaics, excitons

(Some figures may appear in colour only in the online journal)

1. Introduction investigated over recent years [1–3]. A particular focus has

Exciton dissociation in prototypical blends of poly-3-
hexylthiophene (P3HT) and the fullerene derivative
[6,6]-phenyl-C61 butyric acid methyl ester (PCBM), and related
polymer/fullerene combinations have been extensively
been directed at investigating the conditions facilitating ultra-
fast long-range electron–hole separation, as experimentally
observed especially in regioregular materials [4, 5]. A priori, a
much slower, thermally activated dynamics is expected in the
presence of an effective Coulomb barrier, according to the

0953-4075/18/014003+12$33.00 1 © 2017 IOP Publishing Ltd Printed in the UK

J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003 M Polkehn et al

Onsager–Braun model [6]. To explain these observations, band [32]. As mentioned above, these Frenkel-type species
transient effects due to hot states [5, 7, 8], charge delocalization may be intimately coupled, though, to charge transfer exci-
[3, 7, 9–11], the role of the driving energy [7, 12], destabili- tons involving inter-chain charge separation [20–22]. Both
zation of the interfacial charge transfer state [13], the details of types of species are coupled, in turn, to donor/acceptor
the microelectrostatics at the interface [14, 15], and entropic charge separated states. The coupling and interconversion
effects [16] have been invoked. In our recent work [17, 18], we between these three types of electronic configurations will be
have pointed out that the effective lowering of the Coulomb at the center of our discussion.
barrier due to charge delocalization, and the vibronically hot In line with the notation introduced in [17, 18, 23], an
nature of the primary excitonic and charge transfer states can e–h lattice Hamiltonian is formulated and parametrized based
play a central role. upon electronic structure (here, TDDFT) calculations for
In the present study, we build upon our recent investi- relevant fragments. To simplify the model, the fullerene
gations [17–19] of regioregular P3HT-PCBM type systems moiety is represented by an effective, coarse-grained super-
and extend the latter studies so as to include charge separated particle site (ν = 0) [17, 18], while N oligothiophene frag-
species within the P3HT type donor domain. Indeed, as has ments are treated explicitly as individual oligomer sites
been shown in recent experimental investigations [20–22], (ν = 1, K, N). Localized e–h pairs ∣nnñ (for ν = 1, K, N)
charge transfer excitons, or polarons, are observed in oli- correspond to Frenkel excitonic (XT) configurations on the
gothiophene phases, presumably by inter-chain polaron pair OT moieties, ∣XTnñ = ∣n = n , m = nñ. Conversely, non-local
formation in highly ordered, lamellar domains. This raises the e–h states ∣nmñ, m ¹ n (ν = 0, μ = 1, K, N), represent charge
question whether the presence of charge transfer excitons separated (CS) configurations, ∣CSn ñ = ∣n , m = n + nñ,
affects the yield of charge separated species between donor where ν = 0. The CS1 state corresponds to the interfacial
and acceptor domains and, hence, the power conversion charge-transfer state (denoted CT in [17]). Finally, charge-
efficiency. Indeed, a non-negligible amount of polaronic separated inter-chain species in the OT domain are included,
species in the donor phase could open up additional transfer i.e., charge transfer exciton configurations of type ∣CTXn, n ¢ñ =
pathways and enhance the effective charge transfer to the ∣n = n , m = n¢ñ where n , m = 1,¼, N .
acceptor phase. Conversely, polaronic species could turn out In the dynamical treatment detailed below, delocalized
to be stabilized in the donor phase and effectively reduce the Frenkel excitonic states, and delocalized mixtures of Frenkel
reservoir of active electron–hole pairs available for interfacial and charge transfer excitonic states arise as coherent super-
charge separation. positions of e–h configurations ∣nmñ; for the full wavefunction
To investigate the role of charge transfer excitons in the including phonon modes, see equation (7).
oligothiophene domain, we use electronic structure studies at The Hamiltonian is defined in the above e–h basis, in line
a time-dependent density functional theory (TDDFT) level of with [17, 18], i.e.,
relevant molecular fragments to parametrize a multi-state
lattice Hamiltonian [17–19, 23], which is subsequently el
Hˆ = Hˆ + Hˆ
e - ph
combined with quantum dynamical simulations using the on ‐ site coup e - ph
multi-layer multi-configuration time-dependent Hartree (ML- = (Hˆ + Hˆ ) + Hˆ (1 )
MCTDH) method [24–30]. In the present study, high-
el
dimensional lattice models with up to 182 electronic states comprising an electronic part (Ĥ ) and an electron–phonon
and 112 vibrational (phonon) modes are investigated. This coupling part (Ĥ
e - ph
). The electronic part, in turn, is split into
model contains the essential ingredients permitting the on-site contributions (Hˆ
on ‐ site
) and electronic couplings
investigation of the above questions. coup
(Ĥ ). In the following, the individual parts of the Hamil-
The remainder of this article is organized as follows. We
tonian are detailed.
first describe the electron–hole lattice model that is employed
in the present study. Next, we illustrate the modified ener-
2.1. On-site Hamiltonian
getics of the system in the presence of charge transfer exci-
tons. We then turn to a high-dimensional quantum dynamical The on-site part of the Hamiltonian is given as
investigation using the ML-MCTDH method. Finally, we
offer a discussion and conclusion. N N
=  XT å ∣XTnñáXTn∣ + å  nCS∣CSn ñáCSn ∣
on ‐ site
Hˆ
n=1 n=1
N N
2. Electron–hole lattice Hamiltonian
+ åå n ¢= 1
n, n ¢ ∣CTXn, n ¢ñáCTXn, n ¢∣ ,
 CTX (2 )
n=1
In the model system depicted in figure 1, representing a n ¢¹ n

regioregular oligothiophene (OT)-fullerene domain repre-

sentative of P3HT-PCBM, the primary OT photoexcitations
in the self-assembled lamellar structures are inter-chain,
H-aggregate type excitons [31, 32]. These delocalized exci-
tations are typical of face-to-face aligned aggregates whose
bright state is located at the high-energy edge of the excitonic
where the excitonic states ∣XTnñ are taken to have identical on-
site energies ( XT ) while the energies of the charge-separated
states ∣CSn ñ and the OT charge transfer excitonic states
∣CTXn, n ¢ñ are determined by an effective Coulomb barrier as
further discussed next.

2
J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003
The effective barrier potential that defines the on-site
energies of the ∣CSn ñ states is depicted in figure 1 (lower
panel); this effective potential describes the Coulombic
interaction between delocalized electron and hole distribu-
tions, and includes the effect of the internal electric field. As
detailed in [17, 19, 33], the barrier was determined from DFT
calculations in conjunction with a tight-binding model, where
a representative field value of E = 10 V μm−1 was used. The
barrier height is a sensitive function of electron delocalization
within the fullerene moiety and, hence, depends on the
effective size of the fullerene super-particle in our model. In
the present study, two characteristic barrier heights are con-
sidered: (i) around 0.25 eV, for small fullerene clusters (here,
a 7-C60 cluster) representative of disordered domains, (ii)
around 0.05 eV, as a result of delocalization across several
fullerene layers (here, five 61-C60 layers) [17]. These barrier
types will be referred to as barrier I and barrier II in the
following (see figure 1).
Likewise, the on-site energies of the OT charge transfer
excitonic states ∣CTXn, n ¢ñ are determined by a Coulomb bar-
rier, which was taken to be of the standard form
CTX
Vbarrier = -1 (4p 0 r rnn ¢ ). Here the relative permittivity
r = 3.5 was used and rnn ¢ = (∣n - n¢∣rru + r0 ) is the e–h
distance as a function of the sites (n , n¢), with rru the repeat
unit length and r0 the intrinsic e–h distance for a Frenkel
exciton.
2.2. Electronic couplings
Next, the electronic coupling part of the Hamiltonian com-
prises multiple transfer channels and reads as follows,
coupl
Hˆ = l (∣XT1ñáCS1∣ + h.c.) + k (∣CTX1,2ñáCS2 ∣ + h.c.)
⎛N -1 N ⎞
+ k1 ⎜ å ∣XTn ñáCTX n + 1, n∣ + å ∣XTn ñáCTX n - 1, n∣ + h.c.⎟
⎝ n=1 n=2 ⎠ facial ∣CS1ñ state and could modify the overall efficiency of
⎛N -1 N ⎞
+ k 2 ⎜ å ∣XTn ñáCTX n, n + 1∣ + å ∣XTn ñáCTX n, n - 1∣ + h.c.⎟
⎝ n=1 n=2 ⎠
N N -1
+ j å (∣XTn ñáXTn + 1∣ + h.c.) + th
å (∣CSn ñáCSn +1∣ + h.c.)
n=1 n =1
⎛N -1 N
⎜
+ le ⎜ å å ∣CTX n, n ¢ñáCTX n + 1, n ¢∣ + h.c.
⎜ n = 1 n ¢= 1
⎝ n ¢¹ n, n + 1
⎞
N N
⎟ very rapid decrease in magnitude. As compared with the
+ å å ∣CTX n, n ¢ñáCTX n - 1, n ¢∣ + h.c.⎟
n =2 n ¢= 1 ⎟ present values (k1= 0.36 eV, k 2 = 0.14 eV) for 3.5 Å (see
n ¢¹ n, n - 1 ⎠ figure 2), we obtained (k1= 0.17 eV, k 2 = 0.06 eV) for 4.0 Å,
⎛ N -1 N
⎜
+ lh ⎜ å å ∣CTX n, n ¢ñáCTX n, n ¢+ 1∣ + h.c.
n=1
⎝n ¢= 1n ¹ n ¢ , n ¢+ 1
N -1 N
⎞ is clear from the reduced couplings at larger distances that
⎟
+ å å ∣CTX n, n ¢ñáCTX n - 1, n ¢∣ + h.c.⎟.
n=2
n ¢= 1 ⎠
n ¹ n ¢ , n ¢+ 1
The first term relates to the coupling between the excitonic
and donor/acceptor charge transfer manifolds (l = 0.2 eV),
which is restricted to the interfacial ∣XT1ñ and ∣CS1ñ states. All
M Polkehn et al
couplings within the XT and CS manifolds are nearest-
neighbor interactions. As a new feature of the extended model
including OT charge transfer excitons, a coupling arises
between the ∣CTX1,2ñ state and the ∣CS2 ñ state (κ = 0.16 eV),
by electron transfer to the fullerene moiety. Next, the Frenkel-
type excitonic ∣XTnñ states couple to the charge transfer
excitons ∣CTXn, n ¢ñ either by electron transfer to one of the
neighboring sites (k1 = 0.357 eV) or by hole transfer to the
neighboring sites (k 2 = 0.139 eV).
The following terms in equation (3) describe the coupling
between nearest-neighbor excitons ( j = 0.1 eV), the hole
transfer between neighboring ∣CSn ñ states (th = -0.12 eV),
along with electron transfer (le = 0.08 eV) and hole transfer
(lh = 0.08 eV) between neighboring ∣CTXn, n ¢ñ states. Note
that le and lh are taken to be equal, which is a reasonable
approximation for the present system.
Table 1 lists all electronic couplings, and figure 2 illus-
trates the relevant electronic configurations and couplings for
a minimal model comprising two donor sites. All electronic
couplings were computed by a diabatization procedure as
detailed further in [33–35]. Clearly, a complex scenario of
coupled pathways emerges due to the presence of the CTX
states.
Given that the coupling constants λ and κ—which gen-
erate charge-separated ∣CSn ñ states from either the interfacial
∣XT1ñ state or the charge-transfer excitonic ∣CTX1,2ñ state—are
of comparable magnitude, competing transfer channels are
expected to arise for the photogenerated ∣XTñ states: either a
direct transfer to the interfacial ∣CS1ñ state takes place, or else
OT charge transfer excitons ∣CTX1,2ñ are generated first, fol-
lowed by a transfer to the ∣CS2 ñ state. The generation of
charge-transfer excitons should be efficient due to the large
couplings (k1, k 2 ) and favorable energetics. The pathway
∣XTñ ⟶ ∣CTX1,2ñ ⟶ ∣CS2 ñ bypasses the trapped inter-
exciton dissociation at the interface.
The electronic couplings k1 and k 2 that mediate transfer
between the ∣XTñ and ∣CTXñ states are a sensitive function of
the inter-chain distance, and take large values at short inter-
chain distances (here, 3.5 Å) characteristic of regioregular
domains. By contrast, these couplings are expected to be
strongly reduced in regiorandom phases where inter-chain
distances tend to be larger. For comparison, we have calcu-
lated (k1, k 2 ) for several representative distances and found a
and (k1= 0.08 eV, k 2 = 0.02 eV) for 4.5 Å. While changes in
the energetics and oligomer conformations also need to be
taken into account in the description of regiorandom phases, it
charge-transfer excitons will play a much less prominent role.
(3 )
2.3. Electron–phonon coupling
The electron–phonon coupling part of the Hamiltonian is
included within a linear vibronic coupling model, using
3
J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003 M Polkehn et al

Figure 1. Illustration of the oligothiophene-fullerene (P3HT-PCBM type) aggregate model of equations (1)–(3), where the fullerene acceptor
is considered as an effective super-particle. The Coulomb barrier that defines the on-site energies of the successive charge-separated states is
illustrated in the lower panel. Two types of barriers are considered, as explained in the text.

Table 1. Parameters for the coupling Hamiltonian equation (3), and for N ´ NOT oligothiophene modes (where N corre-
specified in eV. sponds to the number of OT units),
λ κ κ1 κ2 j th le lh
N NOT
OT 1
0.2 0.165 0.357 0.139 0.1 −0.12 0.08 0.08 Hˆ e- ph = å å 2 wlOT (( pˆnOT
, l ) + (qn, l ) )
2 ˆ OT 2
n =1 l=1
N NOT
+ å å cCS,
OT
l qˆn, l ∣CSn ñáCSn ∣
OT

fragment-based spectral densities [36] that were obtained n =1 l=1

N NOT
from state-specific Franck–Condon gradients, followed by a
truncated effective-mode expansion [18, 23, 35]. The elec- + å å cXT,
OT
l qˆn, l ∣XTnñáXTn∣
OT

n =1 l=1
tron–phonon coupling Hamiltonian is split into fullerene N N NOT
(C60) and oligothiophene (OT) contributions, + å å å (cXT,
OT
l qˆn, l + cXT, l qˆn ¢ , l )
OT OT OT

C60 OT n = 1 n ¢= 1 l = 1
Hˆ e- ph = Hˆ e- ph + Hˆ e- ph, (4 ) ´ ∣CTXn, n ¢ñáCTXn, n ¢∣. (6 )
where the Hamiltonian reads as follows in mass and fre-
Here, it is assumed that the OT electron–phonon couplings
quency weighted (dimensionless) coordinates, for NC60 full-
are identical for all fragments, such that the vibronic cou-
erene super-particle modes,
plings do not carry site indices n. Furthermore, it is assumed
C60
NC60
1 C60 C60 2 that the vibronic couplings for the ∣CTXn, n ¢ñ states are given,
Hˆ e- ph = å 2
wl (( pˆl ) + (qˆlC60)2 )
to a good approximation, by the sum of XT vibronic cou-
l=1
N NC60 plings of individual OT fragments (see [37]).
+ å å clC60 qˆlC60 ∣CSn ñáCSn ∣ (5 ) As in [18], we used NC60 = NOT = 8 effective modes per
n =1 l=1 fragment (hence, 112 modes overall). The relevant vibronic

4
J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003 M Polkehn et al

Figure 2. For illustration, the full set of relevant electronic configurations is shown for a simplified system comprising two donor sites. Upper
panel: excitonic (∣XTnñ), charge transfer exciton (∣CTXn, n ¢ñ) and charge separated (∣CSn ñ) configurations. Lower panel: on-site energies and
electronic couplings in the basis of these configurations.

couplings are tabulated in table 2. Low-frequency inter-frag- Table 2. Frequencies and vibronic couplings of effective modes
ment modes do not modify the dynamics significantly [17] relating to the electron–phonon coupling part of the Hamiltonian,
and were omitted from the present study. Ĥe - ph , see also supplementary material provided in [18]. All
quantities are specified in eV.
Overall, the Hamiltonian of equations (1)–(6) generalizes
the model of [18] such as to include OT charge transfer Mode
OT OT
excitons. The dynamics resulting from the above Hamiltonian index l wlC60 wlOT clC60 cCS, l cXT, l
reduces to the dynamics described in [18] when the couplings
1 0.2000 0.4012 0.0639 0.0099 0.0057
(k, k1, k 2 ) between XT and CTX manifolds, as well between 2 0.1842 0.3977 0.0929 −0.0001 0.0041
the CS and CTX manifolds are set to zero. 3 0.1778 0.1827 −0.0569 −0.0959 −0.1834
In the following, three different variants of the above 4 0.1411 0.1785 −0.0247 0.0815 0.0663
Hamiltonian will be considered which comprise, besides 13 5 0.0939 0.1345 0.0396 −0.0567 −0.0465
∣XTnñ states and 13 ∣CSn ñ states, (i) a single ∣CTXn, n ¢ñ state at 6 0.0799 0.1118 −0.0192 0.0165 0.0517
the interface, with n = 1, n¢ = 2 (i.e., 27 states overall), (ii) a 7 0.0558 0.0426 −0.0335 −0.0152 −0.0285
subset of ∣CTXn, n ¢ñ states, with ∣n - n¢∣ = 1, yielding a total 8 0.0332 0.0183 0.0139 −0.0174 −0.0109
of 50 electronic states, and (iii) the complete ∣CTXn, n ¢ñ
manifold, yielding a total of 182 electronic states. All systems
involve the full set of 112 vibrational modes.
27-state system involving the XT and CS manifolds along
with the ∣CTX1,2ñ state. The figure shows the eigenstates
3. Coupled XT, CTX, and CS manifolds (panels (a) and (c)) and the energetics (panels (b) and (d)), for
both barrier I and barrier II, evaluated at the Franck–Condon
Complementary to the site-local representation of the Hamil- geometry. The energetics of the manifolds is illustrated in a
tonian, it is instructive to analyze the properties of the elec- partially adiabatic representation (labeled I) where the elec-
el
tronic part, Hˆ = Hˆ
on ‐ site
+ Hˆ
coup
, in terms of its localized tronic coupling between the different manifolds has been set
and delocalized eigenstates. In particular, the mixing of the XT, to zero, and a full adiabatic representation (labeled II) where
el
CTX, and CS manifolds, and the role of trapped interfacial the complete electronic Hamiltonian Ĥ is diagonalized.
states, can be best appreciated from this perspective. From inspection of the energetics, it is clear that an extensive
To this end, figure 3 shows the energetic distribution and mixing of the XT, CTX and CS manifolds is taking place for
eigenstates of the simplest system under study, i.e., the both barriers.

5
J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003 M Polkehn et al

Figure 3. Electronic eigenstates and energetics for barriers I and II. Panels (a) and (c): for barrier I (panel (a)) and barrier II (panel (c)), the
electronic eigenstates of the 27-state model system are shown in ascending energetic order. The abscissa defines a series of electron–hole
basis states pertaining to the OT excitonic manifold (∣XTnñ, n = 1, ¼, 13), the OT charge transfer exciton (∣CTX1,2ñ), and the OT/C60 charge
separated states (∣CSn ñ, n = 1, ¼, 13). Panels (b) and (d): the energetics of the relevant states are shown, for a local adiabatic representation
(labeled I) where electronic couplings between the XT, CTX, and CS manifolds have been turned off and sub-blocks pertaining to the
different manifolds are diagonalized, and for the full adiabatic representation (labeled II) where all electronic couplings are included. The
bright exciton is highlighted by a red ellipse, and the CTX state is highlighted by a blue ellipse.

As can be immediately seen from the site-resolved
eigenstate representation (panels (a) and (c)), the lowest-
energy states are localized at the OT/C60 interface and
involve contributions from the lowest-lying XT, CTX, and
CS states. At higher energies, a distribution of strongly
delocalized states is present, which involves pronounced
mixing of contributions of the XT, CTX, and CS manifolds.
For barrier I, a separate high-energy manifold is visible which
essentially consists of CS states around the top of the Cou-
lomb barrier. Overall, the picture is similar to the situation
described in [18], except for the noticeable contribution of the
∣CTX1,2ñ state, especially to the low-lying states. The latter
states can play a crucial role since they give rise to interfacial
trapping effects.
In figure 3 (panels (b) and (d)), the energetic positions of
the bright exciton and the CTX state are highlighted. This
picture underscores that a substantial amount of excess energy
is present, such that immediate delocalization might take
place, involving participation of the CTX state. Following the
discussion of [18], though, we expect several competing
pathways, all of which involve participation of vibronic
couplings. In particular, ultrafast internal conversion
[18, 38, 39] within the XT manifold, channeling the popu-
lation to localized interfacial states, might happen faster than
delocalization towards long-range charge-separated states.
In a complementary fashion, figure 4 illustrates the
energetics for the 50-state system which comprises the subset
of ∣CTXn, n ¢ñ states, with ∣n - n¢∣ = 1, as explained above.
The participation of a large number of CTX states modifies
the distribution of states substantially. Importantly, a set of
low-energy states appears that mainly exhibit a mixture of XT
and CTX character, with smaller participation of CS char-
acter. These states could act as long-lived traps within the OT
domain.
In the following, a detailed quantum dynamical analysis
will be reported to analyze which pathways will turn out to be
dominant, and to what extent the picture of [18] is modified in
the presence of the CTX manifold.

6
J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003 M Polkehn et al

Figure 4. Analogously to panels (b) and (d) of the preceding figure 3, the energetics is illustrated for the 50-state model, for barrier I (left) and
barrier II (right). As before, a local adiabatic representation (labeled I) is shown, where electronic couplings between the XT, CTX, and CS
manifolds have been turned off and sub-blocks pertaining to the different manifolds are diagonalized, along with the full adiabatic representation
(labeled II) where all electronic couplings are included. Conspicuously, a set of low-energy states appears which exhibit a mixture of XT, CTX,
and CS character. Indeed, it turns out in the case of barrier I that the lowest energetic state exhibits around 50% XT and CTX character,
respectively, and very little admixture of CS character. In the case of barrier II, the lowest energetic states exhibit a strong state mixing involving
XT, CTX, and CS character. The lowest state carrying predominant CS character is located at −0.05 eV (barrier I) and at −0.2 eV (barrier II).

4. Quantum dynamics of charge separation in the
presence of CTX states
Quantum dynamical calculations have been carried out using
the ML-MCTDH method [28–30], as briefly summarized in the
following. We then proceed to the discussion of various results,
for the minimal 27-state system including the ∣CTX1,2ñ state, as
well as the 50-state and 182-state models described above.
4.1. ML-MCTDH simulations
The ML-MCTDH method [28, 30] is a generalization of the
MCTDH technique [24–27] (Heidelberg Package [40]), i.e., a
tensor approximation scheme permitting an efficient propa-
gation of high-dimensional molecular systems. The method
employs a hierarchical representation of the wavefunction in
conjunction with variational equations of motions for time-
dependent coefficients and so-called single particle functions
(SPFs). The latter are in turn represented by a static basis of
discrete variable representation (DVR) type.
In the MCTDH approach [24–27], the time-dependent
wavefunction representing a set of vibrational modes
{q1, ¼, qf } and a set of e–h states ∣nmñ is expanded in terms of
Hartree products, i.e., products of time-dependent SPFs,
with expansion coefficients A j1 , ¼ , jf , mn (t ) º AJ , nm (t ) and time-
dependent SPF configurations kf = 1 j(jk) (qk , t ) º FJ ({qk}, t ).
k
In the ML-MCTDH approach [28, 30], the time-dependent
SPFs are in turn expanded in sum-over-products form.
The wavefunction equation (7) describes correlated vibronic
states involving coherent superpositions of multiple e–h
configurations.
For the three model systems addressed above, all of
which include 112 vibrational (phonon) modes and a variable
number of electronic states (27, 50, and 182), a 6-layer
representation of the wavefunction was used. Table 3 lists the
numbers of SPFs per layer. A primitive harmonic oscillator
DVR representation was chosen for all vibrational modes
comprising 32 DVR points per mode. Typically propagation
times between 300 fs and 1 ps were used.
Initial conditions correspond either to individual elec-
tron–hole states, or else a superposition of such states. In
particular, preparation of an initial localized ∣XT1ñ state is
considered, as compared with a delocalized bright exciton
initial condition constructed by imaginary time propagation
(‘relaxation’ procedure in MCTDH; here, the electronic sub-
system is decoupled from the vibrational modes3).

∣y (q1, ¼, qf , t )ñ
N n1 nf f
3
=å å ¼ å A j1 ,¼,jf ,nm (t )  j(jk) (qk , t )∣nmñ The initial bright delocalized exciton state of figures 5(b) and (d) is generated
k by changing the sign of the excitonic coupling, such that the excitonic ground
n,m j1 jf k= 1
state wavefunction for the corresponding J-aggregate species (with negative
N excitonic coupling) is produced. The latter bright-state wavefunction is
=å å AJ , nm (t ) FJ ({qk}, t )∣nmñ (7 ) subsequently used as an initial state for the real-time propagation for the
n,m J H-aggregate system.

7
J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003 M Polkehn et al

Figure 5. Time-evolving electron–hole state populations resulting from ML-MCTDH calculations, for barrier II. Exciton (XT) state
populations are shown in red, OT/C60 charge separated (CS) populations are shown in blue, and charge transfer exciton (CTX) populations
are shown in light blue. Panels (a) and (b): reference system in the absence of the CTX manifold, for a localized initial condition
corresponding to the interfacial ∣XT1ñ state (panel (a)) and for a delocalized, bright exciton initial condition (panel (b)). Panels (c) and
(d): corresponding time-evolving populations for 27-state simulations including the ∣CTX1,2ñ state. The presence of the CTX state is seen to
significantly modify the nature of the low-energetic trapped states which accumulate a significant part of the overall population. Interestingly,
the population of the ∣CS1ñ state, which is predominantly populated in the 26-state simulations shown in panels (a) and (b), is strongly reduced
in the 27-state simulations of panels (c) and (d). Instead, the ∣CTX1,2ñ state and the ∣CS2 ñ state acquire a non-negligible weight.

Table 3. Wavefunction partitioning for the ML-MCTDH calculations reported in this work. All simulations were carried out for 112
vibrational (phonon) modes.
Layer 1 2 3 4 5 6
27 states SPF [39, 39, 27] [35, 35] [29, 29] [19, 19] [12, 12, 7] [4, 4, 7]
50 states SPF [45, 45, 50] [39, 35] [31, 31] [32, 32] [7, 12, 10] [4, 7, 7]
182 states SPF [32, 32, 182] [29, 29] [24, 24] [15, 15] [7, 7, 7] [4, 4, 4]

4.2. Quantum dynamics of minimal model including ∣CTX1;2 〉
state
Figure 5 compares the result of ML-MCTDH calculations for
the 27-state model comprising the ∣CTX1,2ñ state (panels (c)
and (d)) with the corresponding dynamics in the absence of
the CTX state (panels (a) and (b)). All results illustrated in the
figure refer to barrier II. The figure shows site-resolved
populations of the XT (red), CTX (light blue), and CS (blue)
manifolds as a function of time, for both a localized and
delocalized (bright exciton) initial condition (see panels (a)
and (c), and panels (b) and (d), respectively).
In line with our previous studies [17, 18, 36], we expect a
markedly nonexponential short-time dynamics, in agreement
with experimentally observed ultrafast initial charge separation
on a time scale of t ~ 50–200 fs [41, 42]. The initial dynamics
involves pronounced vibronic effects that mediate the transfer
to the CS manifold. Vibronic effects also give rise to trapping
effects, due to the strong coupling of both inter-chain excitons
and charge-separated states to vibrations—in particular

8
J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003 M Polkehn et al

Figure 6. As an extension to the representation of figure 5, the time-dependent population of the ∣CS1ñ state is shown for the 26-state model
(in the absence of the CTX manifold) as compared with the 27-state model, the 50-state model, and the 182-state model, for barriers I and II
and for both localized and delocalized initial conditions. While the ∣CS1ñ state population is already reduced in the 27-state model, this effect
is found to be much more pronounced in the 50-state model and the 182-state model. Here, the ∣CS1ñ state population is essentially quenched.
The 50-state and 182-state models yield similar results such that the 50-state model—which includes charge-transfer excitons with an
electron–hole separation ∣n - n¢∣ = 1—can be taken to be a good approximation to the full dynamics.

high-frequency CC modes—whose ultrafast reorganization leads
to energetically stabilized electronic distributions. These effects
occur on the same time scale (t ~ 20–100 fs) and cannot be
separated from the charge separation dynamics in the present
system. Also, intra-chain trapping as revealed by transient
anisotropy measurements [43] is not fully resolved in the present
study since we define e–h states in terms of ‘coarse-grained’
oligomer units (for comparison, e–h states can be alternatively
defined in a monomer basis [44], permitting a full analysis of
intra-chain trapping).
Referring to the reference calculations of panels (a) and
(b), we note that (i) the localized initial condition (panel (a))
immediately generates a significant population of the inter-
facial ∣CS1ñ state, on a time scale of t ~ 30 fs, but (ii) a non-
negligible participation of delocalized CS states is observed
early on as well. A somewhat lower participation of deloca-
lized CS states is seen for the delocalized, bright-state initial
condition, where the rise of the interfacial ∣CS1ñ state is found
to follow a slower build-up kinetics, with a t ~ 500 fs time
scale. This build-up can be interpreted in terms of an internal
conversion process [18, 38, 39] which leads to the gradual
population of low-energy states within the excitonic manifold.
At the same time, long-range charge-separated states emerge
and build up steadily. These observations are consistent with
the result that a lower barrier favors ultrafast long-range
charge separation as discussed in [17, 18].
Participation of the ∣CTX1,2ñ state, as shown in panels
(c) and (d), is seen to lead to a tangible reduction of the ∣CS1ñ
population, while the ∣CS2 ñ population rises more rapidly.
This is due to the fact that the ∣CTX1,2ñ state directly couples
to the ∣CS2 ñ state, as explained above. The amount of long-
range CS states is comparable to the reference calculations of
panels (a) and (b). These observations are in line with the
electronic eigenstate picture of the preceding section where a
strong mixing of XT, CTX and CS character in the low-
energy interfacial states was observed.
4.3. Quantum dynamics of 50-state and 182-state models
We now turn to the larger model systems, including 50 or 182
electronic states. Since the site-resolved representation of the
propagation results tends to be cumbersome, we focus on
several integrated properties, notably (i) the population of the
interfacial ∣CS1ñ state and (ii) the free carrier population,
which is calculated as the integrated population over CS states
with an electron–hole separation ∣n - n¢∣ > 8, similarly to the
procedure of [17, 18].
Figure 6 shows the time-dependent population of the
interfacial charge separated ∣CS1ñ state, for the three types of
simulations described above (27, 50, and 182 states), as
compared to reference simulations in the absence of the CTX
manifold. Both localized initial conditions (∣XT1ñ) and delo-
calized initial conditions (bright exciton) are considered, for

9
J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003 M Polkehn et al

Figure 7. In a complementary fashion to figure 6, the time-evolving free carrier populations are shown, for the 26-state model (in the absence
of the CTX manifold) as compared with the 27-state model, the 50-state model, and the 182-state model, for barriers I and II and for both
localized and delocalized initial conditions. Free carrier populations are obtained as integrated populations for the charge separated states
∣CSn ñ, n = 8, ¼, 13. While free carrier populations are not strongly affected by addition of the ∣CTX1,2ñ state in the 27-state model, they are
much reduced in the 50-state and 182-state models.

both types of barriers. Barrier I generates the highest popu-
lation of the ∣CS1ñ state, with an immediate onset in the case of
the localized (∣XT1ñ) initial condition and a gradual rise for the
bright-state initial condition, in line with the dynamics
depicted in figure 5. For barrier II, the ∣CS1ñ state population
follows the same trends, but is significantly reduced.
In the case of a single ∣CTX1,2ñ state, the ∣CS1ñ state
population is reduced to a significant extent, due to the
alternative ∣XT1ñ  ∣CTX1,2ñ  ∣CS2 ñ pathway that was dis-
cussed above (see section 2). Adding more CTX states, in the
50-state calculations (comprising all CTX states with an
electron–hole separation ∣n - n¢∣ = 1) and in the 182-state
calculations (comprising all CTX states), leads to an almost
complete quenching of the ∣CS1ñ state population. This is the
case for both types of barriers. Clearly the pathway via the
CTX manifold becomes dominant. Also, the simulations for
50 states versus 182 states are found to give nearly equal
results, such that one may conclude that CTX states with
∣n - n¢∣ = 1 dominate the picture.
Figure 7 shows the time-dependent free-carrier popula-
tion, i.e., the integrated ∣CSn ñ state populations for n > 8, for
the same simulations as in figure 6. In line with our previous
findings [17, 18], the free carrier yield is tangibly larger for
barrier II as compared with barrier I. While the 27-state
simulations with a single ∣CTX1,2ñ state lead to a comparable
free carrier yield as the reference calculations, the simulations
for 50 and 182 states show a strongly reduced free carrier
yield, both in the case of localized and delocalized initial
conditions. Again, results for the 50-state and 182-state
models are very similar.
5. Discussion and conclusions
The above observations lead us to conclude that the presence
of the CTX manifold, representing inter-chain charge-sepa-
rated polaronic species in the regioregular oligothiophene
domain, reduces the role of the interfacial charge transfer state
(∣CS1ñ); in fact, a dynamical scenario results that entirely
bypasses the ∣CS1ñ state. However, at the same time the CTX
manifold leads to efficient trapping of electron–hole pairs of
mixed XT/CTX character in the oligothiophene donor
domain. Hence, despite the availability of additional CTX-CS
coupling pathways, the CTX mediated channel entails a net
reduction of the free carrier population.
One should note, though, that these conclusions depend
in a sensitive fashion on the energetics and electronic cou-
plings between the different manifolds. For example, for
electronic couplings between the XT and CTX manifolds
reduced by a factor of two (k1 = 0.18 eV, k 2 = 0.07 eV), the
free carrier yield is found to be close to the reference calcu-
lations in the absence of CTX states. It is conceivable that
further modification of the energetics, e.g., involving the XT-
CS energetic offset, could even lead to an enhancement of

10
J. Phys. B: At. Mol. Opt. Phys. 51 (2018) 014003
free carrier yields due to the CTX pathway. In the actual
material, static and dynamic disorder are expected to con-
tribute to fluctuations in both on-site energies and electronic
couplings.
From the perspective of quantum dynamical simula-
tions, the use of the ML-MCTDH technique provides a
unique tool to accurately describe quantum dynamical
evolution of hundreds of electronic states and vibrational
modes. Importantly, the full quantum dynamical description
permits the inclusion of vibronic mechanisms like internal
conversion [18, 38, 39] which play a critical role in med-
iating electronic deexcitation on ultrafast time scales. Fur-
ther, a quantum dynamical description is needed to account
for the complex patterns of delocalization and trapping that
evolve on ultrafast time scales, which cannot be captured by
kinetic models. While the present calculations were carried
out at zero temperature—which is appropriate to describe
the ultrafast part of the photoinduced dynamics—temper-
ature effects will be included in future studies, along with
energetic and structural disorder.
To summarize, the inclusion of the CTX manifold con-
siderably enhances the complexity of transfer pathways at
P3HT-PCBM type junctions, as a result of the coupling
between Frenkel-type excitonic manifolds, charge transfer
excitons, and donor/acceptor CS species. Given that recent
experimental observations [20–22], in agreement with our
calculations and related electronic structure work [45], are
strongly indicative of pronounced XT/CTX mixing effects in
ordered polythiophene materials, it is important to include
these effects in the modeling of donor–acceptor junctions
involving regioregular thiophene-based domains.
Acknowledgments
Funding by the Deutsche Forschungsgemeinschaft (DFG) and
the Agence Nationale de la Recherche (ANR) in the frame-
work of the project MolNanoMat (BU-1032-2), as well as
support by the NAKAMA funds are gratefully acknowledged.
Further, we are grateful to Konstantin Falahati for his assis-
tance with the preparation of one of the figures.
ORCID iDs
I Burghardt https://orcid.org/0000-0002-9727-9049
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