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Cite this: Phys. Chem. Chem. Phys., 2012, 14, 225–233

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Coumarin derivatives for dye sensitized solar cells: a TD-DFT studyw
Rocı́o Sánchez-de-Armas,* Miguel Ángel San Miguel, Jaime Oviedo and
Javier Fdez. Sanz
Received 23rd June 2011, Accepted 21st October 2011
Published on 11 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CP22058F

DOI: 10.1039/c1cp22058f

Time dependent density functional theory (TD-DFT) calculations have been carried out to study
the electronic structure and the optical properties of five coumarin based dyes: C343, NKX-2311,
NKX-2586, NKX-2753 and NKX-2593. We have found out that the position and width of the
first band in the electronic absorption spectra, the absorption threshold and the LUMO energy
with respect to the conduction band edge are key parameters in order to establish some criteria
that allow evaluating the efficiency of coumarin derivatives as sensitizers in Dye Sensitized Solar
Cells (DSSC). Those criteria predict the efficiency ordering for the coumarin series in good
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agreement with the experimental evidence. Presumably, they might be used in the design of new
efficient organic based DSSC.

1. Introduction The usual way to improve the DSSC performance of a given

Dye Sensitized Solar Cells (DSSC)1–3 based on organic dyes
adsorbed on nanocrystalline TiO2 electrodes have attracted con-
siderable attention in recent years because of their high incident
solar light-to-electricity conversion efficiency and low cost of
production.4–7 The photochemical properties of different organic
sensitizers have extensively been investigated in an attempt to
design dyes with maximal visible light absorption coupled to long-
lived excited states. However, major effort is still needed in both
developing new sensitizers and finding optimal working conditions
to improve the photon-to-current conversion efficiencies.
The electronic and optical properties of coumarin based
dyes make them one of the most promising classes of organic
sensitizers and they have been studied systematically by Hara
and Arakawa.8–14 They are considered type-I dyes, in which
electron injection occurs through an indirect mechanism: there
is a photoexcitation of the dye to an excited state, followed by
the electron injection from this state to the semiconductor
conduction band.
The first coumarin based molecule studied as a sensitizer for
DSSC was C343 (Fig. 1a). Ultrafast electron-injection times of
20–200 fs from C343 into the conduction band of TiO2 have
been observed.15,16 However, the conversion efficiency of
DSSCs using C343 is much lower than the efficiencies
of DSSCs based on Ru complex photosensitizers,17 because
of the narrow absorption area that the C343 dye electronic
spectrum presents in the visible region.
Department of Physical Chemistry, University of Seville, Spain.
E-mail: rociosa@us.es
w Electronic supplementary information (ESI) available. See DOI:
10.1039/c1cp22058f
dye, i.e., to widen the absorption in the visible region, consists of
a functionalization by either adding chromophore groups or
expanding the p system. In this context, it has been found that
introducing a methine unit (–CHQCH–) connecting both the
cyano (–CN) and carboxyl (–COOH) groups into the coumarin
framework expands the p conjugation of the dye resulting in a
red shift and an absorption widening in the visible region,
desirable for sunlight harvesting. A conversion efficiency of
5.6%, rather higher than that obtained using C343, was reached
in 2001 with a cell based on NKX-2311 (Fig. 1b).8 The slow
charge recombination, on the order of micro to milliseconds,
between NKX-2311 cations and injected electrons into the TiO2
conduction band resulted in efficient charge separation for this
system.9 Moreover, the structure of NKX-2311, with a carboxyl
group directly connected to the –CHQCH– unit, is advantageous
for effective electron injection from the dye into the conduction
band of TiO2. These dyes are donor–acceptor p-conjugated
(D–p–A) dyes possessing both electron-donating (D) and
electron-accepting (A) groups linked by p-conjugated bridges.
In these dyes, a coumarin skeleton contains an amino group
acting as the donor component and cyanoacrylic acid as the
acceptor component.
The absorption maximum of coumarin dyes gradually red-shifts
with size expansion of their conjugate system (by increasing
the number of methine units) and this shift has been attributed
to decreases in the oxidation potentials caused by destabilization
of HOMO orbitals. The introduction of a cyano group, with a
strong electron-accepting ability, produces an increase in the
dye reduction potential due to a stabilization of the LUMO
orbital.10 Furthermore, the expansion of the p conjugated
system by introducing one or more thiophene rings into the
methine chain of NKX-2311 has also been tested. Thiophene

This journal is c the Owner Societies 2012 Phys. Chem. Chem. Phys., 2012, 14, 225–233 225

Published on 11 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CP22058F
Fig. 1 Coumarin dye structures: (a) C343, (b) NKX-2311, (c) NKX-2586, (d) NKX-2753 and (e) NKX-2593.
simultaneously extended p-conjugation and improved the dye
stability relative to other dyes with a long methine chain
unit.11,12 This modification does not affect the absorption
properties of dyes in solution, but improves the performance
of coumarin based DSSCs. Thus, efficiencies up to 7.7% have
been reached in cells based on coumarin dyes containing two
thiophene units.18
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A drawback related to these coumarin dyes is that they are
liable to experience p-stacked aggregation on TiO2 surfaces. In
particular, dyes containing three methine units (NKX-2586)
are very prone to show this effect. This type of aggregation
would be advantageous for light harvesting, because it induces
a widening in the UV/Vis absorption spectrum. However, it
usually leads to inefficient electron injection because of inter-
molecular energy transfer processes between the dyes, thus
resulting in low cell efficiency.
A strategy to prevent dye aggregation is adding coadsorbates,
like deoxycholic acid (DCA) and 4-tert-butylpyridine (TBP).13
Although these additives improve the electron injection, they
significantly decrease dye adsorption limiting unavoidably the
cell performance. Recently, a new coumarin dye (NKX-2753)
has been synthesized to reduce dye aggregation while keeping
the adsorbed dye amount.14 This molecule has a side ring
linked to the alkene chain that prevents dye aggregation,
ensuring simultaneously a high surface dye concentration
and efficient photon-to-electron conversion. Thus, the use of
NKX-2753 has allowed obtaining efficiencies up to 6.7%.
Theoretical methods are a powerful tool for molecular
design, and conclusions drawn from calculations are valuable
guidelines for synthesis of new efficient dyes. Although coumarin
based dyes have been extensively studied from experimental
methods in recent years, there are not many theoretical studies
about them.19–27 In a recent work, Time-Dependent Density
Functional Theory (TD-DFT/B3LYP) has been used to simulate
the electronic absorption spectra of free coumarin dyes.24
They obtained excitation energies that agree well with experi-
mental data for small molecules but those energies were
underestimated for larger coumarin dyes. Moreover, the inclusion
of methanol solvation effect via a PCM model tends to reduce
the excitation energies, due to a stabilization of the LUMO
orbital. In subsequent works excitation energies that agree
better with experiments have been obtained employing a long-
range-corrected (LC) exchange–correlation functional.25,26
Furthermore, TD-DFT calculations have been used to
226 Phys. Chem. Chem. Phys., 2012, 14, 225–233
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establish a relationship between the electronic structure of free
coumarin dyes and their efficiency as DSSC sensitizers.27 Thus,
the location of the first absorption band and the energy of the
HOMO orbital were used as parameters to evaluate the
electrochemical efficiency of coumarin dyes. It is worth noting
that up to date, all previous theoretical works are limited to
the study of electronic structure and optical properties of free
dyes and none of them tackles the influence of the adsorption
process on the electronic absorption spectra of these dyes.
Recently, we have studied the structural and electronic
properties of some organic dyes that have been used as
sensitizers in DSSC, both free and supported on several
TiO2 clusters with different sizes.28–30 From these works it is
shown that the dye adsorption process on the semiconductor
produces a reorganization of the electronic states and this fact
introduces important changes in the electronic absorption
spectra. Moreover, the electronic coupling between the semi-
conductor conduction band and the dye molecule strongly
influences the electron injection mechanism. Therefore, to
theoretically determine the convenience of using these dyes
as DSSC sensitizers, it is necessary to include the semiconductor
effect explicitly in the model. In addition, the cluster size
should be large enough to well reproduce the electronic
structure of adsorbed dyes.
In this work we have studied the electronic structure and the
optical properties of five coumarin based dyes: C343, NKX-
2311, NKX-2586, NKX-2753 and NKX-2593 (Fig. 1). First,
we consider the geometry of the organic dyes in the electronic
ground state as well as the geometries of the five dyes adsorbed
on a TiO2 cluster. Second, we explore the optical response of
the different structures using TD-DFT. These calculations are
performed in a complementary way to simulate the electronic
spectra through the conventional mode and the real time
propagation within the adiabatic approximation with a basis
of localized orbitals. In a previous work we checked that both
TD-DFT implementations reach very similar results provided
the same exchange–correlation functional even if the employed
basis sets are not exactly the same.28
The aim of this work is to understand the physical–chemical
aspects that govern the light absorption process in the coumarin
based series to find the main parameters that affect the
efficiency of these dyes as DSSC sensitizers. Thus, we intend
to establish some criteria to evaluate the relative efficiency of
coumarin dyes. The use of these criteria could be applied to
This journal is c the Owner Societies 2012

predict the efficiency of other dyes and presumably to design
new more efficient sensitizers, reducing economical cost and
synthesis effort.
2. Computational methods
2.1 Technical details
Two complementary sets of calculations have been carried out
for each model described in Section 2.2.
(1) DFT geometry optimizations have been done by using the
PBE generalized gradient approach functional31 together with
norm-conserving pseudopotentials32 in the fully non-local
Published on 11 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CP22058F
Kleinman–Bylander33 form and an auxiliary real-space grid
equivalent to a plane-wave cut-off of 130 Ry. A non-standard
DZP basis set of Natural Atomic Orbitals (NAOs) constructed
from the eigenstates of the atomic pseudopotential was used.34–36
The optical response was then computed using real time TD-DFT
(time domain) simulations within the SIESTA implementation.37–39
We consider the system in a finite electric field of 0.1 V Å 1 as an
initial state.28 Each system was allowed to evolve for 36 fs with a
time-step of 1.5  10 3 fs. The damping factor used in the Fourier
transformation was 0.1 eV.
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(2) Additionally, linear response (LR) frequency domain
calculations were performed in the gas phase using the PBE
functional and the 6-31G(d,p) basis set. The optical spectra were
simulated by conventional TD-DFT (frequency domain) using
Gaussian03.40 Over 400 singlet transitions were needed in selected
calculations. Before the spectrum calculation, vibrational frequency
calculations were done to confirm the stability of all the optimized
geometries. With the aim of comparing our results with previous
published data, several calculations were repeated using the B3LYP
exchange–correlation functional and a discussion of these results is
included in the ESI.w
There are some advantages associated with the real-time
TD-DFT formulation: all the possible excitations are generated
at the same time, so the spectrum is obtained in a wide range of
energy; the implementation is relatively simple and although
the computational cost is not cheap for small systems, it
becomes competitive with traditional methods as the system
size increases. However, its main disadvantage is that it is not
possible to characterize the nature of the different transitions
because the optical response is obtained from the analysis of
the electronic dipole moment, where the information from the
wavefunctions is integrated. For this reason the combination
with conventional TD-DFT is interesting. In previous work28,29
we performed real-time calculations with clusters as large as
(TiO2)38 and demonstrated that (TiO2)9 is large enough to
reproduce adequately the electronic absorption spectra of the
dye–TiO2 systems. Since the (TiO2)9 cluster is affordable from
frequency domain TD-DFT calculations, a full analysis of the
spectra is possible.
Although it is known that TD-DFT can significantly under-
estimate the energies of long-range charge transfer states,41
that is not the case with the present calculation. The molecules
considered in this paper are not large enough to present a
long-range intramolecular charge transfer and therefore, for
these molecules the photoexcited state shows a moderate
charge transfer (see ESIw). Moreover, it is important to stress
that the aim of this work is to establish some criteria to
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evaluate the relative efficiency of dyes. The established criteria
are general, not depending on technical settings.
2.2 Models
The computational methodology has been applied to: free dyes
(C343, NKX-2311, NKX-2586, NKX-2753, NKX-2593) and
each dye adsorbed onto a (TiO2)9 cluster. The starting geometry
for this cluster was taken from the literature.42,43 It was obtained
via geometry optimization of the originally spherical shape
resulting in a compact structure with only 4-fold coordinated
Ti-atoms and with one terminal Ti–O bond. In a previous
work,28 we have demonstrated that this cluster size is large
enough to reproduce adequately the electronic absorption spectra
of some dye–TiO2 systems. Furthermore, this cluster has a
critical size which is affordable from both TD-DFT approaches
allowing the comparison between them.
For C343 there is only one possible configuration, while for
the other dyes two different conformational isomers exist. The
configuration at the single bond between the coumarin moiety
and the methine chain can have either an s-cis or s-trans
arrangement. From our calculations we conclude that for
the smaller coumarin dyes, such as NKX-2311, the s-cis isomer
is slightly favoured, due to steric repulsion between the CQO
group of the coumarin and the C–N group of the cyanoacrylic
acid in the s-trans isomer. In contrast, for the molecules with
larger methine chains, such as NKX-2586, the repulsion
becomes less important, and the s-trans isomer becomes
slightly more stable than the s-cis isomer. These results agree
well with previous theoretical works.6,19,25 Nevertheless, energy
differences between both isomers are always insignificant (less than
0.03 eV). Moreover, we have checked out that for all dyes the
calculated electronic absorption spectra of both isomers are
almost identical (differences in the absorption maximum position
are less than 0.08 eV).
These dyes also present two different conformations with
respect to the nitrogen atom of the unsaturated rings, syn and
anti, which have been reported to be almost isoenergetic.19 In
this work we have selected the syn conformer which has also
been used in previous theoretical work.24,25 Therefore, it has
been suggested from ab initio calculations that the absorption
spectra of the syn and anti isomers are almost indistinguishable
for a coumarin dye.19
Coumarin dyes adsorb on the TiO2 surface through the
carboxylic group, and several adsorption configurations are
possible, including molecular or dissociative adsorption processes.
FTIR spectra for these systems indicate the presence of carboxy-
late ion after adsorption, which indicates that the deprotonation
of the COOH group takes place on the TiO2 surface.14 The formed
carboxylate group may coordinate to the surface in several forms.
One of them involves the attachment of one dye oxygen atom to
one surface titanium atom, leading to a monodentate structure.
A second possibility is the formation of a bidentate structure which
could be a bidentate bridging (bb) structure with both dye oxygen
atoms bound to two surface titanium atoms or a bidentate
structure with those two dye oxygens bound to the same surface
titanium atom, in a chelating configuration (bc). All previous
works agree that monodentate adsorption is not favoured for this
kind of dye. Nevertheless, there is some controversy about what
Phys. Chem. Chem. Phys., 2012, 14, 225–233 227

bidentate adsorption mode is the most favourable. We carried out
geometry optimization of the dyes adsorbed on a (TiO2)9 cluster in
both bidentate configurations (bb and bc) (see ESIw). In order to
keep the system electroneutrality, the dissociated hydrogen atom
was placed on three different oxygen cluster atoms. From this
study we concluded that the most stable adsorption mode is, in
general, the bidentate chelating configuration (bc), with the two dye
oxygens bound to the same surface titanium atom and with the
dissociated hydrogen bound to an oxygen in the centre of the
cluster. Nevertheless, for some dyes such as NKX-2311, differences
between the two bidentate configurations are small (less than
0.15 eV) suggesting that both structures could exist in real systems.
Published on 11 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CP22058F
In spite of the energetic differences, the absorption maxi-
mum position in the spectra is almost not affected by the
adsorption mode (differences less than 0.07 eV). Nevertheless,
for the bidentate bridging structure (bb) a new band at lower
energy appears in the simulated spectrum, which is not present
in the experimental spectrum (see ESIw). This might be
considered an indirect evidence to rule out the existence of
this adsorption mode, or at least to discard that the bb
structure is a main structure.
Considering the relative stabilities of the different isomers and
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adsorption modes and their (slight) influence on the electronic
absorption spectra, we have chosen the s-cis isomer and the
bidentate chelating (bc) adsorption mode (with the dissociated
hydrogen bound to an oxygen in the centre of the cluster) as a
representative model for our study on the electronic structure
and the absorption spectrum. Thus, all the results presented in
the next section are referred to this model.
3. Results
3.1 Free dyes
The simulated absorption spectra from real-time TD-DFT
calculations for free coumarin dyes are shown in Fig. 2. The
spectra show a similar profile for all dyes; they present a main
intense band with a small shoulder at higher energies. C343
spectrum presents the main peak at 2.96 eV, in excellent
agreement with the experimental value (2.81 eV).17 For the
rest of dyes the main peak appears red-shifted in the spectrum
compared with C343 following the sequence (Table 1): C343
(2.96 eV), NKX-2311 (2.30 eV), NKX-2586 (2.10 eV), NKX-
2753 (2.07 eV) and NKX-2593 (1.96 eV). The most intense
contribution to the main band is an excitation from the
HOMO to the LUMO orbital (Table 1). HOMOs are
Fig. 2 Simulated real-time TD-DFT spectra for free dyes.
228 Phys. Chem. Chem. Phys., 2012, 14, 225–233
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preferentially localized on the coumarin moiety, which acts
as an electron donor, while LUMOs have a large contribution
from cyanoacrylic acid and polimethine/thiophene chain
(Fig. 3).
In the optimized dye geometries, cyanoacrylic acid is coplanar
with the polimethine/thiophene chain, indicating strong
conjugation across the p orbitals of the CQC double bonds.
On extending the polimethine chain, the p electron system
increases and this fact produces a destabilization of HOMO
orbitals (Fig. 4) and a red-shift of the first band. The p electron
systems of NKX-2586 and NKX-2753 have the same extension
and their HOMO and LUMO orbitals are very similar, which
are the reasons why the electronic absorption spectra are
almost identical for these two dyes. On the other hand, the
introduction of a –CN group (a strong electron acceptor)
produces a LUMO stabilization and consequently an important
red shift of the first band in the spectra. In this scenario, the
C343 main peak is then considerably blue-shifted with respect
to the other dyes showing almost no absorption in the visible
region.
The position (related to the gap between HOMO and
LUMO levels) and the width of the first band in the spectrum
are the two first parameters that can be related to the dye
efficiency, since the absorption shift to lower energies favors
the light harvesting process. Nevertheless, in a previous
work,28,29 we have shown that dye adsorption on the semi-
conductor leads to a redistribution of energy levels. For this
reason, to theoretically analyze the behavior and efficiency of
the dyes as DSSC sensitizers, the semiconductor must be
included explicitly in the model. We have to point out that
up to date all theoretical works on coumarin dyes are limited
to the study of free dyes.
3.2 Theoretical criteria to evaluate efficiency
In order to establish some criteria to evaluate the relative
efficiency of coumarin dyes as DSSC sensitizers, it is interesting
to review the working scheme of this type of cells. As can be
seen in Fig. 5, a DSSC working scheme is based on several
processes in which different energy levels are involved. Thus,
we have to consider that the electron injection occurs into a
semiconductor conduction band state and that the oxidized
dye is regenerated through reduction by an electrolyte. Additionally
in a type I cell, the first step is a photoexcitation of the dye to an
excited state, and for an efficient sunlight harvesting the dye
absorption range should cover the whole visible and some of the
near-infrared regions. On comparing two dyes with similar struc-
tures, the light harvesting would be more efficient for the dye with a
lower absorption threshold and a wider first band in the electronic
absorption spectrum. The second step involves the electron
injection from the dye excited state to the semiconductor
conduction band. The rate constant for electron injection is
proportional to the number of accessible states, and the
effective density of states in the TiO2 conduction band is
considered to increase exponentially with energy. It has been
reported that a 0.3 eV shift in relative energy between the dye
excited state and the TiO2 conduction band provokes a 10-fold
change in injection rate.44,45 Therefore, between two dyes with
similar structures, the electron injection would be more
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 View Article Online

Table 1 Lowest band energies (eV) for free dyes from standard (frequency domain) TD-DFT calculations and comparison with experimental
values and experimental efficiencies. Assignments of electronic excitations for free dyes are also included. H stands for HOMO and L for LUMO

Dye Exp./eV Z (%) TDDFT/eV Oscillator strength Wave function

C343 2.81 (MeOH) 0.9 2.96 0.3616 H - L (0.59), H 2 - L + 1 ( 0.14), H 2 - L ( 0.12)
NKX-2311 2.46 (MeOH) 5.2 2.35 1.0538 H - L (0.56), H 1 - L (0.14)
NKX-2586 2.45 (MeOH) 3.5 2.10 1.2318 H - L (0.53), H 1 - L (0.24), H - L + 1 ( 0.14)
2.44 (EtOH)
NKX-2753 2.52 (EtOH) 6.7 2.07 1.0679 H - L (0.54), H 1 - L (0.24), H - L + 1 ( 0.14)
NKX-2593 2.43 (EtOH) 7.2 1.96 0.9762 H - L (0.53), H 1 - L (0.25), H - L + 1 ( 0.20)
Published on 11 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CP22058F
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Fig. 4 Frontier orbital energies for the different free dyes (eV).
Extending the p electron system produces a destabilization of HOMO
orbitals while introducing a –CN group produces a LUMO
stabilization.

Fig. 3 Occupied (left, HOMO) and virtual (right, LUMO) molecular

orbitals responsible for the first band in the electronic absorption
spectrum of free dyes. The isodensity value used is 0.015.

efficient for that dye with the higher excited state related to the
Fig. 5 Schematic representation of the main processes involved in a DSSC.
semiconductor conduction band edge. The composition of an
excitation is routinely obtained from the calculations
and the position of the LUMO level related to the conduction
(see Tables 1 and 2 for instance) although it is customary to
band edge to establish criteria in order to evaluate the relative
simplify and regard the excitation as an HOMO–LUMO one.
efficiency of coumarin dye derivatives.
Therefore, the energy of the excited state has been approxi-
mated as the LUMO orbital energy. In a previous theoretical
3.3 Adsorbed dyes
work, the energy for the conduction band edge was estimated
from experimental measurements.9,44 Nevertheless, in this The simulated absorption spectra from real-time TD-DFT
work, the semiconductor has been included explicitly in the calculations for adsorbed coumarin dyes are shown in
models and consequently the energy levels for the dye and for Fig. 6. The main effect that can be observed in the spectra
the semiconductor are calculated simultaneously. after adsorption is a widening of the first band, while the
In summary, we will use the electronic absorption spectra maximum position remains almost unaltered for all dyes
(position and width of the first band and absorption threshold) (small red-shift of 0.1–0.2 eV). The widening occurs at both

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Table 2 Assignments of electronic excitations for adsorbed NKX-2593. Only selected transitions with enough oscillator strength around the main
peak are included (H stands for HOMO and L for LUMO)

Transition energy/eV Oscillator

(excitation number) strength Wave function
First band
1.39 (8) 0.0427 H - L + 8 (0.63), H - L + 5 (0.27), H - L + 7 ( 0.11)
Second band
1.73 (14) 0.4347 H - L + 13 (0.51), H - L + 5 (0.29), H - L + 12 ( 0.21), H - L + 8 ( 0.16)
1.84 (18) 0.4114 H - L + 13 (0.37), H - L + 14 (0.36), H - L + 5 ( 0.25), H - L + 15 ( 0.25), H - L + 8 (0.14)
1.87 (19) 0.1119 H - L + 14 (0.59), H - L + 15 (0.27), H - L + 13 ( 0.14), H - L + 5 (0.13)
1.94 (21) 0.1800 H - L + 15 (0.58), H - L + 16 (0.17), H - L + 17 (0.16), H - L + 5 ( 0.15), H - L + 13 (0.13),
H - L + 20 (0.12)
1.99 (24) 0.0239 H - L + 16 (0.66), H - L + 17 ( 0.19)
- L + 17 (0.63), H - L + 20 ( 0.19), H - L + 16 (0.12)
Published on 11 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CP22058F

2.04 (25) 0.0596 H

2.16 (32) 0.0811 H 1 - L + 8 (0.59), H 1 - L + 5 (0.33), H 1 - L + 7 ( 0.14)
Third band
2.31 (34) 0.1874 H 2 - L + 4 (0.50), H - L + 21 ( 0.27), H - L + 20 (0.23), H 1 - L + 8 (0.16), H 1 -
L + 5 ( 0.15), H 1 - L + 9 (0.12)
2.32 (35) 0.1254 H 2 - L + 4 (0.48), H - L + 21 (0.38), H - L + 20 ( 0.21), H 1 - L + 8 ( 0.12), H 1 -
L + 5 (0.10)
2.32 (36) 0.2597 H - L + 21 ( 0.51), H 1 - L + 5 (0.23), H 1 - L+8 ( 0.21), H - L + 20 ( 0.15), H 1 -
L + 9 ( 0.14), H 2 - L + 5 ( 0.13), H 2 - L + 10 ( 0.12)
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Fig. 6 Simulated real-time TD-DFT spectra for adsorbed dyes to a

(TiO2)9 cluster.

sides of the main band; the absorption threshold is red-shifted

and consequently it extends into the visible region.
Like in the case of free dyes, the adsorbed C343 main peak is
considerably blue-shifted with respect to the other dyes. The
absorption maximum position for the rest of dyes is very similar,
and there is only a slight red-shift following the sequence: NKX-
2311, NKX-2586, NKX-2753 and NKX-2593. Albeit, adsorbed
NKX-2593 spectrum covers the widest zone in the visible region
and it shows the lowest absorption threshold.
Upon binding the energy levels of dye and cluster are
reorganized. We have analyzed the last occupied and the first
virtual orbitals for the free and the adsorbed systems to gain
insight into the energy levels redistribution. HOMO and LUMO
orbitals of free dyes have been described in Section 3.1 and are
shown in Fig. 3. We can classify free cluster orbitals into four
groups. The inner occupied orbitals (HOMO 6, HOMO 5,
HOMO 4 and HOMO 3) are delocalized over the whole
cluster. The last occupied orbitals (HOMO 2, HOMO 1 and
HOMO) are localized on the cluster region closest to the Ti atom
which the molecule will bind to. The first virtual orbitals
(LUMO, LUMO+1, LUMO+2 and LUMO+3) are localized
on the cluster region farthest to that Ti atom. Finally, next virtual
orbitals (from LUMO+4 to LUMO+10) are delocalized over
the whole cluster. Fig. 7 illustrates a representative orbital of
each group.
Fig. 7 Selected occupied and virtual frontier molecular orbitals of the
(TiO2)9 cluster. (a) HOMO 5, (b) HOMO, (c) LUMO and
(d) LUMO+8.
Adsorbed system orbitals follow the same scheme for all the
dyes except for C343. The main feature of these orbitals is that
there is very little mixing between cluster and dye orbitals. In
general, orbitals are either completely localized on the cluster or
on the dye. The last occupied orbitals (HOMO 3, HOMO 2,
HOMO 1 and HOMO) are very similar to the last free dye
occupied orbitals. In particular, HOMOs of adsorbed systems
are almost identical to the same orbitals for free dyes and they
have no contribution from the cluster. In contrast, first virtual
orbitals correspond to the same orbitals of free cluster, and
they are localized on the cluster region farthest to the dye
molecule. The LUMO orbital of free dyes corresponds to
LUMO+4 for adsorbed NKX-2586 and LUMO+5 for
NKX-2311, NKX-2753 and NKX-2593. These orbitals have
been named LUMO* (or L*) for each system. Finally, the
free dye LUMO+1 orbital corresponds to LUMO+20 for
adsorbed dyes. Some orbitals of adsorbed NKX-2593 have
been represented in Fig. 8.
To better visualize the orbital scheme of the different
systems, in Fig. 9 the computed Kohn–Sham orbital energies

230 Phys. Chem. Chem. Phys., 2012, 14, 225–233 This journal is c the Owner Societies 2012

Published on 11 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CP22058F
Fig. 8 Selected occupied and virtual frontier molecular orbitals of
adsorbed NKX-2593: (a) HOMO, (b) LUMO, (c) LUMO+5 or
LUMO*, (d) LUMO+8, (e) LUMO+17, (f) LUMO+20.
corresponding to free and adsorbed NKX-2593 and (TiO2)9
cluster have been represented. The energies have been shifted
to align the free dye HOMO energy with the adsorbed system
HOMO energy and the free cluster LUMO energy with the
adsorbed system LUMO energy. The free dye HOMO orbital
Downloaded on 24 November 2012
is located within the cluster band gap and free dye LUMO
(and consequently LUMO*) orbitals are located within the
semiconductor conduction band.
Adsorbed C343 presents a different orbital scheme. We
observe more mixing between cluster and dye orbitals and
every orbital has some cluster contribution. LUMO* corresponds
to LUMO+13 for free dye and now, it is delocalized over the
whole system. C343 LUMO is more unstable than the LUMO
orbital for the other dyes arising in a region where there are
much more cluster orbitals, and for this reason the mixing
becomes more notorious.
Similarly to the case for free dyes, we have analyzed the
main contributions to the bands in the spectra for adsorbed
dyes. Important similarities for all dyes can be observed. In all
spectra there is a triad of bands in which the main one is the
most intense and it is in the middle. The first band corresponds
to excitations from the HOMO orbital to virtual orbitals
localized on the cluster. Obviously, these excitations do not
appear in the spectrum of free dyes and they are responsible
for the widening of the first band of the spectra in the low
energy zone after adsorption. For some dyes, in this band
there are minor contributions from the LUMO* orbital. The
presence of this band indicates a direct charge transfer from
Fig. 9 Molecular orbital energies for the ground state. From left to
right free NKX-2593, adsorbed NKX-2593 and free (TiO2)9 cluster.
This journal is c the Owner Societies 2012
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the dye to the semiconductor, which is unexpected since
coumarin dyes are considered type I sensitizers. The presence
of both injection mechanisms could lead to the observation of
different injection rates (as it has been observed for alizarin
dye).46
Next, the main band is contributed from several excitations
from the HOMO orbital to different orbitals delocalized over
the cluster. Nevertheless, all excitations with considerable
intensity involve LUMO+5 (LUMO*) which is an orbital
completely localized on the molecule. Finally, the third band
comprises excitations from HOMO 1 and HOMO 2 (both
localized on the dye) to orbitals of different nature but with
LUMO* contribution. The assignments of the main electronic
excitations for adsorbed NKX-2593 are shown in Table 2.
To complete the analysis the HOMO and LUMO* energies
for the five adsorbed dyes have been represented in Fig. 10.
The energy gap between these two orbitals is related to the
position of the absorption maximum in the spectra. In this
representation the LUMO orbital energy has been set to zero.
As it has been said above, the LUMO orbital is very similar to
the same orbital for free cluster. In consequence, the zero value
corresponds to the lower edge of the semiconductor conduction
band. This figure allows us to combine the different criteria to
evaluate efficiency described in Section 3.2.
HOMO and LUMO* energy gaps are slightly smaller than
HOMO and LUMO gaps for free dyes (differences ranged
from 0.10–0.15 eV). This is due to a stabilization of the
LUMO orbital after mixing with cluster orbitals. HOMO
and LUMO* energy gap of adsorbed C343 dye is rather larger
than those for the rest of dyes. In consequence, its first band in
absorption spectra is blue-shifted in the series and C343 is the
dye with the lowest efficiency as sensitizer. Differences between
NKX-2311, NKX-2586, NKX-2753 and NKX-2593 are small.
Regarding the HOMO–LUMO* energy gap we would predict
the following efficiency ordering: C343 o NKX-2311 o
NKX-2586 = NKX-2753 o NKX-2593.
On the other hand, the higher the LUMO* orbital is located
related to the lower edge of the semiconductor conduction
band, the more efficient the electron injection is. Adsorbed
C343 is the system with the highest-lying LUMO*. Never-
theless, C343 would not be efficient as a sensitizer because it
has almost no absorption in the visible region. For the rest of
Fig. 10 HOMO and LUMO* energies for adsorbed dyes. Energies
have been shifted to set the zero energy to the lower edge of the
semiconductor conduction band.
Phys. Chem. Chem. Phys., 2012, 14, 225–233 231

dyes, the gap between LUMO* and the conduction band edge
increases following the sequence: NKX-2586, NKX-2311,
NKX-2753 and NKX-2593.
When combining these criteria C343 would be the dye with
a lowest efficiency because of its negligible absorption in the
visible region. This prediction agrees with experimental data.9
It could also be stated that the efficiency increases following
the sequence: NKX-2311, NKX-2753 and NKX-2593. In this
series the p electron system increases, the main band becomes
wider, the maximum position of the main band and the
absorption threshold slightly red-shift, the energy gap between
HOMO and LUMO* becomes smaller and the LUMO* is
Published on 11 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CP22058F
located higher related to the lower edge of the semiconductor
conduction band. This efficiency ordering also agrees well with
experimental data.9,11
NKX-2586 and NKX-2753 present similar properties and we
would expect similar efficiencies for both dyes as sensitizers.
Nevertheless for cells sensitized with NKX-2586 the efficiency is
almost 50% of the efficiency obtained in cells based on NKX-2753.
The reason for this discrepancy is that we are not considering all
the factors affecting the global efficiency. As we mentioned in the
Introduction, coumarin dyes are liable to experience p-stacked
Downloaded on 24 November 2012
aggregation. Dyes containing three methine units like NKX-2586
are especially prone to suffer dye aggregation. This effect leads to
inefficient electron injection because of intermolecular energy
transfer between the dyes, resulting thus in a much lower cell
efficiency than for NKX-2753.
4. Conclusions
In this work we have investigated five coumarin based dyes:
C343, NKX-2311, NKX-2586, NKX-2753 and NKX-2593.
TD-DFT calculations have been performed to study their
electronic structure and optical properties. First, optimized
geometries of the free organic dyes as well as adsorbed on a
TiO2 cluster have been obtained in the electronic ground state.
Next, two different TD-DFT implementations (time and
frequency domains) were employed to explore the optical
response of those structures.
From the results, some parameters such as the position and
width of the first band in the electronic absorption spectra, the
absorption threshold and the LUMO energy with respect to
the conduction band edge have been chosen to establish useful
criteria to evaluate the efficiency of these molecules as sensitizers
in DSSCs.
On comparing similar sensitizers, the light harvesting process
is more favorable when the absorption threshold is lower and
the first band in the spectrum becomes wider extending into
the visible region. Secondly, the electron injection in the
semiconductor is more efficient when the excited state is
located higher in the conduction band.
Thus, we predict, in good agreement with experimental
evidences, the following efficiency sequence: C343 { NKX-
2311 o NKX-2753 o NKX-2593. However, our calculations
indicate that NKX-2586 and NKX-2753 would exhibit similar
efficiencies in contrast with the experimental results which
show a much higher efficiency for NKX-2753. The reason lies
on the tendency of NKX-2586 to suffer p-stacked aggregation
phenomena resulting in an inefficient electron injection.
232 Phys. Chem. Chem. Phys., 2012, 14, 225–233
View Article Online
In this work we have established useful theoretical criteria to
evaluate the efficiency of organic molecules as sensitizers in DSSCs.
These criteria will be used in future works to design more efficient
DSSC sensitizers, reducing economical cost and synthesis effort.
Acknowledgements
This work was funded by the Spanish Ministerio de Ciencia e
Innovación, MICINN, projects MAT2008-4918 and CSD2008-
0023. RSA thanks the Junta de Andalucı́a for a predoctoral grant
(P08-FQM-3661 and EXC/2005/FQM-1126). Part of the calcula-
tions has been carried out at the Andalusia Supercomputing
Center–Servicio de Supercomputación del Centro Informático
Cientı́fico de Andalucı́a (C.I.C.A).
References
1 M. Grätzel, Nature, 2001, 414, 338.
2 W. R. Duncan and O. V. Prezhdo, Annu. Rev. Phys. Chem., 2007,
58, 143.
3 Z. Ning, Y. Fu and H. Tian, Energy Environ. Sci., 2010, 3, 1170.
4 A. Mishra, M. K. R. Fischer and P. Bäulere, Angew. Chem., Int.
Ed., 2009, 48, 2474.
5 Y. Ooyama and Y. Harima, Eur. J. Org. Chem., 2009, 2903.
6 Z. Chen, F. Li and C. Huang, Curr. Org. Chem., 2007, 11, 1241.
7 D. Jacquemin, J. Preat, J. E. A. Perpete and C. Adamo, Int. J.
Quantum Chem., 2010, 110, 2121.
8 K. Hara, K. Sayama, Y. Ohga, A. Shinpo, S. Suga and
H. Arakawa, Chem. Commun., 2001, 569.
9 K. Hara, T. Sato, R. Katoh, A. Furube, Y. Ohga, A. Shinpo,
S. Suga, K. Sayama, H. Sugihara and H. Arakawa, J. Phys. Chem.
B, 2003, 107, 597.
10 K. Hara, Y. Tachibana, Y. Ohga, A. Shinpo, S. Suga, K. Sayama,
H. Sugihara and H. Arakawa, Sol. Energy Mater. Sol. Cells, 2003,
77, 89.
11 K. Hara, M. Kurashige, Y. Dan-Oh, C. Kasada, A. Shinpo,
S. Suga, K. Sayama and H. Arakawa, New J. Chem., 2003, 27, 783.
12 Z. Wang, Y. Cui, Y. Dan-Oh, C. Kasada, A. Shinpo and K. Hara,
J. Phys. Chem. C, 2008, 112, 17017.
13 K. Hara, Y. Dan-Oh, C. Kasada, Y. Ohga, A. Shinpo, S. Suga,
K. Sayama and H. Arakawa, Langmuir, 2004, 20, 4205.
14 Z. Wang, K. Hara, Y. Dan-oh, C. Kasada, A. Shinpo, S. Suga,
H. Arakawa and H. Sugihara, J. Phys. Chem. B, 2005, 109, 3907.
15 J. M. Rhem, G. L. McLendon, Y. Nagasawa, K. Yoshihara,
J. Moser and M. Grätzel, J. Phys. Chem., 1996, 100, 9577.
16 H. N. Ghosh, J. B. Asbury and T. Lian, J. Phys. Chem. B, 1998,
102, 6482.
17 R. R. Frontiera, J. Dasgupta and A. Mathies, J. Am. Chem. Soc.,
2009, 131, 15630.
18 K. Deuk Seo, H. Min Song, M. Jun Lee, M. Pastore, C. Anselmi,
F. De Angelis, M. K. Nazeeruddin, M. Gräetzel and H. Kyu Kim,
Dyes Pigm., 2011, 90, 304.
19 R. Impronta, V. Barone and F. Santoro, Angew. Chem., Int. Ed.,
2007, 46, 405.
20 R. Impronta, V. Barone, G. Scalmani and M. J. Frisch, J. Chem.
Phys., 2006, 125, 05410.
21 D. Jacquemin, E. A. Perpète, G. Scalmani, M. J. Frisch, X. Assfeld,
I. Ciofini and C. Adamo, J. Chem. Phys., 2006, 125, 164324.
22 I. Georgieva, N. Trendafilova, A. Aquino and H. Lischka, J. Phys.
Chem. A, 2005, 109, 11860.
23 M. Sulpizi, P. Carloni, J. Hutter and U. Rothlisberger, Phys.
Chem. Chem. Phys., 2003, 5, 4798.
24 Y. Kurashige, T. Nakajima, S. Kurashige and K. Hirao, J. Phys.
Chem. A, 2007, 111, 5544.
25 B. M. Wong and J. G. Cordaro, J. Chem. Phys., 2008, 129, 214703.
26 T. Stein, L. Kronik and R. Baer, J. Chem. Phys., 2009, 131, 244119.
27 X. Zhang, J. Zhang and Y. Xia, J. Photochem. Photobiol., A, 2008,
194, 167.
28 R. Sánchez-de-Armas, J. Oviedo, M. A. San Miguel, P. Ordejón,
M. Pruneda and J. F. Sanz, J. Chem. Theory Comput., 2010,
6, 2856.
This journal is c the Owner Societies 2012

29 R. Sánchez-de-Armas, M. A. San-Miguel, J. Oviedo, A. Márquez
and J. F. Sanz, Phys. Chem. Chem. Phys., 2011, 13, 1506.
30 R. Sánchez-de-Armas, J. Oviedo, M. A. San Miguel and J. F. Sanz,
J. Phys. Chem. C, 2011, 115, 11293.
31 J. P. Perdew and K. Burke, Phys. Rev. Lett., 1996, 77, 3865.
32 N. Troullier and J. L. Martins, Phys. Rev. B: Condens. Matter,
1991, 43, 1993.
33 L. Kleinman and D. M. Bylander, Phys. Rev. Lett., 1982, 48, 1425.
34 E. Artacho, D. Sánchez-Portal, P. Ordejón, A. Garcı́a and
J. M. Soler, Int. J. Quantum Chem. Status Solidi B, 1999, 215, 809.
35 J. Junquera, O. Paz, D. Sanchez-Portal and E. Artacho, Phys. Rev.
B: Condens. Matter, 2001, 64, 235111.
36 E. Anglada, J. M. Soler, J. Junquera and E. Artacho, Phys. Rev. B:
Condens. Matter, 2002, 66, 205101.
37 J. M. Soler, E. Artacho, J. D. Gale, A. Garcı́a, J. Junquera, P. Ordejón
Published on 11 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CP22058F
and D. Sánchez-Portal, J. Phys.: Condens. Matter, 2002, 14, 2745.
38 D. Sánchez-Portal, P. Ordejón, E. Artacho and J. M. Soler, Int. J.
Quantum Chem., 1997, 65, 453.
39 A. Tsolakidis, D. Sánchez-Portal and R. M. Martin, Phys. Rev. B:
Condens. Matter, 2002, 66, 235416.
40 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Rob, J. R. Cheeseman, J. A. Montgomery Jr., T. Vreven,
K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi,
V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega,
G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota,
Downloaded on 24 November 2012
This journal is c the Owner Societies 2012
View Article Online
R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian,
J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts,
R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli,
J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth,
P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich,
A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick,
A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz,
Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov,
G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin,
D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng,
A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson,
W. Chen, M. W. Wong, C. Gonzalez and J. A. Pople, Gaussian 03,
Gaussian, Inc., Wallingford, CT, 2003.
41 M. J. G. Peach, P. Benfield, T. Helgaker and D. J. Tozer, J. Chem.
Phys., 2008, 128, 044118.
42 Z. Qu and G. Kroes, J. Phys. Chem. B, 2006, 110, 8998.
43 S. Hamad, C. R. A. Catlow, S. M. Woodley, S. Lago and
J. A. Mejı́as, J. Phys. Chem. B, 2005, 109, 15741.
44 S. E. Koops, B. C. O’Regan, P. R. F. Barnes and J. R. Durrant,
J. Am. Chem. Soc., 2009, 131, 4808.
45 S. E. Koops, P. R. F. Barnes, B. C. O’Regan and J. R. Durrant,
J. Phys. Chem. C, 2010, 114, 8054.
46 S. Kaniyankandy, S. Verma, J. A. Mondal, D. K. Palit and
H. N. Ghosh, J. Phys. Chem. C, 2009, 113, 3593.
Phys. Chem. Chem. Phys., 2012, 14, 225–233 233