Journal of Photochemistry and Photobiology A: Chemistry 236 (2012) 35–40

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Journal of Photochemistry and Photobiology A:

Chemistry
journal homepage: www.elsevier.com/locate/jphotochem

Density functional theory study on the electronic structure of Monascus dyes

as photosensitizer for dye-sensitized solar cells
Wichien Sang-aroon a,b , Samarn Saekow b , Vittaya Amornkitbamrung b,c,∗
a
Department of Chemistry, Faculty of Engineering, Rajamangala University of Technology Isan, Khon Kaen Campus, Khon Kaen 40000, Thailand
b
Integrated Nanotechnology Research Center, Department of Physics, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand
c
Thailand Center of Excellence in Physics, CHE, Ministry of Education, Bangkok 10400, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: This work presents a theoretical study of electronic and redox properties of Monascus dyes using DFT and
Received 13 January 2012 TDDFT with B3LYP/6-31+G(d,p) level. The dye properties in solvent environment were carried out with
Accepted 12 March 2012 IEF-PCM(UAKS)/TDDFT/B3LYP/6-31+G(d,p) method. The ground and excited state oxidation potentials as
Available online 23 March 2012
well as electron injection from the dyes to semiconductor TiO2 are reported. The calculation shows that
all of the dyes can potentially be good photosensitizers in DSSC. Their LUMOs lie over the Ecb of TiO2 and
Keywords:
their HOMOs lie under the reduction potential energy of the electrolytes (I − /I3− ) corresponding to ability
Monascus purpureus
of electron transfer from the dye excited state to TiO2 and charge regeneration after photooxidation
Natural dyes
Natural pigments
process, respectively.
Dye-sensitized solar cell © 2012 Elsevier B.V. All rights reserved.
DFT calculations

1. Introduction natural pigment (dye) extracted from Monascus, which is a product

Due to the global challenge for searching and developing of
renewable energy sources, photovoltaic technologies become a
topic of interest in the design of solar to electrical energy conversion
cell. Even though multijunction solar cell has been successfully per-
formed in the laboratory scale with up to 40% conversion efficiency
[1], but their high production cost and toxicity to environment are
problem to use as solar electricity in a very large scale [2]. The fea-
sibility to develop a solar cell, organic molecules and polymers are
two of the most alternatives. The thin film technology introduced
to development of solar cell leading to a dye-sensitized solar cell
(DSSC) [3–5]. These cells composed of a wide band gap semicon-
ductor deposited on a transparent conducting oxide (TCO) glass,
molecular sensitizer and a redox electrolyte [6–10].
N3 and N719 are well-known ruthenium complex compounds
using as sensitizer in DSSC. The energy conversion efficiency of
10% has been reported for Ru-based DSSCs [5,11,12]. However,
Ru-based dyes are not yet suitable for a large scale DSSCs due to
expensive cost of Ru complex compounds and toxicity to environ-
ment. To solve this problem, the numerous metal-free dyes have
been tested and they showed good potential candidates as sensi-
tizers in DSSCs [13–23]. Recently, DSSCs using Xanthomonasin A, a
∗ Corresponding author. Tel.: +66 43 203359; fax: +66 43 203359.
E-mail addresses: wichien.sa@rmuti.ac.th (W. Sang-aroon), vittaya@kku.ac.th
(V. Amornkitbamrung).
of Monascus purpureus fermentation, has been reported [24]. The
DSSC showed energy conversion efficiency as high as 2.3%. Other
natural dyes possess the energy conversion efficiency not over 2%
except for chlorophyll dyes (4%) [25,26].
Eight major pigments produced by the Monascus fungus. The
four dyes were selected to study in this work as depicted in
Fig. 1. Xanthomonascin A its isomer (1,2) are yellowish colorant.
Monascin is also yellowish colorants. Rubropunctatin and Rubrop-
unctamine are orange and reddish colorants, respectively. The dyes
with C7 H11 alkyl group (e.g. Xanthomonascin B) were neglected
because electronic structure of the dye have not affected by the
alkyl chain lengths. Due to high energy conversion efficiency found
in the recently DSSC experiment as mentioned above, a class of
Monascus dyes is interesting to theoretical study as photosensitizer
for DSSC. To predict the photophysical property of photosensitizer
in DSSC, it is important to understand of electronic influences con-
tribute to electron injection of this dye into TiO2 surface. Calculation
of the excited state oxidation potential energy as well as electron
injection relative to TiO2 conduction band edge is not important
only for interpretation of photovoltaic data but also for seeking tool
a new photosensitizer with more suitable electronic property.
To investigate the electronic and optical properties, the most
favorite method; density functional theory (DFT) is the method of
choice according to an accurately describe and less computational
cost in comparison to other high-level quantum approaches. Time-
dependent DFT (TDDFT) has been widely used to investigate excited
state property because the high accuracy is reasonable to correlate

1010-6030/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jphotochem.2012.03.014
36 W. Sang-aroon et al. / Journal of Photochemistry and Photobiology A: Chemistry 236 (2012) 35–40

Fig. 1. Chemical structures of Monascus dyes.

with ab initio method but less computational cost. In this work, the
electronic structure and optical properties, electronic transition,
oxidation potential energy and electron injection force relevant to
charge transfer of the Monascus dyes were investigated using DFT
and TDDFT with computational methods were reported.
2. Computational methods
The ground-state geometries of Monascus series were opti-
mized with DFT at the B3LYP/6-31+G(d,p) level [27–31]. The
vertical excitation energies were examined using TDDFT at the
same level. The free energy change (in eV) for electron injection
from dyes to TiO2 surface can be expressed as [32]
dye∗
Ginject = EOX − ECB
TiO2
dye∗
where EOX is the oxidation potential energy of the dyes in the
dye∗
excited state. Based on Rehm and Weller equation [33], EOX
be estimated by
dye∗ dye
EOX = EOX − E00 + ωr
dye
where EOX is the oxidation potential energy of the dyes in the
ground state while E00 is vertical excitation energy and ωr is a
coulombic stabilization term. The later term can be negligible as
dye∗
mentioned in the previous work [34], so EOX is approximately
dye TiO2 is corresponding to the conduction
estimated EOX − E00 . ECB
band of the TiO2 semiconductor. The ECB TiO2 = −4.0 eV [35] used
in this work obtained from experiment because of the presented
value has been observed in the condition where the semicon-
ductor is in contact with aqueous redox solution at fixed pH [4].
Recently, Preat et al. [36] proposed equation to calculate Ginject
reliable to relax excited state, the Ginject calculated by unrelax
paths are approximately 0.5 eV differs from those the relax path.
The previous work is concluded that the calculation with unre-
lax path is reliable. Thus, Ginject for the dyes is estimated using
unrelax path in this work. The solvation effects were evaluated
using the integral-equation formulation polarizable continuum
model (IEF-PCM) [37–43]. Single-point calculation in various sol-
vent media of the optimized structures has been performed with
IEF-PCM(UAKS)/B3LYP/6-31+G(d,p) level. Based on the previous
work, the maximum wavelength of UV–vis absorption spectra of
other Monascus dyes observed in methanol [44]. Thus, in this work,
UV–vis absorption spectra in water and methanol were simulated.
All of the calculations were performed with Gaussian 03 program
package [45]. The Molekel is utilized in molecular graphic [46].
(1)
3. Results and discussion
3.1. Electronic structure
can
The ground state structures for four-selected Monascus dyes
(2) were carried out at the B3LYP/6-31+G(d,p) level. The discussion
based on geometrical parameter of the ground state structure is
neglected. The dipole moments, the highest occupied molecular
orbital energies (EHOMO ) and the lowest unoccupied molecular
orbital energies (ELUMO ) of all Monascus dyes computed at the
B3LYP/6-31+G(d,p) level in vacuo, water and methanol are listed
in Table 1. The ELUMO levels for all dyes in various media are in
increasing order: vacuo < MeOH < water. In contrast, the EHOMO is
in random order in the media. It can be noted that the environmen-
tal media plays a major role in stabilization of EHOMO . However, the
most positive value of (ELUMO − EHOMO ) is found in water media. The
dipole moments of all Monascus dyes in all media are in increas-
ing order: Xanthomonascin A1 < Monascin < Xanthomonascin A2

Table 1
The highest occupied molecular orbital energies (EHOMO ), the lowest unoccupied molecular orbital energies (ELUMO ) and dipole moments of all dyes obtained at the B3LYP/6-
31+G(d,p) level.

Dye EHOMO a ELUMO a b

Vacuo Water MeOH Vacuo Water MeOH Vacuo Water MeOH

Xanthomonascin A1 −6.75 −6.50 −6.60 −2.87 −2.69 −2.71 3.953 6.404 6.266
Xanthomonascin A2 −6.18 −6.15 −6.22 −2.97 −2.88 −2.91 9.555 14.377 14.186
Monascin −6.10 −5.88 −5.94 −2.50 −2.34 −2.37 7.932 11.206 11.054
Rubropunctatin −6.18 −6.04 −6.04 −3.07 −2.94 −2.97 10.329 14.728 14.575
Rubropunctamine −5.77 −5.69 −5.78 −2.91 −2.75 −2.78 13.419 20.372 19.808
a
In eV.
b
Dipole moment in Debye.
 W. Sang-aroon et al. / Journal of Photochemistry and Photobiology A: Chemistry 236 (2012) 35–40 37

Table 2
The vertical singlet states, transition character and oscillating strength (with f > 0.01) of the absorption bands in UV–vis region for all dyes computed at the TDDFT/B3LYP/6-
31+G(d,p) level.

Dye Energiesa Transition characterb f

Vacuo H2 O MeOH Vacuo H2 O MeOH Vacuo H2 O MeOH

Xanthomonascin A1 3.03 3.02 3.01 H−1 → L (39%) H → L (77%) H → L (77%) 0.089 0.633 0.62
3.10 3.44 3.44 H → L (58%) H−1 → L (49%) H−1 → L (58%) 0.426 0.012 0.01
4.22 4.29 4.29 H → L + 1 (87%) H → L + 1 (88%) H → L + 1 (87%) 0.088 0.12 0.12
Xanthomonascin A2 3.50 3.37 3.36 H−1 → L (77%) H−2 → L (77%) H−2 → L (79%) 0.028 0.052 0.03
3.64 3.45 3.45 H → L (66%) H → L (71%) H → L (72%) 0.470 0.542 0.54
3.79 3.55 3.54 H−3 → L (49%) H−1 → L (87%) H−1 → L (84%) 0.019 0.401 0.06
Monascin 3.31 3.17 3.17 H → L (72%) H → L (78%) H → L (78%) 0.449 0.566 0.56
3.38 4.57 4.57 H−1 → L (84%) H−3 → L (69%) H−3 → L (69%) 0.026 0.105 0.10
4.66 4.87 4.88 H−3 → L (56%) H → L + 2 (48%) H → L + 2 (47%) 0.074 0.018 0.02
Rubropunctatin 2.73 2.68 2.67 H → L (49%) H → L (63%) H → L (62%) 0.201 0.405 0.41
3.21 3.10 3.10 H → L + 1 (51%) H → L + 1 (70%) H → L + 1 (70%) 0.635 0.588 0.59
3.47 3.27 3.26 H−2 → L (48%) H−2 → L (90%) H−2 → L (90%) 0.043 0.023 0.02
Rubropunctamine 2.41 2.44 2.43 H → L (67%) H → L (77%) H → L (77%) 0.157 0.284 0.28
3.14 3.16 3.15 H−1 → L (90%) H → L + 1 (79%) H → L + 1 (79%) 0.578 0.577 0.58
3.36 3.37 3.35 H−2 → L (64%) H−1 → L (89%) H−1 → L (88%) 0.045 0.020 0.02
a
In eV.
b
Major contribution to the transitions are in parenthesis.

< Rubropunctatin < Rubropunctamine. Nevertheless, the dipole Table 3

Maximum absorption wavelengths for UV–vis absorption spectra of all dyes in var-
moments in water are a bit higher than in methanol.
ious media computed at TD/DFT/B3LYP/6-31+G(d,p).
Energy gap (Egap ) and the isopotential plot of HOMO
and LUMO for all dyes are depicted in Fig. 2. Egap of Dye Maximum absorption band (nm)
all dyes in all three media are in increasing order: Vacuo H2 Oa MeOHa
Rubropunctamine < Rubropunctatin < Xanthomonascin A2 <
Xanthomonasin A1 340.2 359.2 358.7
Monascin < Xanthomonascin A1. This means that the highest reac- Xanthomonasin A2 399.0 411.0 410.9
tivity was found in Rubropunctamine while Xanthomonascin A2 Monascin 374.9 391.6 391.6
was found as the lowest reactivity. In case of Xanthomonascin A, Rubropunctatin 386.0 399.6 399.7
it was found that their MOs were obviously affected by the Rubropunctamine 394.3 392.4 392.8

isomeric form. EHOMO is down shift from A1 to A2 while ELUMO a

is inversed. So, the larger energy gap is found from A1 to A2
form. The different in chemical structure of these isomers is the
conversion of keto-enol form between ring A and C (see Fig. 1).
As can be seen in Fig. 2, HOMO of isomer A1 is located at C O
moiety, spread out across the ␲-bond on the adjacent A and B
rings. Inversely, a small loop of HOMO is found at OH moiety in
isomer A2. The electron distributions in LUMO are in contrast to
HOMO. Less electron distribution on ring C is found for isomer A1
while high distribution is found for isomer A2. It can be noted that
the C O moiety in ring A stabilize HOMO (EHOMO A1 < A2) while
OH moiety in ring C stabilize LUMO (ELUMO A2 < A1).
Due to the two OH moieties are found in the ring B and either
ring A/C, so which one is attached to TiO2 surface. Considering the
LUMO, it was found that OH moiety on ring B is assumed to be
an anchoring group attached to TiO2 surface as high electron den-
sity loop can be found on. Additionally, the distances between the
anchoring hydroxyl proton and the nearest LUMO site are approx-
imately 0.971 Å for ring B and 2.301 Å for both rings A and C
(indicated by red arrow). The result of MO calculation for Xan-
thomonascin A can describe that which OH moiety attached to
TiO2 surface in the previous experiment [24]. However, HOMO and
LUMO of all dyes were not affected by the aldehyde (ring C), propy-
lene (ring B) and pentyl (ring A) moieties as electron distributions
located on such moieties were not located on such moieties.
For the other three dyes, it was found that Egap of Monascin is
higher than those Rubropunctatin due to lacking of two conjugate
double bonds in rings A and B. The highest ELUMO of Monascin indi-
cated by less electron distribution in the LUMO. Rubropunctamine
has a narrow Egap in comparison to Rubropunctatin. It indicated that
the substitution of nitrogen in ring C can improve distribution and
localization of electron in HOMO and LUMO in Rubropunctamine.
This may be due to the electronegativity of nitrogen is lesser than
those of oxygen atom. Based on isopotential plot of their MOs, dis-
tributions of HOMO in a whole skeleton were found in the three
Due to IEF-PCM(UAKS)/TD/DFT/B3LYP/6-31+G(d,p) method.
dyes but high distribution of LUMO was found only in Rubropunc-
tamine while the other two dyes were in contrast.
3.2. Electronic absorption spectra
TD/B3LYP/6-31+G(d,p) and IEF-PCM(UAKS)/TD/B3LYP/6-
31+G(d,p) methods were employed to simulate the optical
property of the dyes. The computed vertical excited sin-
glet states, transition energies and oscillating strength of all
dyes in vacuo and solvent media are tabulated in Table 2.
The first vertical excitation energies (Eexcit ) of the dyes
are in decreasing order: Xanthomonascin A1 > Monascin >
Xanthomonascin A2 > Rubropunctatin > Rubropunctamine. Eexcit
for all dyes is lowering from vacuo to solvent phase except for
Rubropunctamine. The transition energy in water is almost equal
to in methanol. The transition characters related to the excitation
in water and in methanol are similar but different from vacuo. This
is due to the effect of polar environment.
According to the transition character, most of the dyes show
the HOMO → LUMO transition (in solvent) as the first singlet exci-
tation except for Xanthomonascin A1. The major contribution of
the transition characters in vacuo differs from those solvent due
to the effect of polar environment on the electronic energy level.
The maximum (max ) wavelengths for UV–vis absorption spectra
of all dyes simulated in various media are shown in Table 3. The
calculated max in water and methanol are not different. The max
is ∼20 nm red shift were found for all dyes from vacuo to solvent
phase. The ∼50 nm red shift was found from A1 to A2 isomer of Xan-
thomonascin due to the smaller gap of EHOMO−LUMO . The absorption
band near 400 nm is mainly related to ␲ → ␲ transition.
38 W. Sang-aroon et al. / Journal of Photochemistry and Photobiology A: Chemistry 236 (2012) 35–40

Fig. 2. Isopotential plot of frontier molecular orbital of Monascus dyes and their corresponding energy gap, Egap (eV) in vacuo, in water (are in parenthesis) and in methanol
[are in blanket].

3.3. Excited state oxidation potential energy and electron
injection force
dye
The electron injection free energy (Ginject ), ground (EOX ) and
excited
dye∗
(EOX )
state oxidation potentials computed in vacuo and
solvent phases for the series of Monascus dyes are represented
in Table 4. Based on Koopman’s theorem, ground state oxidation
dye
potential energy related to ionization potential energy. EOX can be
estimated as negative EHOMO [47]. The estimated value is in fair
dye∗
agreement with experimental values [48]. EOX is calculated based
dye∗
on Eq. (2) where coulombic stabilization term is neglected. EOX of
the dyes falls within a range 2.62–3.11, 2.53–3.13 and 2.63–3.21 eV
in vacuo, water and methanol, respectively. Most of the dyes
dye∗
show the cathodic shift in EOX going from vacuo to solvent was
found for all dyes except for Xanthomonascin A1. Nevertheless,
dye∗
anodic shifts of EOX from water to methanol were found for
dye∗
all dyes. EOX of all dyes in solvent media is decreasing order:
Xanthomonascin A2 > Xanthomonascin A1 > Rubropunctatin >
dye∗
Monascin > Rubropunctamine. According to EOX , it shows that
the most convenient oxidizing species is Rubropunctamine while
Xanthomonasin A2 is the worst.
All Ginject estimated from Eq. (1) is in negative value for all
dyes. More negative of Ginject from gas to solvent media were
found. Only Xanthomonascin A2 shows more positive Ginject in
solvent than in gas phase. The value in water and methanol is
not different. From these results, it indicated that the effect of
dielectric surrounding to Ginject values is huge with a shift of
∼1.3 eV from gas to aqueous media found in Xanthomonascin A1
and Monascin. As expected, the solvent also stabilized oxidation
potential and electron injection driving force. The negative Ginject
shows that the electron injection from the dye to TiO2 is sponta-
neous.
Thermodynamically, the spontaneous charge transfer process
from the dye excited state to conduction band of TiO2 requires
LUMO energy with more positive potential than ECB TiO2 (−4.0 eV)
while HOMO energy with more negative than reduction poten-
tial energy of the I − /I3− electrolyte (−4.80 eV) [49] requires for the
spontaneous charge regeneration. The energy level diagram of the
HOMO and LUMO of the dyes and Ecb in water of TiO2 and redox
potential energy of the electrolyte is depicted in Fig. 3. The LUMOs
of all dyes lies over the Ecb of TiO2 while their HOMOs are lower
than the redox potential energy of electrolyte. Thus, it can be noted
that all of them possesses a positive response to charge transfer and
regeneration related to photooxidation process.
3.4. Relationship between electronic structure of the dyes and
photovoltaic performance
The overall efficiency () of the DSSC can be calculated from
the integral of short-circuit photocurrent density (JSC ), open cir-
cuit potential (VOC ), the fill factor (ff) and the intensity of light (Is ),
expressed by
JSC VOC ff
= (3)
Is
From this expression, JSC , VOC , and ff are only obtained by the
experiment. The relationship among these values and electronic
structures of the dyes is still unknown. To analyse relationship
between VOC and ELUMO of the dyes based on electron injection from
 W. Sang-aroon et al. / Journal of Photochemistry and Photobiology A: Chemistry 236 (2012) 35–40 39

Table 4
dye∗ dye
Estimated Ginject , EOX and EOX (all in eV) for Monascus dyes in various media calculated at TDDFT/B3LYP/6-31+G(d,p) level.

Dye Vacuo H2 O MeOH

dye dye∗ inject dye dye∗ inject dye dye∗
EOX EOX G EOX EOX G EOX EOX Ginject

Xanthomonasin A1 6.75 3.11 −0.89 6.50 2.96 −1.04 6.60 3.15 −0.85
Xanthomonasin A2 6.18 3.10 −0.93 6.15 3.13 −0.87 6.22 3.21 −0.79
Monascin 6.10 2.79 −1.21 5.88 2.71 −1.29 5.94 2.83 −1.17
Rubropunctatin 6.18 2.97 −1.03 6.04 2.94 −1.06 6.04 2.96 −1.06
Rubropunctamine 5.77 2.62 −1.37 5.69 2.53 −1.47 5.78 2.63 −1.37

Table 5 Table 6
Estimated open-circuit voltage (eVOC ) and light harvesting efficiency (LHE) of all Photovoltaic performance of DSSC with Xanthomonascin A as dye-sensitizer.
dyes in various media.
Dye JSC (mA cm−2 ) VOC ff  (%)
Dye eVOC a LHEb a,b
Xanthomonascin A 6.1 0.057 0.66 2.3
Vacuo H2 O MeOH Vacuo H2 O MeOH
a
Ref. [24].
Xanthomonasin A1 1.13 1.31 1.29 0.661 0.765 0.760 b
Not specify isomer of the dye.
Xanthomonasin A2 1.03 1.12 1.09 0.625 0.712 0.712
Monascin 1.50 1.66 1.63 0.644 0.724 0.724
Rubropunctatin 0.93 1.06 1.03 0.768 0.743 0.743 including acetic treatment of TiO2 surface and using protic solvent
Rubropunctamine 1.09 1.25 1.22 0.736 0.737 0.737 (ethanol) as a rinsing solvent leading to the overall conversion
a
In eV. efficiency () as high as 2.3%. Based on the relationship of exper-
b
Due to the most oscillating strength. imental VOC and ELUMO , Monascin should give the highest overall
efficiency while Rubropunctatin shows the lowest ones without
LUMO to conduction band of TiO2 (Ecb ), the energy relationship can consideration of other parameter.
be expressed [50]: Another factor relates to efficiency of DSSC is the performance
of the dyes in responsibility to the incident light. Based on the light
eVOC = ELUMO − Ecb (4) harvesting efficiency (LHE) of the dyes, the value has to be as high
It is known that the higher the ELUMO , the larger the VOC . as possible to maximize the photocurrent response. The LHE can be
The approximated eVOC based on Eq. (4) for the dyes are tab- expressed as [51]
ulated in Table 5. It should be noted that experimental VOC is LHE = 1 − 10−A = 1 − 10−f (5)
in voltage but the ELUMO − Ecb in Eq. (4) is in eV, certainly, this
formula expects further test by experimental and theoretical where A(f) is the absorption (oscillating strength) of the dyes asso-
calculation. It was found that eVOC of the dyes are within the ciate to the absorption energy (E00 ). TDDFT is less efficient for the
range 0.93–1.50, 1.06–1.66 and 1.03–1.63 in vacuo to methanol, evolution of transition probabilities than for transition energies.
respectively. eVOC of all dyes is in decreasing order: Monascin > The LHE has to be underweighted for the calculation. It is important
Xanthomonascin A1 > Rubropunctamine > Xanthomonascin A2 > to underline that TDDFT calculation can reliably estimate Ginject
dye
Rubropunctatin. Table 6 is tabulated photovoltaic performance and EOX where the values is important to charge transfer process
of DSSC with Xanthomonascin A [24]. In the optimized condition in DSSC. So, the LHE is regarded to underweight in this work. The

Fig. 3. Schematic energy diagram of Monascus dyes, TiO2 and electrolyte (I − /I3− ). EHOMO and ELUMO of the dyes are in water.
40 W. Sang-aroon et al. / Journal of Photochemistry and Photobiology A: Chemistry 236 (2012) 35–40
LHE of the dyes fall within the range: 0.625–0.768, 0.713–0.767 and
0.712–0.760 in vacuo to methanol (Table 5). The LHE values for the
dyes are in narrow range. This means that all the dyes will give
similar photocurrent.
It can be concluded that a class of selected Monascus dyes
shows a good photophysical properties related to DSSC use but in
different outstanding properties. To now, Monascus yellow (Xan-
thomonascin A) was found to be the best photosensitizer for use
in DSSC compare to other natural dyes except for chlorophyll dyes.
Even though many factors were taken into account such as surface
modification of TiO2 with acetic acid or rinsing solvents for remov-
ing excess dyes have been done to improve JSC , VOC , and ff. This work
suggested that other Monascus dyes including Monascin, Rubrop-
unctatin and Rubropunctamine will be the good photosensitizer in
DSSC as the calculation results show their good oxidation poten-
tial energy and electron injection force lie over the Ecb of TiO2 and
under reduction potential energy of the electrolyte.
4. Conclusion
This work is reported as a theoretical study of Monascus pig-
ment using DFT and TDDFT method. The ground and excited state
oxidation potential energies as well as electron injection of the dyes
show that these dyes are potential to be a good photosensitizer in
DSSC. The LUMO of the dyes with more 1.0 eV upper than Ecb of
TiO2 indicated that these dyes are thermodynamically favorable in
charge transfer into conduction band of TiO2 . At the same results,
the HOMO of the dyes lies under the reduction potential energy
of the electrolyte (I − /I3− ) which means charge recombination of
the dye would be occurred after their photooxidation reaction.
Interestingly, Monascus shows the highest estimated eVOC and also
higher than those of Xanthomonascin A (experimentally observed
in DSSC) where the value is related directly to the efficiency of
DSSC. It can be noted that the other three Monascus dyes in this
calculation work might also give the better DSSC efficiency than
Xanthomonascin A. However, we suggest that the further chemi-
cal modification of the dye such as adding high effective anchoring
groups, bridges or electron donors groups could raise the IPCE, JSC
and VOC of the DSSC with these photosensitizers.
Acknowledgments
This work was financially supported by the National Research
University Project, Khon Kaen University through the research
Grant No. PD.54401. Faculty of Engineering, Rajamangala Univer-
sity of Technology Isan, Khon Kaen Campus was also acknowledged
for partially financial support.
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