A DFT AND TD-DFT INVESTIGATION OF ELECTRONIC AND

OPTICAL PROPERTIES OF NEW CARBAZOLE DYES WITH D-π-A

STRUCTURE: APPLICATION IN DYE – SENSITIZED SOLAR CELLS

DOCTOR OF PHILOSOPHY
IN
CHEMISTRY
By
Macherla.Yanadi Rao, M.Sc.,

Under the supervision of

Dr. M. SUBBARAO, M.Sc. M.Phil. Ph.D.,
Head and Chairman, Board of Studies (PG)
DEPARTMENT OF CHEMISTRY
ACHARYA NAGARJUNA UNIVERSITY
NAGARJUNA NAGAR
GUNTUR-522 210, A.P., INDIA
 objective
❑ The main objective of this research is to design
dyes for efficient solar cells.

❑ The work described in this thesis relates to the

design and computational modelling of
conjugated dyes for bulk hetero junction organic
solar cells.

❑ It focuses on the design of materials of

conjugated donor dyes through band gap
engineering such as backbone manipulation, as
well as through the incorporation of newly
developed building blocks.
 Back ground of the study
❑ Seeking new sustainable and clean energy is
imminent.
❑ exhaustion of fossil fuels
❑ sustained environmental pollution
❑ Solar energy is an ideal candidate.
❑ clean
❑ tremendous reserve
❑ Solar cell is the core device for converting solar
energy into electric energy.
❑ Present solar cells use silicon.
❑ expensive
❑ perilous to the environment
Working principle of DSSC
 in the DSSC, the dye is oxidised (loses an electron).
 The oxidised dye receives an electron from an iodide ion, which
reduces the dye back to its original form.
 In this process the iodide ions undergo oxidation.

3Iˉ→ I3ˉ + 2eˉ

 the electron that returns to the DSSC from the external circuit
reduces the I3ˉ ion back to iodide ions.
I3ˉ + 2eˉ→ 3Iˉ

 coordination complexes of ruthenium metal noble metal which is

pricey and necessitates a challenging purification process.
 coordination complexes of ruthenium, which are
present in these devices and provide DSSCs with
extraordinarily high photoelectric conversion
efficiencies, have attracted a lot of attention. A cobalt
electrolyte and ruthenium-based dyes have been used in
devices with power conversion efficiency above 12% .
 However, because these dyes contain the noble metal
ruthenium, which is pricey and necessitates a challenging
purification process, they are seldom suitable for use in
lucrative and ecologically responsible photovoltaic
systems.
 Organic dyes
 Organic dyes are simple synthesis, high molar
extinction coefficient, tenable absorption spectrum
response from the visible to infrared area, as well as
their ecologically friendly and low-cost production
procedures, organic dyes have been the focus of
intensive research efforts In recent years, significant
improvements in conversion efficiency have been
made using this type of dye, with levels ranging from
7.1% in 1991 to 13% in 2014.
 Due to its efficient photo induced interamolecular
charge-transfer properties, donor-linker-acceptor (D-
π -A) structures are designed into most organic dyes.
 D- π –A dyes
 Due to their efficient photo induced intramolecular charge transfer
capabilities most organic dyes are created with a donor-linker-acceptor
dipole (D- π –A) structures.
 These organic dyes with donor groups like carbazole, triphenylamine
,indole, and indoline have been created and have produced reports of
DSSCs with extraordinary efficacies.

carbazole indole triphenylamine

indoline
 The carbazoles and their derivatives are one significant class of hetero
aromatic chemicals demonstrating substantial electron-donating capacity.
 These units are preferred for synthesizing organics due to their unique
electrochemical and optical properties,high structural stability and co-
planarity with donor and acceptor units.
 The tight packing of carbazole molecules helps prevent intramolecular
aggregation.
 Cyanide groups in cyanoacrylic acid have high electron – withdrawing
abilities, they are frequently utilized as an electron – accepting moiety.

 The link between electron donors and acceptors is called a bridge or spacer (π).
 Aim, focus and overview of this work
 In this study we analyze several organic dyes of the
D-π-A type, where the electron acceptor (A) is
cyanoacrylic acid and the electron donor (D) is
carbazole.
 Present studied are in this dyes, designated S1
through S9, are produced when carbazole is
substituted with various terminal electron donors (d),
including thiophene, thienothiophene, carbazole, 1,3-
dimethoxyphenyl, and indole. The compounds'
structural, optical, and electrochemical characteristics
are investigated.
 Through "chemical modification" and "computational
modelling," it is intended to develop highly functional
organic dyes with increased spectrum sensitivity
logically. In addition, this research explores the feasibility
of designing new organic dye sensitizers with redshifted
(also known as bathochromic) absorption spectra using
rational in silico design.
 The dye sensitizer's HOMO-LUMO energy gap can be
decreased to achieve such bathochromic shifts. This
project's primary focus is on the correlation between
molecular structure, the HOMO-LUMO gap, and the
UV-Vis absorption spectra of organic dyes. It is outside
the purview of this work to investigate further features,
including long-term stability, adsorption to
semiconductor surfaces, electron injection kinetics, and
migration.
 Computational quantum chemistry
 The Nobel Prize in Chemistry 1998 was divided equally between

 Walter Kohn for his “development of the density-functional theory” and

 John A. Pople “for his development of computational methods in quantum

chemistry”

❑ The 2013 Nobel prize in chemistry has been awarded to

❑ Martin Karplus of Harvard University, US,

❑ Michael Levitt of Stanford University, US, and

❑ Arieh Warshel of the University of Southern California, US,

for “the development of multi-scale models for complex chemical systems”.

 What is computational chemistry
 Computational chemistry, alternatively sometimes called
theoretical chemistry.
 The term computational chemistry is generally used
when a mathematical method is sufficiently well
developed that it can be automated for implementation
on a computer.
 Computational chemistry is used in several different
ways.
 One particularly important way is to model a molecular
system prior to synthesizing that molecule in the
laboratory.
 This is very useful information because synthesizing a
single compound could require months of labour and
raw materials and generate toxic waste.
 What is computational chemistry
 A second use of computational chemistry is in
understanding a problem more completely.
 Some properties of a molecule that can be obtained
computationally more easily than by experimental
means.
 Molecular bonding, which can be obtained from the
results of computations, that cannot be obtained
from any experimental method.
 The tools of computational chemistry

❑Molecular mechanics (MM)

❑ Ab initio calculations

❑ Semiempirical (SE) calculations

❑ Density functional calculations

❑ Molecular dynamics calculations

 The tools of computational chemistry
 Molecular Mechanics (MM)
In 1970 molecular mechanics was invented to describe the
applicability of classical mechanics for calculating the stable
characteristics of a molecule or molecules, like energy,
electrostatics or structure.
 Ab initio calculations:
Ab initio (Latin for “from the beginning” or “from first
principle”) group of techniques where the structure of
molecules can be estimated with the use of the
schrodinger equation, fundamental constant values and
atoms, atomic numbers.
 These techniques are usually utilized for small systems.
 The tools of computational chemistry
 Semiempirical (SE) calculations:
Semiempirical methods utilize experimental data
estimations to provide inputs to arithmetical models.
 Semiempirical estimates are speedy compared to their
ab initio counterparts and are usually applied for a
medium size.
 Density functional theory calculations (DFT):
According to the schrodinger equation estimated
solutions. The central feature of ab initio and
semiempirical method is wave function by passing.
 The tools of computational chemistry
 Time dependent DFT calculations:
Time dependent DFT is used to investigate the properties
and dynamics of many body systems in the presence of
time – dependent potentials like electric or magnetic
fields.
 Molecular dynamics calculations:
Motion of molecules can be studied by the molecular
dynamics method.
 Methodology
 Using the Gaussian 09 software, all computations
are performed in an isolated setting with
chloroform as the solvent .
 Density functional theory (DFT) and the hybrid
functional B3LYP are used to optimize the ground-
state geometry fully, and the B3LYP and the
identical 6-311G++ basis set are used to calculate
the unpaired electron spin densities of radical
cations .
 To simulate the ultraviolet-visible (UV-Vis)
absorption spectra in acetonitrile solvent with the
polarizable continuum model of solvation (PCM) ,
excited-state calculations are also carried out using
time-dependent (TD) DFT with B3LYP using the
same basis set.
 methodology
 The GAUSSVIEW program and Gabedit software
simulate the plots of the optical absorption spectra
and the graphical display of the estimated optical
absorption spectra. The electronic density
distribution utilized to explain the optical and
electronic characteristics of the sensitizers is
displayed using the energy evels of the extracted
molecular orbitals.
 In the DSSC, electron injection and dye
regeneration are accomplished using the
semiconductor TiO2 and the iodine/iodide redox
pair, respectively. The total reorganization energy
(total) of the dyes is determined by optimizing their
cationic and anionic states at the B3LYP/6-31G++
level.
 Rational design of new dyes
 9-vinyl-9H-carbazole, thiophene and its derivatives are
used in theis work as a series of D-π-A, d-D-π-A and
D-A'-π-A types as electron donors (D).
 Analyze the organic pigments of cyanoacrylic acid as an
electron acceptor and conjugate bridge (A).
 As a result 26 organic dyes are produced by substituting
carbazoles with different terminal electron donors (d)
and acceptors (A').
 The structural optical and electrochemical
characteristics of the compounds are investigated.
Rational design of D-π-A dyes
Rational design of d-D-π-A
Rational design of D-A'-π-A
DFT AND TD-DFT STUDIES OF D-π-A STRUCTURAL SENSITIZERS

Nine novel sensitizers S1 – S9 were developed in this

computational work. According to the study, the
created molecules exhibit side visual absorption bands.
In addition, energy gap, light harvesting efficiency (LHF),
open circuit voltage (Voc), frontier molecular orbital
(FMO) are among the parameters that have been
calculated.
DFT and TD-DFT Molecular structure of the designed (D-π-A) dyes
Geometrical parameters

Optimized
structures
of D-π-A
sensitizers
in the gas
phase
Geometrical parameters

Optimized
structures
of D-π-A
sensitizers
in the gas
phase
Geometrical parameters

Optimized
structures
of D-π-A
sensitizers
in the
solvent
phase
Geometrical parameters
Optimized
structures
of D-π-A
sensitizers
in the
solvent
phase
 Dihedral angles
 The dihedral angles between donor and spacer (D-π)
spacer and acceptor (π-A) calculated by DFT/B3LYP/6-
311G++ level in gas and acetonitrile solvent.

 Dihedral angles in the gas and solvent phases.

 S7>S9>S6>S1>S3>S8>S5>S4>S2.
 S2~S4~S6>S8>S7>S5>S1>S3.
 S2,S3,S4 and S5 have a lower dihedral angle value.
 Frontier molecular analysis and electronic properties
 Fundamental dye intramolecular charge transfer (ICT)
occurs in different regions of the investigated dyes
according to the electron density distribution analysis
across the frontier molecular orbitals.
 The LUMO is distributed between the spacer and
central acceptor moieties, where as his HOMO in
molecules S2,S3,S4,S6,S7 and S5 localize to the 9-vinyl-
9H-carbazole donor group.
 The HOMO electrons are widely distributed in the
proposed molecules S9,S8 and S1with the highest
density in the donor group and the lowest density in
the acceptor group.
 Frontier molecular analysis and electronic properties
 The number of cyanoacrylic acid units mainly
determines the location of LUMO, Dye S1-S6 has
significant LUMO charge density in contrast.
 This shows that the injection of high electrons caused
the dye to create a semiconductor electron bond.
Counterplots
of molecular
orbitals
HOMO of
studied dyes
S1 – S9 at
B3LYP/6-
311G++
level of
theory in
the gas
phase
Counterplots
of molecular
orbitals
LUMO of
studied dyes
S1 – S9 at
B3LYP/6-
311G++
level of
theory in
the gas
phase
Counterplots of molecular orbitals HOMO of studied dyes S1-S9 at
B3LYP/6-311G++ level of theory in the solvent phase
Counterplots of molecular orbitals LUMO of studied dyes S1-S9 at
B3LYP/6-311G++ level of theory in the solvent phase
HOMO – LUMO ENERGY GAP (Eg)
 Eg = EHOMO – E LUMO
 A low HOMO-LUMO gap promotes a bathochromic shift and
conversely,improves the efficiency of photovoltics
 Dyes S5 and S7 have a low Eg of 1.8 ev and 1.7 ev in the gas and
solvent phases. S5 and S7 were connected to nitrogen and oxygen.
Absorption spectra
 Light harvesting efficiency (LHF)
 LHE = 1-10-f (f= Exicited state oscillator)

 LHE increased in gas phase: S1>S9>S3>S7>S6>S5>S4>S2>S8

 LHE increased in solvent phase: S9>S7>S3>S5>S1>S4>S6>S8>S2.
 The findings indicate that the LHE values for S1 and S9
are the greatest.
 This is because π- conjugated double bonds with lone
pairs of electrons have a significant capacity to donate
electrons. As a result, it is suggested as a strong
contender for DSSC application.
Electron injection efficiency (ΔG inject )

 in gas phase: S3>S7>S8>S5>S9>S1>S2>S6>S4.

 In solvent phase: S8>S3>S9>S7>S5>S1>S6>S2>S4.
 The results show that S4 has a higher value of ΔG inject

 It is suggested to be good in the applications of DSSCs.

Electron regeneration energy (ΔG regen )
 S1,S9 dyes had greater electron regeneration efficiency
values in the gas and solvent phases than the other dye
molecules.
 The efficiency of electron regeneration is trending
downward in solvent phase :
 S3>S8>S7>S9>S1>S2>S6>S4>S5.
 The efficiency of electron regeneration is trending
downward in Gas phase:
 S3>S8>S7>S9>S3>S1>S4>S5>S6
OPEN CIRCUIT PHOTO VOLTAGE (Voc )
 S1,S9 it is evident that higher LUMO energy causes a
rise in Voc value, which is essential for greater
photocurrent conversion efficiency in DSSCs.

The newly created S5 and S9 dyes should be created to

create highly effective dye-sensitized solar cells.
DFT AND TD-DFT STUDIES OF d-D-π-A DYE
SENSITIZERS
Geometrical parameters
Optimizatin
structure
s in the
gas phase
calculated
by
DFT/6-
311G++
basis set
Geometrical parameters

Optimizatin
structurs
in the
solvent
phase
calculated
by DFT/6-
311G++
basis set
 Dihedral angles
 The D-π is almost similar for S1-S5 (in the range 142
to 145)degrees. And S6-S9 are different (in the range
175-179) while the values of A-π vary between (129
and 150) degree, which indicates a tendency that is
close to coplanarity for S7-S8 .
 This difference can be ascribed to the steric effect of
the hydrogen atoms for the π-conjugated linker. The
conjugation dihedral angle between the π-linker and
the acceptor were all close to 126 and 150 degrees.
 The differences probably indicated that the different
substituted acceptors could not affect the conjugation
significantly.
 Frontier molecular analysis and electronic properties
 d-D-π-A components HOMO and LUMO values are
crucial indicators of the efficient charge transfer that
takes place between D and A.
 The HOMO-LUMO electron density patterns of the
investigated dyes. The LUMO exhibits bonding between
two neighbouring fragments, the HOMO exhibits
antibonding.
 The carbazole – containing orbitals of the donor, the
terminal electron donor, and the π-linker are where the
LUMO electron density is most strongly localized for all
investigated compounds.
 The dyes S2,S3,S4,S6and S5 the electronic transition
from HOMO to LUMO contributed more than 65%
where as S1,S5,S7 and S8 contributed about 50%.
Counter plots of molecular orbitals HOMO of studied dyes S1-S8 at
B3LYP/6-311G++ level of theory in the gas phase.
Counter plots of molecular orbitals LUMO of studied dyes S1-S8 at
B3LYP/6-311G++ level of theory in the gas phase.
Counter plots of molecular orbitals HOMO of studied dyes S1-S8 at
B3LYP/6-311G++ level of theory in the solvent phase.
Counter plots of molecular orbitals LUMO of studied dyes S1-S8 at B3LYP/6-
311G++ level of theory in the solvent phase.
 HOMO-LUMO energy gap (Eg)

 The HOMO energies decline in the following order:

 S3<S2<S7<S6<S5<S8<S1<S4, where as the LUMO
energies were identical for all compounds in the gas and
solvent phases except S3.
 The dye S4 has a smaller gap than the other dyes under
study due to its high HOMO energy.
Absorption spectra
 Light Harvesting Efficiency (LHE)
 LHE values increased as follows:
S1>S3>S7>S6>S5>S4>S8>S2 in the gas phase.
S8>S7>S3>S5>S1>S4>S6>S2 in the solvent phase.

 Electron injection Efficiency (Δ G inject):

 S3>S7>S8>S5>S1>S2>S6>S4 in the gas phase.
 S8>S3>S7>S5>S1>S6>S2>S4 in the solvent phase.
 * S4 has a greater value for Δ G inject

 Elctron regeneration Energy ((Δ G regen):

 S1-S9 dtes had greater electron regeneration efficiency values in the gas and solvent
phases than the other dye molecules. Large
 (Δ G regen) can therefore encourage pigment renewal and raise Jsc.
 The efficiency of electron regeneration is trending downward as seen below:
 S3>S2>S7>S6>S5>S1>S8>S4 in the gas phase.
 S3>S2>S7>S8>S5>S1>S6>S4 in the solvent phase.
* The results show that these dyes, especially S4 with
cyanoacrylic acid as the terminal electron donor, exhibit
favourable opto electronic characteristics for DSSCs.
DFT and TD-DFT studies of D-A'-π-A structural sensitizers
Geometrical parameters

Optimized
structures
of studied
dyes using
DFT/B3LYP
/6311G++
level of
theory in
the gas
phase.
Optimized
structures
of studied
dyes using
DFT/B3LY
P/6311G+
+ level of
theory in
the gas
phase.
Optimized
structures
of studied
dyes using
DFT/B3LY
P/6311G+
+ level of
theory in
the
solvent
phase.
Optimized
structures
of studied
dyes using
DFT/B3LY
P/6311G+
+ level of
theory in
the solvent
phase.
 Dihedral angles
 The D-A'-π-A molecules, the π-spacer is used as the
bridge of intramolecular charge transfer(ICT), so the
bridge bonds between the donor (D) and acceptor
(A') and π-spacer and acceptor (A) give an account of
the interaction among themselves.
 Two parameters were introduced to indicate the
molecular planarity D-A', A'-π.
 S1 – S6 (range 142 to 144) degree, S7-S9 (175-
179)degree, the values of A'-π (126-150)degree.
 That is close to coplanarity for S7-S9.
Counterplots of molecular orbitals HOMO of studied dyes
S1-S9 at B3LYP/6-311G++ level of theory in the gas phase
Counterplots of molecular orbitals LUMO of studied dyes S1-S9 at
B3LYP/6-311G++ level of theory in the gas phase
Counterplots of molecular orbitals HOMO of studied dyes S1-S9 at
B3LYP/6-311G++ level of theory in the solvent phase
Counterplots of molecular orbitals LUMO of studied dyes S1-S9 at B3LYP/6-
311G++ level of theory in the solvent phase
HOMO-LUMO ENERGY GAP(Eg)
Absorption spectra
 Light harvesting efficiency (LHE)

 LHE values increased in the gas phase

S1>S9>S3>S7>S6>S5>S4>S2>S8.
S9>S7>S3>S5>S1>S4>S6>S4>S2 in the solvent phase.

 The result indicates that S1 and S9 have the highest

LHF values. This is because they have strong electron-
donating ability through the π-conjugated unshared
electron-pair double bond.
The dyes with D-A'-π-A configuration could S8
and S9 dyes has better performance in DSSCs.
 Final conclusion in my work
in this work we investigate a series of D-π-A , and
d-D-π-A and D-A'-π-A type organic dyes with 9-vinyl –
9H-carbazole as the electron donor (D), thiophene and its
Derivatives as the π-conjugated bridge and cyanoacrylic
acid as the electron acceptor (A) substitution of carbazole
by various terminal electron donors (d) and different
acceptors (A) results in the formation of 26 organic dyes.
The structural optical and electrochemical properties of
the compounds are investigate.
“D-A'-π-A architecture is more suitable than D-π-A , and
d-D-π-A architectures”
publications
publications