Quantum Chemical Studies, Electronic & Optical properties ...
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Quantum Chemical Studies, Electronic & Optical properties and
Light Harvesting Efficiency of 4-Methoxybenzylchloride as -linker
with Donor-Acceptor variations effect for DSSCs performance
V. Sivagami1, *M. Karnan2 and M. Anuradha3
1,2,3PG & Research Department of Physics, Srimad Andavan Arts & Science College (Autonomous),
Trichy-620 005, Tamil Nadu, India
[email protected] [email protected]*
ABSTRACT:
The optimized molecular structure of 4-Methoxybenzylchloride (4-MBC) has been
investigated using density functional theory (DFT) method. The HOMO - LUMO energies
and their band gap are calculated from DFT using the B3LYP/ 6311G++d,p basis set. The
local and global reactivity descriptors of 4-MBC are studied. Many approaches have
recently been proposed to extend the efficiency of solar cells greater than the theoretical
limit. In solar cell technology the application of methoxybenzene is used for improving sun-
light harvesting efficiency (LHE). LHE of the titled molecule and new designed dyes are
investigated using TD-DFT by using series of organic sensitizers including donors, acceptors
and binary linker conjugated bridges. The free energy change for electron injection, exciton
binding energy and open circuit voltage of 4-MBC were also obtained.
Keywords: 4-Methoxybenzylchloride; HOMO – LUMO; Local and global reactivity
descriptor; LHE; Exciton binding energy
1. Introduction
Methoxybenzene has lot of electron rich than aromatic hydrocarbon as results of the
resonance impact of methoxy cluster upon the aromatic ring and it reacts with electrophiles
within the electrophilic aromatic susbstitution reaction more quickly than benzene [1]. It may
be recognized as a monosubstituted aromatic hydrocarbon by-product that has associate in
uneven substituent connected to the phenyl ring. It’s of sizeable interest due to the
environmental concern and conjointly as a model compound for an excellent deal with
chemicals and biologically interesting system [2]. The titled compound 4-
Methoxybenzylchloride was worn to benzylate the aniline nitrogen [3]. 4-MBC is employed
as a chemical agent within the preparation of pyridone conjugated monobactam antibiotics
with gram-negative activity from Pseudomonas aeruginosa, Klebsiella pneumonia and
Escherichia coli [4]. It has been additionally utilized in the composite of 1-napthamide [5]
and diarymethanes via Suzuki cross-coupling potassium aryltrifluoroborates [6].
Dye-sensitized solar cells (DSSCs) have attracted lot of interest for the conversion of
solar power into electricity as a result of their high efficiency and low price [7]. The design
and synthesis of functional dyes became focus on current analysis in sight of their potential
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applications as sensitizers in dye-sensitized solar cells (DSSCs) technologies [8]. Many
analysts are investigating the event of latest dyes (design and synthesis) to reinforce the
photovoltaic performance of the DSSCs. During this context, theoretical studies plays a vital
role as they will offer semi-quantitative information on the effectiveness of sensitizers in dye
sensitized solar cells even before their synthesis. Many structures are developed for the
sensitizer like D-D--A [9], D-A--A [10], D--A-A [11], (D--A)2 [12].
The foremost extensively studied organic dyes sometimes adopt the donor-pi-spacer-
acceptor (D--A) structural motif so as to enhance the efficiency. The photovoltaic
properties of such dyes could also be clearly tuned by selecting appropriate groups inside the
D--A structure. The density functional theory (DFT) has emerged as a reliable standard tool
for the theoretical treatment of structures as well as electronic and absorption spectra. It’s
time-dependent extension, referred to as time-dependent DFT (TD-DFT), will give reliable
values for the valence excitation energies with standard exchange correlation functional. The
computational cost of TD-DFT calculation has maintains an uniform accuracy for open-shell
and closed-shell systems.
This paper presents the analysis of quantum chemical parameters, first order
hyperpolarizability and excitation energy of 4-Methoxybenzylchloride. The functional
groups present in methoxybenzene ends up in the variation of charge distribution within the
molecule and consequently have an effect on the structural, vibrational and electronic
parameters. The electronic property, optical property and LHE of the titled molecule and new
designed dyes are obtained theoretically. The reactive description of the compound 4-MBC
is understood by calculating local and global reactivity descriptors.
2. Computational Details
The molecular geometry optimization of 4-MBC were carried out with Gaussian 0W
software packages developed by Frisch and co-workers [13]. The global and local reactivity
descriptors of the titled compound with standard 6-31+G (d) basis sets was calculated by
using B3LYP, i.e. Becke’s three hybrid functional parameter with Lee-Yang-Parr correlation
method [14, 15].
3. Result and Discussions
3.1. Molecular Geometry
The photovoltaic performance of the titled compound can be understood by having
necessary data of an optimized molecular geometry and electron density distribution of the
organic dyes. This knowledge supports to learn the electronic and spectroscopic behaviour of
the -conjugated spacers [16]. The geometrical parameters of the titled compound 4-MBC
were optimized with Becke3-Lee-Yang-Parr (B3LYP) at 6-31G+(d) and 6-311G++(d,p) basis
sets using GAUSSIAN 09 [17]. The molecule does not possess any rotational, inversion or
reflection symmetry, the molecule is considered under C1 point group symmetry. The
optimized molecular structure of the titled molecule in accordance with the atom numbering
scheme is shown in Fig. 1. The bond length, bond angle and dihedral angle are also
calculated for the titled compound and it is appeared in Table 1. The computed bond lengths
and bond angles at B3LYP with 6-31G+(d) and 6-311G++(d,p) are compared with the
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experimental values. Both the values (calculated and experimental) are more or less
same. The theoretical calculations are executed upon isolated molecule in the gaseous phase
but the experimental results are executed to the molecules in solid state [18].
The optimized molecular geometry shows that O-CH3 is substituted in the first position and
benzyl chloride in the fourth position of the ring. The bond length between C4-C5 has
highest value with other C-C bonds in the ring. The calculated bond length of C1-O7 is
1.362Å which is 0.008 Å lower than the reported experimental value of 1.370 Å [19]. The
optimized bond angle of C3-C4-C5 has lowest value than the other C-C-C bonds in the ring.
The bond angle of C2-C1-C6 is 1.4938 Å compressed than the bond angle of C4-C5-C6, due
to the effect O-CH3 at C1 [20]. From this result it is clear that the phenyl ring appears to be
little distorted and the angles are slightly out of the perfect hexagonal structure due to the
substitution of methoxy group and benzyl chloride instead of H atom.
3.2 Designed Dyes
This was carried out to design new sensitizers for dye sensitized solar cell (DSSC).
The new designed dye has donor (D), pi-linker (), and acceptor (A) as shown in Fig. 2(a)
New dyes were designed by the structural modification of 4-Methoxybenzylchloride.
Structure of 4-MBC dyes is given in Fig. 2(b). In this structure, Benzene and Thiophene were
used as an electron-donor and Carboxyl, Cyano and Nitro groups (-COOH, -CN and -NO2)
were as an electron acceptor because of their high ability of electron- withdrawing and
bonding to semiconductor while the titled compound 4-Methoxybenzylchloride as -linker to
the donor-acceptor systems.
Fig. 1 Optimized molecular structure of 4-Methoxybenzylchloride
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Table 1: The calculated geometric parameters of 4-Methoxybenzylchloride using DFT/B3LYP/631G+d and 6311G++d,p basis set
Parameters
Bond Length (A˚)
Exp. Parameters
Bond Angle (A˚)
Exp. Parameters
Dihedral angles(A˚)
6-31G+(d) 6-311G++(d,p) 6-31G+(d) 6-311G++(d,p) 6-31G+(d) 6-311G++(d,p)
C1-C2 1.4012 1.3978 1.362 C2-C1-C6 119.6845 119.6308 120.7 C6-C1-C2-C3 0.0901 0.1383
C1-C6 1.4047 1.4015 1.384 C2-C1-O7 124.5804 124.589 C6-C1-C2-H12 -179.7804 -179.7455
C1-O7 1.3646 1.362 1.370 C6-C1-O7 115.735 115.78 O7-C1-C2-C3 179.944 179.9771
C2-C3 1.3982 1.3947 1.427 C1-C2-C3 119.4588 119.499 120.8 O7-C1-C2-H12 0.0736 0.0933
C2-H12 1.0842 1.0815 C1-C2-H12 121.201 121.1556 C2-C1-C6-C5 -0.0746 -0.1594
C3-C4 1.3984 1.3946 1.385 C3-C2-H12 119.34 119.3453 C2-C1-C6-H19 179.8536 179.8268
C3-H13 1.0879 1.0852 1.08 C2-C3-C4 121.543 121.5012 119.9 O7-C1-C6-C5 -179.9411 179.9879
C4-C5 1.4062 1.4028 1..363 C2-C3-H13 118.8758 118.922 O7-C1-C6-H19 -0.0129 -0.0258
C4-C14 1.4947 1.4917 C4-C3-H13 119.5807 119.5766 C2-C1-O7-C8 0.8987 0.8798
C5-C6 1.3886 1.3846 1.440 C3-C4-C5 118.1332 118.1827 119.3 C6-C1-O7-C8 -179.2422 -179.2758
C5-H18 1.0878 1.0851 C3-C4-C14 120.9567 120.939 C1-C2-C3-C4 -0.0748 -0.0866
C6-H19 1.0859 1.0832 C5-C4-C14 120.91 120.8782 C1-C2-C3-H13 179.6737 179.7373
O7-C8 1.4225 1.4222 1.422 C4-C5-C6 121.1594 121.1246 121.4 H12-C2-C3-C4 179.798 179.7993
C8-H9 1.0977 1.0951 1.09 C4-C5-H18 119.5831 119.5837 H12-C2-C3-H13 -0.4534 -0.3768
C8-H10 1.0912 1.0886 1.09 C6-C5-H18 119.2567 119.2914 C2-C3-C4-C5 0.0418 0.0527
C8-H11 1.0978 1.0953 1.09 C1-C6-C5 120.0209 120.0616 118.5 C2-C3-C4-C14 179.9342 -179.8224
C14-H15 1.0908 1.0875 C1-C6-H19 118.6872 118.6072 H13-C3-C4-C5 -179.7051 -179.77
C14-H16 1.0906 1.0874 C5-C6-H19 121.2918 121.3312 H13-C3-C4-C14 0.1874 0.3549
C14-Cl17 1.8488 1.849 C1-O7-C8 118.7109 118.7223 C3-C4-C5-C6 -0.0253 -0.0733
* Ref. [20]
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4. Global and Local reactivity descriptors
4.1 Global reactivity descriptor
The global reactivity descriptors such as hardness, chemical potential, softness,
electronegativity and electrophilicity index are widely used to understand the global nature of
the molecules in terms of their stability and it is possible to obtain knowledge about reactivity
of molecules based on density functional theory. From Koopman’s theorem, the ionization
potential (I) and electron affinity (A) are the Eigen value of HOMO and LUMO with the
change of sign [21]
Ionization potential (I) = - E HOMO
Electron affinity (A) = - E LUMO
Electron affinity refers to the capability of a ligand to accept precisely one electron
from a donor. Ionization potential is characterized as the amount of energy required to extract
an electron from the atom. High ionization energy demonstrates high stability and chemical
inertness and small ionization energy shows high reactivity of the atoms and molecules [22].
Absolute hardness and softness are the most important property to measure the
molecular stability and reactivity. Using Koopman’s theorem for closed shell compounds,
hardness (), softness (S) and chemical potential () can be defined as,
----------1; ----------2 and ----------3
Chemical hardness is useful in studying the stability and reactivity of compounds
in terms of HOMO and LUMO energies [23]. It measures the resistance to change the
electron distribution in a collection of nuclei and atoms. The large chemical hardness have
large excitation energies or their electron densities are difficult to alter, while the small
chemical hardness has small excitation energies ie., the electron densities are easily altered.
Fig. 2 (a): Different parts of Donor- spacer-Acceptor system
2 (b): Chemical structure of 4-Methoxybenzylchloride
R1-Benzene, Thiophene; R2 – CN, COOH, NO2
R1
R2
Fig. 2 (b)
e
D
A
h
Fig. 2 (a)
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The electrochemical potential measures an escaping tendency of an electron from an
equilibrium system and it is very well related with the molecular electronegativity in a
compound [24].
Parr et al. [25] have characterized another descriptor to compute the global
electrophilic power of the compound as electrophilicity index () as a measure energy
lowering due to maximal electron flow among donor and acceptor. It is a combined
descriptor contains electronic chemical potential and chemical hardness which explicit
tendency of nature to accept electron. They characterized electrophilicity index () as
follows:
----------4
The maximum charge transfer Nmax measures the tendency of molecule to acquire
additional electronic charge from the environment in the direction of the electrophile. It is
calculated by the following equation.
-------(5)
The two new reactivity indices nucleofugality (En) and electrofugality(Ee) are
proposed by Ayers and co-workers to quantify the nucleophilic and electrophilic capabilities
of leaving group. They can be defined as follows,
---------(6)
---------(7)
Gomez et al. proposed an uncomplicated charge transfer exemplary for donation and
back-donation of charges [26]. An electronic back-donation mechanism is an interaction
between the inhibitor molecule and the metal surface. This idea builds up that if both the
progresses occur, namely charge transfer to the molecule and back-donation from the
molecule. Thus the energy change is preciously proportional to the hardness of the molecule.
It can be denoted by the subsequent equation,
----------(8)
The E back-donation signifies that, when >0 and E back-donation <0 the charge
exchange to a molecule pursue by a back-donation from the molecule is energetically
favoured. In this practice, it is feasible to equity the stabilization among inhibiting
molecules.
The values of chemical hardness, electrochemical potential, electrophilicity index,
maximum charge transfer and E back-donation are listed in Table 2. It is shown that the value of
4-MBC has largest chemical hardness compared with the new designed dyes. The value is
decreased by substituting various donor and acceptor to the titled compound as pi-conjugated
molecule. From the results, the designed dye 4-MBC6 Thiophene as donor and NO2 as
acceptor have the lowest hardness value compared with all those dyes. If the value of
chemical potential is progressively negative, it is increasingly hard to lose an electron but
easier to increase one. It shows that the titled compound 4-MBC is less stable and more
reactive among all other compounds. It is noticeable that 4-MBC6 has the high value of
electrophilicity index which indicates that it have strong electrophiles than the others. The
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maximum charge transfer is obtained in 4-MBC6 (whose energy gap is very low) compared
to the others. The calculated value of E back-donation shows that the dye 4-MBC6 is the best
inhibitor (ie. it has the highest value) than other dyes.
Table 2: Quantum Chemical Parameters: HOMO-LUMO energies, Energy gap, Global
reactivity descriptors and Back donation of 4-Methoxybenzylchloride calculated at
B3LYP/6-311++G(d,p) basis set.
4.2 Local reactivity descriptor
Fukui function (FF) is one of the broadly used local reactivity descriptor to display
chemical reactivity and site selectivity [23]. The atom with highest Fukui function is highly
reactive compared to other atoms in the molecule. Fukui function is characterized as the
subordinate of electron density (r) as for the complete number of electrons N in the system,
at uniform external potential v(r) following on an electron due to all the nuclei in the system,
where is chemical potential of the system.
In chemical reaction, a change in the number of electrons involves the addition or
subtraction of at least one electron in the frontier orbital. During the reaction, behaviour of
electrophilic and nucleophilic attack depends on the local behaviour of molecule. Thus, the
calculated Fukui function helps us to determine active sites of a molecule, based on the
electron density changes experience by it.
However, for studying the local reactivity at the atomic level, the more convenient
way of calculating Fukui function is through the condensed forms of the Fukui functions for
an atom k in a molecule which are expressed as follows: [27]
, for nuclephilic attack,
, for electrophilic attack,
, for radical attack
Parameters
Values (eV)
4-MBC 4-MBC1 4-MBC2 4-MBC3 4-MBC4 4-MBC5 4-MBC6
HOMO energy -6.3669 -6.3312 -6.1881 -6.5293 -6.0997 -5.9590 -6.2923
LUMO energy -0.8941 -1.6650 -1.7847 -2.6645 -1.7115 -1.8179 -2.6784
Energy gap 5.4728 4.6662 4.4033 3.8648 4.3881 4.1410 3.6139
Hardness(η) 2.7364 2.3331 2.2017 1.9324 2.1941 2.0705 1.8070
Softness(S) 0.1827 0.2143 0.2271 0.2587 0.2279 0.2415 0.2767
Chemical potential(μ) -3.6305 -3.9982 -3.9865 -4.5970 -3.9057 -3.8885 -4.4854
Electrophilicity index (ω) 2.4084 3.4258 3.6091 5.4678 3.4762 3.6514 5.5670
Charge Transfer (ΔNmax) 1.3268 1.7137 1.8107 2.3789 1.7801 1.8780 2.4823
Nucleofugality (ΔEn) 0.1461 0.5942 0.7234 1.8370 0.6676 0.7981 1.9851
Electrofugality (ΔEe) 7.4072 8.5905 8.6964 11.0309 8.4789 8.5752 10.9558
Back donation (ΔEback-donation) -0.6841 -0.5833 -0.5504 -0.4831 -0.5485 -0.5176 -0.4517
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Where qk(N) is the charge on the kth atom for neutral molecule while qk(N+1) and
qk(N-1) are the same for its anionic and cationic species respectively. These calculations are
performed at the equilibrium geometries of the neutral charge state of the molecule. Fukui
functions and will give the regions at which the molecule is most able to accommodate
the addition and removal of an electron, respectively. The large values of will point out
the molecular regions most susceptible to nucleophilic attacks, while large values will
couple with regions susceptible to electrophilic attacks. In molecular system, the atomic site
which posses highest condense Fukui function favours the higher reactivity. Lee et al. [28]
have studied the condensed Fukui function and concluded that the most reactive site during
the chemical reaction has the higher value of fk.
Morel et al., [29] have recently proposed a dual descriptor (f(r)), which is defined as
the difference between nucleophilic and electrophilic fukui function. It is given by the
equation,
]
According to dual descriptor fr provides the difference between nucleophilic and
electrophilic attack at a particular site with their sign. If fr > 0, the site is favoured for a
nucleophilic attack, whereas if fr < 0, then the site is favoured for an electrophilic attack.
The values of local reactivity descriptors are calculated at B3LYP/6-311G++(d,p) method
from Mulliken atomic charges in molecules which are presented in Table 3. According to
the condition for dual descriptor, the nucleophilic site for titled compound 4-MBC Positive
i.e. fr>0 is C1, C2, C4, C5, C6, O7, C8, H9, H10, H11, H12, H13, H16, H18 and H19.
Similarly the electrophilic site Negative i.e. fr<0 is C3, C14, H15 and Cl17.
Table 3: Condensed Fukui functions for 4-Methoxybenzylchloride calculated at B3LYP/
6-311G++(d,p) method
Atom qk(N+1) qk(N) qk(N-1) fkn fk
e fkr Δfr sk
n ske sk
r ωk+ ωk
- ωk°
C1 -0.124 -0.163 -0.159 0.039 -0.005 0.017 0.044 0.015 -0.002 0.007 0.128 -0.015 0.056
C2 0.141 0.190 0.295 -0.049 -0.105 -0.077 0.056 -0.019 -0.040 -0.030 -0.160 -0.344 -0.252
C3 -0.681 -0.346 -0.180 -0.335 -0.166 -0.251 -0.169 -0.129 -0.064 -0.097 -1.097 -0.543 -0.820
C4 0.773 0.320 0.156 0.452 0.164 0.308 0.288 0.174 0.063 0.119 1.479 0.537 1.008
C5 -0.057 -0.099 -0.093 0.042 -0.006 0.018 0.048 0.016 -0.002 0.007 0.136 -0.020 0.058
C6 -0.450 -0.571 -0.491 0.121 -0.080 0.020 0.202 0.047 -0.031 0.008 0.397 -0.263 0.067
O7 -0.362 -0.345 -0.238 -0.016 -0.108 -0.062 0.092 -0.006 -0.042 -0.024 -0.053 -0.353 -0.203
C8 -0.420 -0.410 -0.382 -0.010 -0.028 -0.019 0.017 -0.004 -0.011 -0.007 -0.033 -0.090 -0.062
H9 0.224 0.230 0.271 -0.006 -0.041 -0.023 0.034 -0.002 -0.016 -0.009 -0.021 -0.133 -0.077
H10 0.213 0.234 0.281 -0.021 -0.048 -0.034 0.027 -0.008 -0.018 -0.013 -0.067 -0.156 -0.111
H11 0.224 0.227 0.269 -0.003 -0.042 -0.022 0.038 -0.001 -0.016 -0.009 -0.010 -0.136 -0.073
H12 0.227 0.212 0.264 0.015 -0.051 -0.018 0.066 0.006 -0.020 -0.007 0.049 -0.168 -0.060
H13 0.188 0.200 0.262 -0.012 -0.063 -0.037 0.051 -0.004 -0.024 -0.014 -0.038 -0.206 -0.122
C14 -0.801 -0.604 -0.528 -0.197 -0.076 -0.136 -0.121 -0.076 -0.029 -0.053 -0.643 -0.249 -0.446
H15 0.163 0.280 0.309 -0.116 -0.030 -0.073 -0.087 -0.045 -0.011 -0.028 -0.380 -0.097 -0.239
H16 0.271 0.276 0.310 -0.004 -0.035 -0.019 0.030 -0.002 -0.013 -0.007 -0.014 -0.113 -0.064
Cl17 -0.916 -0.066 0.097 -0.850 -0.163 -0.506 -0.687 -0.327 -0.063 -0.195 -2.779 -0.532 -1.656
H18 0.180 0.205 0.262 -0.024 -0.057 -0.041 0.033 -0.009 -0.022 -0.016 -0.080 -0.188 -0.134
H19 0.207 0.233 0.295 -0.025 -0.062 -0.044 0.037 -0.010 -0.024 -0.017 -0.083 -0.203 -0.143
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5. Electronic and UV-Vis spectral properties
5.1 Electronic Properties
Inhibition efficiency of the molecule is closely related to frontier molecular orbital
[30]. The HOMO and LUMO are combined to form the frontier molecular orbital (FMO).
Among electronic applications of these materials as an organic solar cell, the theoretical
knowledge about the energy levels (HOMO and LUMO) of the components is mandatory
[31]. HOMO means the Highest Occupied Molecular Orbital which is the outer most orbital
acts as an electron donor, similarly LUMO means Lowest Unoccupied Molecular Orbital
which is the inner most orbital contains free places to accept electrons [32]. The HOMO and
LUMO energy levels of the donor and the acceptor segments for photovoltaic devices are an
appropriate essential element to decide if the effective charge transfer will occur among
donor and acceptor [33].
The calculated frontier orbital such as HOMO energy, LUMO energy and band gaps
by using B3LYP/6-311G++(d,p) basis set of the titled compound and for six newly designed
dyes are listed in Table.2. The corresponding HOMO-LUMO images for 4-MBC and
designed dyes are shown in Fig. 3(a) & (b). The calculated energy gap (Eg) of the studied
compounds decreases in the following order 4-MBC > 4-MBC1 > 4-MBC2 > 4-MBC4 > 4-
MBC5 > 4-MBC3 > 4-MBC6. However, the dye 4-MBC6 has the most outstanding photo
physical property than the others (ie. band gap value is smaller than that of other Dyes and
the titled compound). The much lower band gap of 4-MBC6 shows a powerful impact of
intramolecular charge transfer.
E HOMO =-6.367
eV E LUMO = -0.894 eV E =5.472 eV
Fig. 3(a) HOMO – LUMO plot of 4-Methoxybenzylchloride
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E LUMO =-1.665 eV EHOMO = -6.331eV E = 4.666eV
E LUMO = -1.784eV EHOMO = -6.188eV E = 4.403eV
E LUMO = -2.664eV EHOMO = -6.529eV E = 3.864eV
E LUMO = -1.711eV E = 4.388eV EHOMO = -6.099eV
E LUMO = -2.678eV
E LUMO = -1.817eV E = 4.141eV
E =3.613 eV
EHOMO = -5.959eV
EHOMO = -6.292eV
Fig. 3(b) HOMO – LUMO plot of different D--A
4-MBC1
4-MBC2
4-MBC3
4-MBC4
4-MBC5
4-MBC6
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5.2 Non-Linear Optical Properties
Dipole moment is another necessary electronic criterion that results from uneven
distribution of charges on different atoms in a molecule. It is primarily helps to investigate
the intermolecular interactions associate with Van-der Waal’s dipole-dipole forces etc., As a
result, if the dipole moment is large it which has stronger intermolecular attraction [34]. The
first order hyperpolarizability of titled compound 4-MBC is calculated using B3LYP/6-
31G+(d) and 6311G++(d,p) basis set, established on finite field approach. The components
of first order hyperpolarizability () are characterized as the coefficient in Taylor’s series
expansion of energy in an external electric field [35].
The energy of an uncharged molecule under a weak, general electric field can be
expressed by Buckingham type expansion [36].
E= E0 - F - FF - FFF+.....
where, E is the energy of a molecule under the electric field F, E0 is the energy of an
unperturbed free molecule, F is the field at the origin, , and are the components of
dipole moment, polarizability and the first order hyperpolarizabilities respectively. The total
static dipole moment (), the mean polarizability (0), the anisotropy of the polarizability
() and the mean first order hyperpolarizabilty (0), are defined by using the x, y and z
components. It is as follows,
The total static dipole moment is,
The isotropic polarizability is,
The anisotropic polarizability is,
The mean first order hyperpolarizability is,
Where,
Since the output values of polarizabilities () and first order hyperpolarizability ()
using Gaussian 09 are reported in atomic units (a.u.). The calculated values are converted
into electrostatic units (e.s.u.) (Note: 1 a.u. = 8.639 10-33 e.s.u.)
The values of total dipole moment () and first order hyperpolarizability () of 4-
MBC for monosubstituted molecule and the new designed dyes are calculated and listed in
Table 4. Total dipole moment and first order hyperpolarizability for 4-MBC is 3.3156 Debye
(2 times greater than those of Urea) and 5.362210-30 e.s.u. (14 times greater than those of
Urea) respectively for the basis set B3LYP/6-31+G(d) (Note: and of urea are 1.3732
Debye and 0.372810-30 e.s.u). The better results were obtained by using different donors and
acceptors and the titled compound is as - linker (D--A).
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Table 4: The DFT/ B3LYP/6-31G+(d) and B3LYP/6311G++(d,p) calculated dipole moments (Debye), polarizability (a.u), β components
and βtot (esu) value of 4-Methoxybenzylchloride and its derivatives (NON LINEAR OPTICAL PROPERTIES)
Parameters B3LYP/
6-31+G(d)
B3LYP/
6-311++G(d,p)
631G+d
(Ben+CN)
631G+d
(Ben+COOH)
631G+d
(Ben+NO2)
631G+d
(Thio+CN)
631G+d
(Thio+COOH)
631G+d
(Thio+NO2)
x 2.7138 2.693 2.7538 0.2252 3.2416 2.9161 -0.2174 -3.5147
y -1.0032 -1.0089 1.8874 -4.1404 2.2186 0.954 -3.4845 -1.2707
z 1.6193 1.5768 -0.0002 0.0033 0.0003 -0.0016 0.002 -0.0011
tot 3.3156 3.2796 3.3385 4.1465 3.9281 3.0682 3.4913 3.7374
xx -66.5115 -66.5003 -127.2485 -112.3741 -128.196 -125.791 -113.222 -127.1023
yy -62.157 -62.1015 -100.6668 -107.1696 -109.771 -104.451 -108.6588 -113.1657
zz -69.0163 -68.9277 -114.0532 -119.4689 -117.943 -114.622 -120.04 -118.5047
xy -6.1297 -6.1046 5.6076 -10.8488 2.7142 5.3201 -12.6338 1.5725
xz -6.3957 -6.212 0.0193 0.0018 0.0172 0.0142 0.0069 -0.0112
yz -0.4115 -0.4124 -0.0073 0.0001 -0.0108 -0.0049 -0.0036 0.0083
Δ(esu) -65.894933 -65.843167 -113.9895 -113.0042 -118.63667 -114.95467 -113.9736 -119.5909
xxx 73.5557 72.6741 157.1295 10.9559 97.6919 156.508 -21.0129 -108.9558
yyy 2.9578 2.8828 68.5268 -86.2186 76.5731 52.3436 -82.5801 -64.1085
zzz -6.4244 -6.4153 -0.0112 0.011 0.0152 -0.0053 0.0166 0.021
xyy 0.8919 0.9673 42.0855 0.3818 35.1522 54.6303 3.3881 -41.9025
xxy -15.336 -15.1788 -58.6036 -42.6494 -34.0679 -69.4425 -36.7703 41.0374
xxz 8.9992 8.6291 -0.077 0.0537 -0.0442 -0.0803 0.032 -0.0549
xzz -4.1443 -3.93 -15.1825 28.4926 -31.8744 -10.8873 23.7622 26.9589
yzz -1.8406 -1.9025 1.8109 -3.8961 5.6823 3.3028 -6.3605 -8.2553
YYZ 0.9769 0.9818 0.0362 0.0689 0.044 0.0076 0.0551 0.0195
XYZ 1.4543 1.41 0.0548 -0.0109 0.052 0.0789 0.0078 0.0755
tot(esu) 5.3622E-30 5.3174E-30 1.3769E-29 1.035E-29 8.3537E-30 1.4988E-29 9.3976E-30 9.5423E-30
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From the results the new designed dye 4-MBC4 (ie. Thiophene and Cynate are
substituted as donor and acceptor) has the total dipole moment 3.0682 Debye (2 times greater
than those of Urea) and first order hyperpolarizability 1.498810-29 e.s.u., (40 times greater
than those of Urea) respectively. The large value of hyperpolarizability is a measure of non-
linear optical activity of the sub-atomic system is related with the intermolecular charge
transfer, resulting from the electron cloud movement through pi-conjugated system from
electron benefactor to electron acceptor gatherings.
5.3 UV-Visible Absorption Spectra
The absorption wavelength (), vertical excitation energy (E) and oscillator strength
(f) of 4-MBC and therefore the new designed dyes are calculated by using TD-DFT/
B3LYP/6-31G+(d) level. The calculated values are listed in Table 5 that demonstrates the
Fig. 4 (a), (b), (c) & (d) Theoretical UV-Vis spectrum of 4-Methoxybenzylchloride and designed dyes
Fig. 4 (a) Fig. 4 (b)
Fig. 4 (c) Fig. 4 (d)
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lowest singlet electronic excitation is characterized as a typical - transition. They are
because of electron motions between the frontier molecular orbital. All transitions from
ground state to excited state (i.e. HOMO to LUMO), the most probable transition is which has
the largest oscillator strength [33]. The theoretically calculated absorption spectra of 4-MBC
and their new designed dyes are shown in Fig. 4. The dye 4-MBC6 has maximum absorption
wavelength whose value is 369.58 nm. From the results, it is clear that the maximum
absorption wavelength shows a red-shift with respect to 4-MBC.
6. Photovoltaic Properties
6.1 Light Harvesting Efficiency for DSSCs
The Light Harvesting Efficiency (LHE) is incredibly vital factor for the organic dyes
considering the role of dyes within the DSSC, i.e. absorbing photons and injecting photo
excited electrons to the conduction band of semiconductor [37]. It often be expressed as,
LHE = 1 – 10-A = 1 – 10-f
Where, f is that the oscillator strength of dye associate to the wavelength max. We
have a tendency to determine that the larger value of f, obtained the higher LHE value. For an
efficient photocurrent response, the LHE of the dye molecule ought to be high. The D--A
structure scheme is shown in Fig. 9a and chemical structure for designing new dyes is shown
in Fig. 9b. All these theoretically calculated LHE values are performed in gas phase and it is
shown in Table 5. The dye 4-MBC1 has the largest light harvesting efficiency value
compared with other dyes and also the titled compound.
Table 5: Calculated light harvesting efficiency (LHE) of 4-Methoxybenzylchloride and
the designed dyes using TD-DFT/B3LYP/6-31G+(d) basis set.
System Wavelength
(λ) nm
Excitation
energy (E) eV
Oscillator
Strength (f) LHE
4-MBC 215.65 5.7492 0.2335 0.41588
4-MBC1 ( Ben+CN) 285.91 4.3365 0.4953 0.68033
4-MBC 2 (Ben+COOH) 304.15 4.0765 0.4665 0.65684
4-MBC3 (Ben+NO2) 348.01 3.5626 0.3622 0.56569
4-MBC4 ( Thio+CN) 302.37 4.1004 0.4926 0.67834
4-MBC 5 (Thio+COOH) 321.34 3.8583 0.4688 0.66022
4-MBC 6 (Thio+NO2) 369.58 3.3548 0.3572 0.56066
6.2 Electron injection
Preat et al. [38-40] theoretically proposed a method to quantify the electron injection
from an excited state of the molecule to the conduction band. The efficiency of solar cell is
highly depends on the amount of electron injection from excited state of the molecule to the
conduction band of the semiconductor (TiO2).
The free energy change (in eV) for the electron injection can be expressed as,
--------(1)
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Where is the oxidation potential of the dye in the excited state and is the
reduction potential of the semiconductor conduction band. Two models can be used for the
evaluation of [41].
In the first method, it is assumed that the electron injection occurs from an unrelaxed
excited state of the dye molecule and the excited state oxidation potential is calculated from
the redox potential of the ground state ( ) and the absorption energy associated with the
photoinduced intramolecular charge transfer ( )
------(2)
------(3)
In the second method, it is assumed that the electron injection occurs from the relaxed
excited state of the dye molecule and is calculated as,
------(4)
The 0-0 transition energy is calculated using max, total energy of first excited
state in ground state symmetry Es1(Qs0) and the total energy of first excited geometry Es1(Qs1)
as,
The and values for 4-MBC and new designed dyes are calculated
using eqn. (1) and (2) and it is shown in Table 6. For the effective functioning of solar cell,
the amount of electron injection from dye molecule to the conduction band of the
semiconductor should be high. If the calculated value of is negative which implies
that they are exergonic injection reaction which is favourable for electron transfer [42]. This
means that the excited state of dyes lie above the conduction band of TiO2, thus favouring the
electron injection from the excited state dyes to the conduction band of TiO2 (-4.0 eV). This
shows a good electron injection from these dyes to the acceptor TiO2, indicating that these
dyes may be good candidates for application in photovoltaic devices.
Table 6: The calculated redox potential of the ground state (EOXdye), oxidation potential
of the dye ( ), absorption energy ( ), free energy change for electron injection
(Ginject) of 4-Methoxybenzylchloride and the designed dyes using B3LYP/631G+d basis
set.
System EOXdye EOX dye* max max
ICT G inject
4-MBC 6.3669 1.19 239.49 5.1769 -2.81
4-MBC1 ( Ben+CN) 6.3313 1.9948 285.91 4.3365 -2.0052
4-MBC 2 (Ben+COOH) 6.1881 2.1116 304.15 4.0765 -1.8884
4-MBC3 (Ben+NO2) 6.5294 2.9668 348.01 3.5626 -1.0332
4-MBC4 ( Thio+CN) 6.0997 1.9993 302.37 4.1004 -2.0007
4-MBC 5 (Thio+COOH) 5.9590 2.1007 321.34 3.8583 -1.8993
4-MBC 6 (Thio+NO2) 6.2924 2.9376 369.58 3.3548 -1.0624
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6.3 Exciton binding energy and Open circuit voltage
Excitons arise from an electron – hole attraction in gapped periodic systems like bulk
insulators, semiconductors as well as in many varietites of nano-scale systems, polymers and
biomolecules [43, 44]. Certain excitons seem in optical spectra of extended systems as
distinct absorption peaks below the quantum gap, whereas continuum excitons enhance the
band-edge absorption [45]. Excitons play a vital role in photovolatics, wherever photoexcited
excitons propagate to hetero-junctions and dissociate to yield currents.
Table 7: Exciton binding energy (Eb) and open circuit voltage (VOC) of 4-
Methoxybenzylchloride and designed dyes are calculated using B3LYP/631G+d basis
set.
System EHOMO
(eV)
ELUMO
(eV) Eg (eV) Ex (eV) Eb (eV) VOC (eV)
4-MBC -6.3669 -0.8942 5.4728 5.1769 0.2959 3.1058
4-MBC1 ( Ben+CN) -6.3313 -1.6651 4.6662 4.3365 0.3297 2.3349
4-MBC 2 (Ben+COOH) -6.1881 -1.7848 4.4033 4.0765 0.3268 2.2152
4-MBC3 (Ben+NO2) -6.5294 -2.6645 3.8648 3.5626 0.3022 1.3355
4-MBC4 ( Thio+CN) -6.0997 -1.7116 4.3881 4.1004 0.2877 2.2884
4-MBC 5 (Thio+COOH) -5.9590 -1.8180 4.141 3.8583 0.2827 2.182
4-MBC 6 (Thio+NO2) -6.2924 -2.6784 3.6139 3.3548 0.2591 1.3216
To attain high energy conversion efficiency, the excited electron and hole pairs should
dissociate to separate positive and negative charges to escape from recombination due to the
coulombic attraction. To achieve this process, the binding energy has to be overcome i.e. the
dye molecule should posses less exciton binding energy for high energy conversion. The
exciton binding energy was calculated using the following formula [44, 46].
where Eg is the band gap (i.e. energy difference between HOMO-LUMO) and EX is
the optical gap and is defined as the first singlet excitation energy max. The maximum open
circuit voltage (VOC) is an important photovoltaic parameter that can be determined
theoretically by the difference between HOMO of the dye and LUMO of an electron acceptor
TiO2. The theoretically calculated data of VOC is determined from the following equation
[47]:
--------- (5)
While in DSSCs, VOC can be approximately estimated as the difference energy
between LUMO of the dye and conduction band (CB) of the semiconductor TiO2 (ECB = - 4.0
eV):
---------(6)
The calculated exciton binding energy and open circuit voltage of 4-MBC and the
designed dyes are listed in Table 7. The result shows that the dye 4-MBC6 is most suitable
for DSSC application by the substitution of Thiophene as donor and NO2 as acceptor. If the
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values of VOC are positive, suggests that the electron transfer will be easy from the dyes to
TiO2. Further, these values are sufficient to obtain the high efficient electron injection.
Besides, these compounds can be utilized as sensitizers by virtue of an electron injection
process from an excited molecule to the conduction band of semiconductor (TiO2).
7. Conclusion
In this present work, the active sites for an electrophilic and nucleophilic
reactions are also observed by the local reactivity descriptors (Fukui function) of 4-
methoxybenzylchloride. The theoretical analysis on organic sensitizers including various
donor and acceptors of 4-MBC and the designed dyes 4-MBC1 to 4-MBC6 have been studied
by TD-DFT / B3LYP / 6-31G+(d) method. The Non-linear optical property of the titled
compound is calculated theoretically by the determination of first order hyperpolarizability.
From the results, it have been seen that 4-MBC4 has the greater value than those of Urea, and
then the titled compound is good candidature for NLO study. Light Harvesting Efficiency
(LHE), free energy change for electron injection ( ), exciton energy (Eb) and open
circuit voltage (VOC) for the titled compound and new designed dyes are calculated. The
global reactivity descriptors (such as chemical hardness, electrochemical potential,
electrophilicity index) UV-Visible absorption spectra were also obtained theoretically. All
the new designed dyes are red shifted as compared with the titled compound. From the above
results, it is clear that the compound 4-MBC based dyes having the best photovoltaic
properties for the dye sensitized solar cells (DSSCs).
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Journal of Information and Computational Science
Volume 9 Issue 8 - 2019
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