Crystal growth and characterization of second- and third-order nonlinear optical Chalcone derivative: (2E)-3-(5-bromo-2-thienyl)-1-(4-nitrophenyl)prop-2-en-1-one

Article abstract of DOI:10.1107/S1600576718006386

Experimental and computational studies of linear and nonlinear optical (NLO) properties of (2E)-3-(5-bromo-2-thienyl)-1-(4-nitrophenyl)prop-2-en-1-one (5B2SNC) single crystals are reported. Good-quality and large-sized single crystals of 5B2SNC were succe

Full text of DOI:10.1107/S1600576718006386

research papers
Crystal growth and characterization of second- and
third-order nonlinear optical chalcone derivative:
(2E)-3-(5-bromo-2-thienyl)-1-(4-nitrophenyl)prop-
2-en-1-one
ISSN 1600-5767
Parutagouda Shankaragouda Patil,a Shivaraj R. Maidur,a Mohd Shkir,b* S. AlFaify,b
V. Ganesh,b Katturi Naga Krishnakanthc and S. Venugopal Raoc
Received 27 November 2017
Accepted 25 April 2018
aDepartment of Physics, KLE Institute of Technology, Opposite Airport, Gokul, Hubballi 580030, India, bAdvanced
Functional Materials and Optoelectronic Laboratory (AFMOL), Department of Physics, Faculty of Science, King Khalid
University, PO Box 9004, Abha 61413, Saudi Arabia, and cAdvanced Centre of Research in High Energy Materials
(ACRHEM), University of Hyderabad, Hyderabad 500046, India. *Correspondence e-mail: shkirphysics@gmail.com
Edited by G. Kostorz, ETH Zurich, Switzerland
Keywords: chalcone derivatives; nonlinear
optical materials; X-ray diffraction; z-scan
technique; density functional theory (DFT).
Experimental and computational studies of linear and nonlinear optical (NLO)
properties of (2E)-3-(5-bromo-2-thienyl)-1-(4-nitrophenyl)prop-2-en-1-one
(5B2SNC) single crystals are reported. Good-quality and large-sized single
crystals of 5B2SNC were successfully grown and characterized by powder X-ray
diffraction and high-resolution X-ray diffractometry techniques. 5B2SNC was
found to crystallize in the monoclinic noncentrosymmetric space group Cc and
possesses moderately good crystalline perfection. The linear optical properties
were investigated using the absorption spectrum, which reveals a direct optical
band gap of 3.1 eV. The thermal stability was studied with thermogravimetric
analysis/differential thermal analysis. The powder second harmonic generation
efficiency was evaluated by the Kurtz and Perry method, and 5B2SNC was found
to be 26 times more efficient than urea standard. Third-order NLO properties
were studied by the z-scan technique with a femtosecond laser. The second
hyperpolarizability was obtained to be ꢀ1.45 ꢁ 10ꢂ31 e.s.u. The molecule reveals
a strong reverse saturation absorption and negative nonlinear refraction. The
molecule exhibited good optical limiting properties, and its limiting threshold
was measured to be ꢀ3.2 mJ cmꢂ2. In addition, static electric dipole moments,
linear polarizabilities, and first- and second-order hyperpolarizabilities were
calculated by density functional theory (DFT). Highest occupied molecular
orbital/lowest unoccupied molecular orbital band gaps were also evaluated by
DFT calculations. The experimental and theoretical results showed that
5B2SNC exhibits excellent second- and third-order nonlinear optical properties.
Supporting information: this article has
supporting information at journals.iucr.org/j
1. Introduction
Second- and third-order nonlinear optical (NLO) materials
have a wide range of practical applications (Suresh &
Arivuoli, 2012), such as optical limiting (Patil et al., 2015;
˚
Singh et al., 2014), optical data storage (Astrand et al., 2000),
terahertz wave generation (Krishnakumar & Nagalakshmi,
2008) and two-photon excited fluorescence microscopy
(Ftouni et al., 2013). In such applications, organic NLO
materials are more promising than inorganic materials (Boyd,
2003; Bosshard et al., 2001). Among the studied organic NLO
materials, chalcone derivatives are attractive for their future
use in NLO device functions like frequency conversion and
optical limiting (Sunil Kumar Reddy et al., 2014; Gu, Ji, Patil &
Dharmaprakash, 2008; Ramkumar et al., 2013; D’silva et al.,
2012a; Kiran et al., 2010). The presence of a carbonyl group, a
# 2018 International Union of Crystallography
J. Appl. Cryst. (2018). 51
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long conjugated chain and various donor/acceptor substi-
tuents to two aromatic rings makes chalcone derivatives
potential materials for NLO applications. Several studies have
been published on chalcones, with the aim of optimizing the
nonlinear optical properties (Goto et al., 1990; Zhao et al.,
2000; Ramkumar et al., 2015; Shkir et al., 2015; Gu et al., 2009,
Gu, Ji, Patil, Dharmaprakash & Wang, 2008; D’silva et al.,
2012b). The main idea behind these studies was to introduce
various substituents [OCH3, N(CH3)2, NH2, F, Cl, Br, I, CH3,
thiophenecarbaldehyde and 4-nitroacetophenone in 60 ml of
methanol as illustrated below (Patil, Rosli, et al., 2007):
NO2, COCH3] on either side of the benzene rings. The C
O
group was always the acceptor. In this way, a number of
acentric chalcone crystals exhibiting high nonlinear optical
susceptibilities and transparent in the blue spectral region
have been synthesized (Sunil Kumar Reddy et al., 2014; Gu, Ji,
Patil & Dharmaprakash, 2008; Ramkumar et al., 2013, 2015;
D’silva et al., 2012a,b; Kiran et al., 2010; Goto et al., 1990; Zhao
et al., 2000; Shkir et al., 2015; Gu et al., 2009; Gu, Ji, Patil,
Dharmaprakash & Wang, 2008).
It appeared to us of great interest to modify the chromo-
sphere chalcone group by substituting a thiophene cycle with a
bromo group as a substituent for the benzene ring in the styryl
part of the molecule and to study the resulting NLO proper-
ties (Patil, Rosli et al., 2007; Patil, Ng et al., 2007). Recently, the
single-crystal structure of one such synthesized chalcone
derivative, (2E)-3-(5-bromo-2-thienyl)-1-(4-nitrophenyl)prop-
2-en-1-one (5B2SNC), has been reported (Patil, Rosli et al.,
2007). It crystallizes in the monoclinic noncentrosymmetric
space group Cc with lattice constants a = ꢃ6.3062 (2), b =
The final product was obtained as a red–brown microcrystal-
line solid.
A solubility study revealed that a mixture of acetone–N,N-
dimethylformamide (DMF) (1:1) was a suitable solvent
proportion for 5B2SNC crystal growth. Crystals were grown
by a slow evaporation solution growth technique at room
temperature. Solvent evaporation was controlled by a tight
covering at the top of beaker, provided by a pored polythene
sheet. Transparent red–brown bulk crystals of size 10 ꢁ 4 ꢁ
3 mm with definite morphology were obtained within 2 weeks
(Fig. 1). The crystals are non-hygroscopic and stable at room
temperature.
˚
30.3062 (8), c = 13.1854 (4) A, ꢀ = 94.549 (1) , and there are
eight molecules per unit cell (Patil, Rosli et al., 2007; Patil, Ng
et al., 2007). It possess a D–ꢁ–A–ꢁ–A type structure. The
5-bromo-2-thienyl group acts as donor on one end, with C
O
as electron-withdrawing assembly in the center and NO2 as
acceptor at other end of molecule (see scheme below). As a
part of extensive research on this molecule, herein we present
a study of the bulk crystal growth, powder X-ray diffraction
(PXRD), high-resolution X-ray diffraction (HRXRD),
thermal expansion, transmittance, and second- and third-order
NLO properties. The aim of this study is also to determine the
linear and nonlinear properties of 5B2SNC through density
functional theory (DFT) and Hartree–Fock (HF) methods. To
this end, we present a DFT study using the procedure of
supermolecular polarization to calculate the linear polariz-
ability (ꢂ), first hyperpolarizability (ꢀ) and second hyperpo-
larizability (ꢃ). The computed values are in agreement with
experimental findings. The study provides useful information
for the design of new and efficient chalcone derivatives.
2.2. Characterization
The crystalline perfection was studied through HRXRD
curves using a multicrystal X-ray diffractometer (Lal &
Bhagavannarayana, 1989). The powder second harmonic
generation (SHG) efficiency of 5B2SNC in comparison with
urea standard was measured by a generic method devised by
Kurtz and Perry using a Q-switching pulsed Nd:YAG laser
2. Experimental procedures
2.1. Synthesis and crystal growth
All reagents and solvents employed were commercially
available and used without further purification. 5B2SNC was
prepared by the Claisen–Schmidt condensation reaction
between equimolar quantities (0.01 mol each) of 5-bromo-2-
Figure 1
Photograph of grown single crystals of 5B2SNC.
ꢄ
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(YAG is yttrium aluminum garnet; duration of pulses 8 ns,
repetition rate 10 Hz) operating at 1064 nm (Kurtz & Perry,
1968; Patil & Dharmaprakash, 2007). A finely powdered
crystal of 5B2SNC was densely packed in a microcapillary and
exposed to a laser beam. The generated second harmonic
wave of 532 nm was detected by a photomultiplier tube
(Hamamatsu R5109, visible PMT) and converted into elec-
trical signals. For the analysis of third-order NLO properties
the z-scan technique was used, and its experimental details are
given in the supporting material.
is found to be monoclinic with space group Cc, which confirms
the noncentrosymmetric structure. This is a necessary condi-
tion for the material to possess second-order NLO properties.
The XRD data were used as input in the POWDERX software
(Dong, 1999) to obtain lattice parameters a = 6.30642, b =
ꢃ
˚
30.29775, c = 13.18594 A, ꢂ = 90.014, ꢀ = 94.521, ꢃ = 120.000 ,
3
V = 2172.81482 A , which are in good accord with the reported
˚
single-crystal data (Patil, Rosli et al., 2007).
3.2. Molecular geometry study
The obtained geometry of 5B2SNC at the B3LYP/6-31G*
level of theory is shown in Fig. 2. The initial geometry of
5B2SNC as an asymmetric unit (single molecule) was taken
from the previous report (CCDC 636774; Patil, Rosli et al.,
2007). The respective bond lengths of 3O—21H and 2S—19H
2.3. Computational details
Geometry optimization and calculation of molecular prop-
erties were achieved with the Gaussian 09 program (Frisch et
al., 2009). The obtained results were visualized with the
GaussView 5 program (Dennington et al., 2009). To obtain a
stable molecular geometry and photophysical and NLO
properties, the B3LYP/6-31G*, HF/6-31G*, CAM-B3LYP/6-
31G* and wb97XD/6-31G* levels were applied. It is widely
recognized that these methods are advantageous for deter-
mining sensible and precise geometries, vibrational frequen-
cies, and photophysical and NLO properties, and the obtained
results are found to be well correlated with those obtained by
conventional experimental methods (Johnson et al., 1993;
Reshak & Khan, 2014; Wong et al., 2009; Jia et al., 2014;
Karakas et al., 2016; Shkir, Patil et al., 2017). Detailed infor-
mation on the calculations of various nonlinear parameters is
available in the literature (Abbas et al., 2015; Shkir, AlFaify et
al., 2017).
˚
˚
are found to be 2.89 and 2.44 A at HF/6-31G*, 2.90 and 2.43 A
˚
at B3LYP/6-31G*, 2.88 and 2.40 A at CAM-B3LYP/6-31G*,
˚
and 2.88 and 2.43 A at wb97XD/6-31G* levels of theory. These
bond lengths are in agreement with the reported experimental
˚
values (2.88 and 2.44 A; Patil, Rosli et al., 2007). The other key
bond lengths and angles computed at B3LYP are found to be
˚
1Br—27C = 1.87 A, 2S—27C = 1.73 A, 2S—22C = 1.76 A,
˚
˚
˚
3O—17C = 1.22 A, 4O—6N = 1.23 A, 5O—6N = 1.23 A, 6N—
˚
˚
ꢃ
˚
11C = 1.47 A, 27C—2S—22C = 90.89 , 4O—6N—5O =
124.78ꢃ, 4O—6N—11C = 117.62ꢃ, 5O—6N—11C = 117.59ꢃ,
3O—17C—18C = 121.53ꢃ and 3O—17C—16C = 119.22ꢃ,
which are also close to experimental values (Patil, Rosli et al.,
2007). The results suggest that the parameters of the optimized
molecular geometries at different levels of theory are in close
accord with experimental values.
3. Results and discussion
3.1. Structural analysis
3.3. Multicrystal X-ray diffractometry
The recorded HRXRD curve of the 5B2SNC crystal is
shown in Fig. 3. The solid line of the convoluted curve fits well
with the experimental points, displayed as filled circles. The
diffraction curve comprises two other peaks, which are 81 and
7600 from the main peak. These extra peaks are due to internal
structural low-angle (tilt angle ꢅ 10 but less than a degree)
For structural confirmation and lattice parameter determi-
nation, the PXRD pattern of a homogeneously powdered
5B2SNC specimen was recorded; this is shown in Fig. 1S (see
supplementary information) with hkl indexing. The sharp
peaks of the diffraction pattern confirm the high crystallinity
of the grown crystals. The crystal system of the grown crystals
Figure 2
Optimized molecular geometry of the 5B2SNC molecule at the B3LYP/6-
31G* level of theory.
Figure 3
High-resolution diffraction curve recorded for a 5B2SNC single crystal.
ꢄ
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Table 1
boundaries (Sheik-Bahae et al., 1990; Patil et al., 2016). The
full widths at half-maximum (FWHMs) of the main peak and
low-angle boundaries are 66, 73 and 6400, respectively, with an
angular spread of ꢀ60. These characteristics demonstrate the
high crystalline perfection of the grown 5B2SNC crystal.
The values of ꢄabs (nm), E (eV) and f0 and the major contributions for
transitions obtained at different levels of theory.
Methods
Experimental
B3LYP
ꢄabs
E
f0
Major contributions
366
274
3.10
2.95
3.88
4.45
4.60
7.33
3.88
5.01
3.94
5.06
–
–
–
–
319.54
278.40
269.73
169.11
319.31
247.49
314.78
245.22
0.55
0.19
0.71
0.94
0.83
0.18
0.86
0.33
H ! L + 1 (67%)
H ꢂ 4 ! L (60%)
H ! L (48%)
H ꢂ 1 ! L + 2 (58%)
H ! L (63%)
H ! L + 1 (41%)
H ! L (60%)
H ꢂ 4 ! L (56%)
3.4. Optoelectronic studies
HF
3.4.1. Optical and TD-DFT analyses. The measured UV–
vis–NIR spectrum of 5B2SNC is shown in Fig. 4(a). The grown
crystals are transparent in the 440–1500 nm wavelength
region. The spectrum consists of three absorption bands, at
ꢀ366, 274 and 215 nm. The direct and indirect band gap values
were calculated to be 3.1 and 2.95 eV, respectively [see inset of
Fig. 4(a)].
CAM-B3LYP
wb97XD
DFT methods reproduced the absorption bands reasonably as
detected in the experimental spectrum. The excitation ener-
gies determined at the TD-B3LYP/6-31G* level of theory are
found to be very close to experimental values for all the
applied methods. The calculated absorption wavelengths
(ꢄabs) are 278 and 319 nm with oscillatory strength (f0) of 0.55
and 0.19 at the TD-B3LYP/6-31G* level of theory, which are in
close conformity with the experimentally observed values of
274 and 366 nm [see inset of Fig. 4(a)]. The oscillatory strength
indicates the strength of optical/molecular interaction
between molecules and in the current work its value is
observed to be 0.18–0.94 for different methods (Shkir, 2017).
The values of ꢄabs, energy (E) and f0 and the major contri-
butions obtained with all applied methods are given in Table 1.
The absorption bands at 278 and 319 nm are mainly due to
H ꢂ 4 ! L (60%) and H ! L þ 1 (67%) transitions (one-to-
one).
For UV–vis analysis of the 5B2SNC molecule, the TD-DFT
methods such as TD-B3LYP, TD-HF, TD-CAM-B3LYP and
TD-wb97XD were used at the 6-31G* basis. Fig. 4(b) shows
the UV–vis absorption spectra of 5B2SNC computed using the
above-mentioned TD-DFT methods. Note that all of the TD-
3.4.2. HOMO–LUMO (highest occupied molecular orbital/
lowest unoccupied molecular orbital) analysis. Fig. 5 shows
the three-dimensional images of HOMO, HOMOꢂ1, LUMO
and LUMO+1 determined at the B3LYP/6-31G* level of
theory, and their values are given in Table 1S (see supple-
mentary information). The calculated energy gap (3.401 eV)
Figure 4
(a) Experimental UV–vis–NIR absorption and (b) computed spectra of
5B2SNC, obtained with different TD-DFT methods using the 6-31G*
basis set.
Figure 5
Plots of HOMO–LUMO orbitals of the 5B2SNC molecule.
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and chemical hardness (1.701 eV) values confirm the 5B2SNC
molecule’s good kinetic solidity. By using B3LYP/TD-DFT,
the electronic transition of the 5B2SNC molecule has been
found to be 3.41 eV. The observed value of 3.41 eV is related
to charge transfer of electrons from the highest occupied
states to the lowest occupied states and transfer of charges
between ground and excited states of 5B2SNC molecules. The
present theoretical values, 3.401 eV (HOMO–LUMO gap)
and 3.88 eV (TD-DFT), are very close to the experimentally
calculated value of 3.10 eV. The studied molecule comprises
an NO2 group at one terminal as a result of the strongly
electron-withdrawing nature of the inductive and resonance
effects. This effect also disables the benzene ring and brings
the LUMO onto the NO2 group adjacent to the ring. The
HOMO is situated at the opposite end of the molecule, and
the locations of the HOMOꢂ1 and LUMO+1 orbitals explain
the supremacy of the NO2 group by transferring the charges
from one part of the molecule to another.
In equation (1), x = z/z0, z0 is the Rayleigh range, Leff is the
effective length of the sample, Leff = ½1 ꢂ expðꢂꢂ0LÞꢆ=ꢂ0, L is
the thickness of the sample, and ꢂ0 and ꢂ2 are the linear and
´
two-photon absorption coefficients (Hernandez et al., 2008,
Maidur et al., 2017).
The phase change ÁÈ0 is related to the nonlinear refractive
index n2 as
n2 ¼ ÁÈ0=kI0Leff;
ð2Þ
where I0 is the input intensity of the laser beam at the focus
(z = 0), and k = 2ꢁ/ꢄ is the wavevector.
The respective n2 and ꢂ2 values are obtained to be
ꢀꢂ3.93 ꢁ 10ꢂ14 cm2 Wꢂ1 and ꢀ1.85 ꢁ 10ꢂ9 cm Wꢂ1. The
obtained nonlinear coefficients are two orders of magnitude
higher than those of 3,4,5-trimethoxy chalcones (Gu, Ji, Patil
& Dharmaprakash, 2008) and approximately of the same
order as those of 3,4-dimethoxy-40-methoxychalcone under
femtosecond excitation (Patil et al., 2016). The results for n2
and ꢂ2 allow us to compute the real and imaginary parts of the
third-order optical susceptibility, ꢅ(3), respectively, by the
following equations (Kumar et al., 2010):
3.5. Thermal analysis
The thermogravimetric analysis/differential thermal
analysis (TGA/DTA) curves of 5B2SNC are depicted in Fig. 2S
(see supplementary information). In the DTA curve, there is
an irreversible endothermic peak at a temperature of
439.40 K, corresponding to the 5B2SNC melting point. The
sharpness of the peak demonstrates the good crystallinity and
purity of the chalcone. The exothermic peaks of the DTA at
560.76 and 678.10 K correspond to a loss of weight in the TGA
plot due to degradation and evaporation of the sample. The
open-capillary technique is also used to confirm that the
melting point of 5B2SNC is ꢀ439 K, which is similar to the
result obtained by thermal analysis.
ꢀ
ꢁ
10ꢂ4 "0C2n20n2
Reꢅð3Þðe:s:u:Þ ¼
;
ð3Þ
ꢁ
3.6. Nonlinear optical studies
3.6.1. Second harmonic generation. The SHG efficiency of
5B2SNC is observed to be 26 times higher than that of urea
crystals of similar particle size. The 5B2SNC crystal is a D–ꢁ–
A–ꢁ–A type of system, in which the charge transfer takes
place from donor to acceptor of the molecule. The high value
of SHG is due to the presence of strong electron donor and
acceptor groups, in a head-to-tail configuration, and inter- and
intramolecular hydrogen bonding (Patil, Rosli et al., 2007).
3.6.2. Third-order nonlinear optical properties. Open-
aperture and closed-aperture z-scan transmittance curves of
5B2SNC are shown in Fig. 6. In the open-aperture z-scan (S =
1) (Fig. 6a), the valley of transmittance is representative of
reverse saturable absorption (RSA). The closed-aperture
z-scan trace exhibits a peak–valley configuration, signifying a
negative refractive nonlinearity (self-defocusing behavior)
(Fig. 6b).
To evaluate the nonlinear parameters, the experimental
transmittance was fitted by the expression (Ftouni et al., 2013)
ꢂ2I0Leff
2ð21=2Þð1 þ x2Þ
Figure 6
(a) Open-aperture and (b) closed-aperture z-scan curves of 5B2SNC for
800 nm, 80 MHz laser pulse excitation.
TðzÞ ¼ 1 ꢂ
:
ð1Þ
ꢄ
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Table 2
The third-order NLO parameters of 5B2SNC in DMF solution (0.01 M) at 800 nm wavelength and 80 MHz laser repetition rate.
ꢂ0
ꢂ2
n2
Re ꢅ(3)
Im ꢅ(3)
ꢅ(3)
ꢆg
ꢆex
ꢃh
Limiting threshold
)
(cmꢂ1
)
(10ꢂ9 cm Wꢂ1
)
(10ꢂ14 cm2 Wꢂ1
)
(10ꢂ12 e.s.u.) (10ꢂ12 e.s.u.) (10ꢂ12 e.s.u.) (10ꢂ17 cm2) (10ꢂ15 cm2) (10ꢂ31 e.s.u.) (mJ cmꢂ2
0.36
1.85
ꢂ3.93
ꢂ3.36
1.01
3.52
5.96
11.4
1.45
3.2
ꢀ
ꢁ
10ꢂ2 "0C2n0ꢂ2ꢄ
4ꢁ2
good optical limiting properties (Zhou & Wong, 2011;
Sauteret et al., 1976; Samuel et al., 1994; Zhou et al., 2009; Dini
et al., 2016; Zhou et al., 2007).
Imꢅð3Þðe:s:u:Þ ¼
;
ð4Þ
ð5Þ
h
i
1=2
ꢂ
ꢂ
ꢂ
ꢂ
ꢀ
ꢁ
ꢀ
ꢁ
2
2
3.6.4. First hyperpolarizability study. The first hyperpolar-
izability value was calculated using methods including B3LYP/
6-31G*, HF/6-31G*, CAM-B3LYP/6-31G* and wb97XD/6-
31G*. The parameters obtained from the B3LYP/6-31G* level
of theory, such as electronic total dipole moment (ꢇtot),
molecular total and anisotropy of polarizability (ꢂ0 and Áꢂ),
and static and total first hyperpolarizability (ꢀ0 and ꢀtot), are
given in Table 2S (see supplementary information). To eluci-
date the nature of the above-mentioned parameters using HF,
the results for CAM-B3LYP and wb97XD are also provided in
Tables 1R–3R. From these calculations, it is clear that the
polarizability and hyperpolarizability values are provided by
the diagonal components (i.e. components along the dipole
moment axis) of ꢂxx and ꢀxxx. However, the present calcula-
tions also indicate that the hyperpolarizability values in
B3LYP theory are higher than those in the other applied
techniques as given in Fig. 3S. ꢇtot is observed to be 5.944 D
and the largest of its components is ꢇx (= ꢂ5.756 D), which is
a major contributor to the hyperpolarizability. The value of
total first hyperpolarizability (ꢀtot) is found to be 53 ꢁ
10ꢂ30 e.s.u., which is 241 times superior to that of urea (0.22 ꢁ
10ꢂ30 e.s.u.) computed with the same theory, and the SHG
efficiency measured by the Kurtz powder technique was found
to be 26 times higher than that of urea in our experimental
studies. The observed values are found to be many times
higher than those for many organic and other molecules
obtained at same level of theory in the literature (Shkir et al.,
2015; Shkir, Patil et al., 2017). Hence, the higher values of ꢀtot
and SHG make the studied molecule a unique candidate for
optical device applications.
ð3Þ
ꢅ
¼
Reꢅð3Þ þ Imꢅð3Þ
;
where n0 is the linear refractive index, "0 is the permittivity of
free space and ꢂ2 is the two-photon absorption coefficient.
Additionally, ꢅ(3) is interrelated to the second-order hyper-
polarizability (ꢃ) as
ꢅð3Þ
ꢃh ¼
;
ð6Þ
4
½ð1=3Þðn20 þ 2Þꢆ N
where N (= NAC ꢁ 10ꢂ3 cmꢂ3) is the molecular density at a
given concentration C and NA is Avogadro’s number. All
calculated NLO parameters are given in Table 2.
Excited-state absorption data provide vital information to
judge the lasing capability of a medium. The excited-state
absorption cross section (ꢆex) of 5B2SNC can be obtained by
fitting the open-aperture curve with the equation
ꢃ
ꢄ
ln 1 þ q0=ð1 þ x2Þ
ꢃ
ꢄ
T ¼
;
ð7Þ
q0=ð1 þ x2Þ
where T is the normalized transmittance, x = z/z0 and q0 =
ꢂ0ꢆexF0Leff/2hv. F0 = 2E/ꢁ!20, F0 and !0 being the laser fluence
and beam radius at the focus, hv is the incident photon energy,
E is the average energy of the laser pulses and ꢂ0 is the linear
absorption coefficient. We also define ꢆg ¼ ꢂ0=NAC (Patil et
al., 2017). The value of ꢆex > ꢆg (Table 2), which signifies the
RSA condition.
3.6.3. Optical limiting. In the past two decades, much
importance has been given to materials with strong optical
limiting characteristics to guard optical instruments, particu-
larly the human eye, from powerful laser beams (Suresh &
˚
Arivuoli, 2012; Patil et al., 2015; Singh et al., 2014; Astrand et
al., 2000). Optical limiting refers to a high transmittance for
low level inputs and decay of transmittance at intermediate
levels of input as the intensity of the incident light rises
(Krishnakumar & Nagalakshmi, 2008). Here, we establish the
optical limiting performance of 5B2SNC in DMF solvent. The
position-dependent fluence was evaluated from the equation
ꢀ
ꢁ
1=2
2
FðzÞ ¼ 4ðln 2Þ Ein=ꢁ3=2 !ðzÞ ;
ð8Þ
where F(z) is the input fluence, Ein is the laser energy and !(z)
is the beam radius at a given position z along the beam.
5B2SNC displays a steady reduction in transmittance with
increasing incident energy of the femtosecond pulses at
800 nm (Fig. 7), indicating a broadband response. When the
normalized transmittance was reduced to 50% the equivalent
incident power was 3.2 mJ cmꢂ2. 5B2SNC exhibits relatively
Figure 7
Broadband optical limiting property of 5B2SNC in DMF.
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Table 3
to the Deanship of Scientific Research at King Khalid
University for funding this work through the Research Groups
Program under grant No. R.G.P. 2/10/39.
The static second hyperpolarizability ꢃ(0; 0, 0, 0) components and their
isotropic average values for 5B2SNC at the B3LYP/6-31G* level of
theory.
Components
ꢃxxxx
ꢃyyyy
ꢃzzzz
ꢃxxyy
ꢃxxzz
ꢃyyzz
ꢃ (iso)
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Funding information
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under DST-SERB Scheme for Young Scientists (grant No. SB/
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