Synthesis, characterization and the nonlinear optical properties of newly synthesized 4-((1,3-dioxo-1-phenylbutan-2-yl)diazenyl)benzenesulfonamide

Article abstract of DOI:10.1016/j.saa.2021.119487

The dye of azo compound is prepared by coupling reaction of dizonium salt of sulfanilamide with benzoylacetone. The product is characterized by FTIR spectroscopy, Mass spectroscopy and ¹H NMR spectroscopy. The geometries of the synthesized dye is optimized using B3LYP method and 6-31G (d,p) basis sets. Nonlinear optical properties are investigated theoretically by calculation of some quantum chemical descriptors using the DFT/B3LYP method with a 6-31G(d,p) basis set in comparison with urea as a standard. The UV–visible spectrum of synthesized azo dye are calculated using TD-DFT with B3LYP/6-31G(d,p) level. The nonlinear refractive index of the prepared dye is calculated via the diffraction ring patterns and Z-scan techniques using 473 nm visible, continuous wave laser light. The diffraction ring patterns are numerically simulated using the Fresnel-Kirchhoff theory with reasonable agreements. The property of optical limiting of the azo dye is tested.

Full text of DOI:10.1016/j.saa.2021.119487

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Synthesis, characterization and the nonlinear optical properties of newly
synthesized 4-((1,3-dioxo-1-phenylbutan-2-yl)diazenyl)
benzenesulfonamide
b
a
b
H.A. Sultan a, Adil Muala Dhumad b, Qusay M.A. Hassan a, , Tarek Fahad , C.A. Emshary , Nabeel A. Raheem
⇑
a Department of Physics, College of Education for Pure Sciences, University of Basrah, Basrah 61001, Iraq
b Department of Chemistry, College of Education for Pure Sciences, University of Basrah, 61001, Iraq
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Optimized structure of azo compound NA4.
ꢀ
The azo compound was prepared by
coupling reaction of dizonium salt of
sulfanilamide with benzoylacetone.
We studied the nonlinear optical
properties of azo compound.
The nonlinear refractive index of this
sample is determined using
diffraction ring patterns and Z-scan
techniques.
ꢀ
ꢀ
ꢀ
The sample exhibits self-diffraction
ring patterns due self-phase
modulation.
a r t i c l e i n f o
a b s t r a c t
Article history:
The dye of azo compound is prepared by coupling reaction of dizonium salt of sulfanilamide with ben-
zoylacetone. The product is characterized by FTIR spectroscopy, Mass spectroscopy and 1H NMR spec-
troscopy. The geometries of the synthesized dye is optimized using B3LYP method and 6-31G (d,p)
basis sets. Nonlinear optical properties are investigated theoretically by calculation of some quantum
chemical descriptors using the DFT/B3LYP method with a 6-31G(d,p) basis set in comparison with urea
as a standard. The UV–visible spectrum of synthesized azo dye are calculated using TD-DFT with
B3LYP/6-31G(d,p) level. The nonlinear refractive index of the prepared dye is calculated via the diffrac-
tion ring patterns and Z-scan techniques using 473 nm visible, continuous wave laser light. The diffrac-
tion ring patterns are numerically simulated using the Fresnel-Kirchhoff theory with reasonable
agreements. The property of optical limiting of the azo dye is tested.
Received 6 November 2020
Received in revised form 6 January 2021
Accepted 11 January 2021
Available online 15 January 2021
Keywords:
Azo compound
Z-scan
Nonlinear refractive index
Optical limiting
Optical materials
Ó 2021 Elsevier B.V. All rights reserved.
1. Introduction
such as having large nonlinear refractive indexes and fast response
times grew almost exponentially. Such effects are of technological
During the last three decades the interest in finding or/ and syn-
thesizing of new materials exhibiting nonlinear optical properties
importance for the future use in applications viz., optical limiting,
optical delay, optical switching, all-optical modulation, optical
phase conjugation, in data storage [1–16], to name a few. To date,
vast number of materials has been studied, shows excellent optical
properties and proved their abilities use in number of photonic
⇑
Corresponding author.
E-mail address: qusayali64@yahoo.co.in (Q.M.A. Hassan).
https://doi.org/10.1016/j.saa.2021.119487
1386-1425/Ó 2021 Elsevier B.V. All rights reserved.

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
applications. Among these materials organic materials are consid-
ered as prime one with excellent optical properties owe to their
large nonlinearities which were studied by the present authors
during the last four years [17–36].
Change of index of refraction as a result of the passage of a laser
beam through a medium can lead to number of nonlinear phenom-
ena in the spatial domain viz., self-phase modulation (SPM), self-
focusing, self-defocusing, self-diffraction, optical bi-stability, etc.
[37]. Due to the SPM, concentric diffraction ring pattern distribu-
tions can be induced on a screen in the far-field post the beam
traversing the nonlinear medium.
Sulphanilamide and its derivatives were studied for various rea-
sons since 1965, viz., in the study of the crystal structure of
a-
sulphanilamide [38], its effect on 13C fluxes [39], its biological eval-
uation [40], its antibacterial activity [41], its antibiotics to soil
organic sorbents [42], its bioglogical screening [43], the spectral
study of chelating [44], its antimicrobial activity [45], its pharma-
cological screening [46], its pharmacological evolution [47], its
antimicrobial drugs [48], its spectroscopic, antimicrobial and
antioxidant activities [49] etc.
Benzoylacetone and its derivatives have been studied exten-
sively too, viz., toxicity studies [50], tautomery and acid properties
[51], synergistic extraction equilibrium of lanthanide (III) ions [52],
spectrophotometric study [53], as building block in heterocyclic
synthesis [54], etc.
The changes of refractive index induced by the laser light usu-
ally written as follows:
n ¼ no þ n2I
ð1Þ
In addition to the fact that azo dyes are widely used in the man-
ufacturing of dyes and textiles, azo compounds are of great impor-
tance in many industrial, pharmaceutical, and other fields [55–57].
In the pharmaceutical field, there are a lot of researches indicating
the use of azo compounds in the preparation of antipyretic [58],
anti-inflammatory [59], anti-tumor [60,61] and anti-bacterial
agents [62].
where n0 is the linear refractive index of the medium, n2 is the non-
linear index of refraction and I is the laser light intensity. Based on
the number of rings resulted in the diffraction ring patterns tech-
nique, the total change in the medium refractive index,
Dn, and
n2 can be determined. The Z-scan is another technique which is
simple, versatile and effective in determining n2, the nonlinear
absorption coefficient, b, the magnitude of the real and imaginary
parts of the nonlinear susceptibility and the sign of n2 and of real
part of the susceptibility.
Azo (AN@NA) chromophore group conjugated with aromatic or
heterocyclic substitutes that formed azo compounds. The
p elec-
tron delocalization on the acceptor - donor units across the azo
Fig. 1. Synthetic route of azo compound NA4.
100
%T
90
80
70
60
50
40
30
20
10
-0
`
4000
3600
3200
2800
2400
2000
1800
1600
1400
1200
1000
800
600
Fig. 2. FTIR spectrum of 4-((1,3-dioxo-1-phenylbutan-2-yl)diazenyl) benzenesulfonamide.
2

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
linkage and reorganization of electronic density make this type of
compounds exhibited excellent photophysical properties [63]. Ani-
sotropy properties and photoresponsive behavior of azobenzenes
compounds made these compounds broadly interesting, Therefore,
there are many applications of azobenzenes compounds in areas
such as nonlinear optical (NLO) devices, optical switching and liq-
uid crystal displays (LC) [64–66]. Quantum mechanical computa-
tions investigations have given useful guidelines in the NLO
properties study of organic materials [67].
The main objective of the current study is to find a new material
that can be used as an optical limiter for continuous wave (CW)
laser beams in low power regime. In this work new material is syn-
thesized for the first time, which is 4-((1,3-dioxo-1-phenylbutan-
2-yl) benzensulfonamide by the interaction of sulfanilamide and
benzoylacetone. The new material nonlinear properties viz., the
nonlinear refractive index and the nonlinear absorption coefficient
have been obtained via the diffraction ring patterns and Z-scan
techniques using a CW laser beam of wavelength 473 nm.
2.2. Synthesis
2.2.1. Synthesis of the azo compound NA4
The first step sulfanilamide (1.2 g, 0.007 mmol) was dissolved in
a 10 mL of distilled water containing 1.5 mL of HCl (36%), the solu-
tion was cooled to 0–5 °C in an ice-bath and kept at this tempera-
ture. The second step the sodium nitrite solution (0.6 g, 10 mmol)
in 5 mL of distilled water was prepared, and added dropwise to the
solution obtained from the first step with stirring for 10 min at the
same temperature. The obtained diazonium salt solution was
added portion wise to the solution of benzoylacetone (1.135 g,
0.007 mol) in 10 mL of ethanol and the corresponding azo com-
pound NA4 precipitated, then dried. The synthesis of the azo com-
pound NA4 is displayed in Fig. 1.
2.2.2. 4-((1,3-dioxo-1-phenylbutan-2-yl)diazenyl)
benzenesulfonamide (NA4)
Orange powder. Yield: 70%. m.p.: 198–200 °C. FT-IR (KBr,
m,
cmꢁ1): 3346 (NAH), 3061 (CAH Ar.), 2900 (CAH Aliph.), 1653
(C@O), 1636 (C@C), 1479 (N@N), 1323 (CAN). 1H NMR (500 MHz,
DMSO d6) d 11.25 (s, 2H), 7.78 (dd, J = 25.4, 8.4 Hz, 2H), 7.56 (t,
J = 7.7 Hz, 2H), 7.48 (d, J = 8.5 Hz, 2H), 7.24 (m, 1H), 2.52 (s, 3H).
MS (EI, m/z (%)): 345 (M+, 106). UV/Vis kmax (nm): 360 (N@N);
300 (C@O); 250 (Ar-CN).
2. Experimental
2.1. Instrumentation
All the chemicals were used as received without further purifi-
cation except for aniline, was distilled before use. FT-IR spectrum
of the prepared compound was obtained in the range 4000–
500 cm-1 using KBr disc on Shimadzu FT-IR 8400S spectrometer.
1H NMR spectrum was recorded on Bruker 500 spectrometer using
TMS as an internal reference and DMSOd6 as a solvent. Mass spec-
trum for the compound was recorded on Agilent Technologies-
5975C (EI, 70 eV).
FTIR, Mass and 1HNMR spectra of prepared azo compound are
shown in Figs. 2–4.
2.3. Characterization method
A 10 mM concentration of NA4 solution was prepared by dis-
solving the NA4 compound in an ethanol solvent. UV–visible spec-
Fig. 3. Mass spectrum of 4-((1,3-dioxo-1-phenylbutan-2-yl)diazenyl) benzenesulfonamide.
3

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
trophotometer (PD-303 Japan) was used to measure the absor-
bance, A, spectrum of the NA4 compound solution placed in a
quartz cell with thickness d = 1 mm, at room temperature. Fig. 5
displays the absorbance, A, spectrum of the NA4 compound solu-
tion. UV–visible absorbance of group (N@N) in azo compound is
given in range 350–370 nm [68]. The prepared azo compound
showed an absorption at 360 nm. The UV–visible spectrum also
shows a second absorption close to 300 nm due to the carbonyl
Fig. 4. 1H NMR spectrum of 4-((1,3-dioxo-1-phenylbutan-2-yl)diazenyl) benzenesulfonamide.
Fig. 5. NA4 compound solution absorbance (A) spectrum.
4

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
group (C@O) as a result of the transfer n -
250 nm is caused by the transition of
an aromatic ring and Ar-CN group [69].
p
*. Another absorption at
p – p* due to the presence of
By finding the absorbance, A , value of the NA4 compound solu-
tion from the Fig. 5 at the wavelength 473 nm and using Eq. (2)
[70], we found that the value of the linear absorption coefficient,
a
, equals 0.207 cmꢁ1
.
A
¼ 2:303
d
a
ð2Þ
The UV–visible spectrum of synthesized azo dye NA4 com-
pound was calculated using TD-DFT with B3LYP/6-31G(d,p) level.
According to the results of the UV–visible spectrum, there are
bands in the visible range. The calculated theoretical main bands
of NA4 compound came at 355.51, 300.82 and 294 nm respectively,
Fig. 7. Optimized structure of azo compound NA4.
Fig. 6. UV–visible spectrum of NA4 compound calculated by TD-DFT/B3LYP 6-31G(d,p).
Table 1
Excited states of NA4 calculated using TD-DFT with B3LYP/ 6-31G(d,p).
Excited states* (HOMO ? LUMO)
State
Percentage contribution (%)
Energy (eV)
Calculated
kmax (nm)
446.58
Exp.
360
f
89 ? 91
90 ? 91
1
2
38.4
57.1
2.7763
3.4875
0.001
84 ? 91
84 ? 92
86 ? 91
89 ? 91
89 ? 92
18.7
14.8
11.8
51.1
16.1
355.51
0.209
84 ? 91
84 ? 92
86 ? 91
86 ? 92
87 ? 91
89 ? 91
89 ? 92
3
20.3
17.0
44.1
13.2
11.3
23.4
26.9
3.8306
323.67
0.094
87 ? 91
88 ? 91
4
5
15.0
68.4
3.9236
4.1216
316.00
300.82
0.010
0.072
87 ? 91
89 ? 91
89 ? 92
90 ? 92
21.8
10.0
25.8
59.3
300
250
85 ? 91
86 ? 91
89 ? 92
90 ? 92
6
55.2
19.5
29.7
12.2
4.2087
294.59
0.0718
NA4*, HOMO = 90, LUMO = 91.
5

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
Table 2
Observed and calculated vibrational frequencies and relative intensities of NA4 compound.
Obsd.
Calcd.a
(cmꢁ1
Obsd.
Calcd.a
(cmꢁ1
t
(cmꢁ1
)
Int.b
t
)
Int.c
t
(cmꢁ1
)
Int.b
t
)
Int.c
3346
3257
3061
2900
1653
1595
1479
1346
m
m
vw
s
s
s
3412
3300
3014
2914
1656
1587
1484
1343
41.4
56.1
16.3
11.9
100
28.6
15.2
100
1323
1294
1234
1201
1157
1095
975
m
w
s
m
vs
m
s
1319
1311
1236
1212
1141
1090
965
39.1
100
100
47.7
100
31.3
99.8
w
m
a
b
c
Calculated at the DFT/B3LYP/6-31G level scaling 0.94 is used.
Very strong (vs), strong (s), medium (m), weak (w) and very weak (vw) intensities.
Relative intensities.
meter and a circular aperture of 2 mm diameter while the sample
cell usually sweeped, by fixing it on a translation stage, across the
lens focal point (z = 0) between (ꢁz) and (+z). Such a set-up is the
closed aperture, CA, Z-scan. By removing the circular aperture and
replaced it with another glass positive lens to collect the entire
beam passing through the sample cell, an open aperture, OA, Z-
scan is obtained.
The optical limiting property of the sample was obtained using
the same set-up used before and fixing the sample at the valley
position of the closed aperture Z-scan curve i.e. behind the focal
point of the positive lens and using a power meter to measure
the output beam power post traversing the sample cell against
the variation of input power.
2.5. Computational details
Fig. 8. Plot of the observed vs. the calculated 1H NMR chemical shift of NA4
compound.
All computations were performed using the Gaussian 09 [71]
software package. Full geometry optimizations were performed
using the Density Function Theory (DFT) at B3LYP by the 6-31G
(d,p) basis set level. Fig. 7 shows the optimized structure of the
prepared NA4 azo compound.
as shown in Fig. 6, while the experimentally measured UV–visible
spectrum showed values at 360, 300 and 250 nm as shown in
Fig. 5. Excited states of synthesized azo dye NA4 compound were
determined by TD-DFT/B3LYP 6-31G(d,p) are given in Table 1.
2.5.1. Vibrational spectra
2.4. Experimental setups
The band of N-H stretching vibration coupled doublet at
3346 cmꢁ1 and 3257 cmꢁ1 due to the asymmetric and symmetric
stretching respectively in primary amine. Absorption of C@O at
The laser beam used in the set of experiments was obtained
from a solid state laser device at 473 nm wavelength, CW with sin-
gle fundamental, TEM00, mode and spot size of 1.5 mm (at 1/e2)
and output varies from zero to 66 mW. A glass 1 mm thickness
sample cell 40 cm away from the laser device output coupler. To
focus the laser beam onto the sample cell a glass positive lens of
50 mm focal length was used. The resulted diffraction ring patterns
were casted onto a semitransparent 30x30 cm screen, 85 cm from
the exit plane of the sample cell. Setup can be seen elsewhere [22].
The Z-scan measurements were conducted using the same
setup previously detailed [22], with the screen replaced by a power
lower wavenumbers (1653 cmꢁ1) due to delocalization of the
p
electrons of C@O with aromatic C@C, thus reduces the double-
bond character.
The observed and calculated infrared spectra and the relative
intensities of synthesized azo dye NA4 are listed in Table 2. The
theoretical vibrational frequency spectra of NA4 calculated using
DFT by the B3LYP at the 6-31G(d,p) basis set level. The scaling fac-
tors 0.94 was used in the calculation of stretching frequencies
modes. The scaled calculated frequencies [72], show good agree-
ment with the experimental data.
Table 3
Some calculated quantum chemical descriptors of synthesized dye NA4 and urea.
Comps. EHOMO (eV)
ELUMO (eV)
Ionization potential IE (eV)
Electron affinity EA (eV) (-ELUMO
)
Egap (ELUMO-EHOMO) (eV)
(-EHOMO
)
NA4
Urea
Comps. Hardness
ꢁ6.7647
ꢁ6.7587
ꢁ2.7537
6.7647
6.7587
2.7537
4.0110
8.0621
Chemical potential CP (eV)
ðCP ¼ ꢁvÞ
1.3034
ꢁ1.3034
g
(eV)
Softness S (eVꢁ1
)
Optical softness So (eVꢁ1
)
Electron delocalization
v
(eV)
1
g
S
ðg
¼
ðIEꢁEAÞÞ
ðv
¼
ðIEþEAÞÞ
ðS ¼
Þ
ðSo
¼
2Þ
2
2
NA4
Urea
2.0055
4.0310
0.4986
0.2480
0.2493
0.1240
4.7592
2.7276
ꢁ4.7592
ꢁ2.7276
6

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
2.5.2. 1H NMR spectroscopy study
are compared with the observed data. A good linear relationship
with r2 = 0.999, between the observed and calculated data has been
obtained as shown in Fig. 8.
The chemical shift values for 1H MR measurements of NA4 (as
shown in Section 2.2.2) shows four different proton environments,
which is in agreement with the suggested structure.
The theoretical 1H NMR chemical shift of the prepared com-
pound NA4 have been calculated at B3LYP methods and standard
6-31G (d,p) basis set using the standard GIAO (Gauge-
Independent Atomic Orbital) approach [73]. The calculated values
2.5.3. Orbital energies of the molecule NA4
Highest occupied molecular orbital energy (EHOMO) represents
the ability to donate an electron, while lowest unoccupied molec-
ular orbital energy (ELUMO) as an electron acceptor represents the
Fig. 9. Diffraction ring patterns appears in NA4 compound solution at input laser beam power (mW): (a) 10 (b) 30 (c) 44 (d) 59.
Fig. 10. Diffraction ring patterns in the NA4 compound solution where the laser beam wave front is (a) convergent, (b) divergent at input power of 59 mW.
7

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
Fig. 11. Temporal development of a chosen diffraction ring pattern in NA4 compound solution at input power of 59 mW: (a) 100 msec (b) 200 msec (c) 300 msec (d) 400 msec
(e) 500 msec (f) 600 msec (g) 700 msec (h) 800 msec (i) 1000 msec.
ability to obtain an electron. The HOMO-LUMO energy calculations
of the prepared compound were performed using DFT/B3LYP
method with 6-31G(d,p) basis set. The energy of the HOMO and
LUMO are identified via the ionization potential and the electron
affinity respectively [74].
and hardness of synthesized dye NA4 are ꢁ2.7537 eV,
4.0110 eV and 2.0055 eV respectively were less than their val-
ues in urea, where they are 1.3034 eV, 8.0621 eV and
4.0310 eV respectively. The softness and optical softness values
of prepared compound NA4 are 0.4986 eVꢁ1 and 0.2493 eVꢁ1
respectively, where they are higher than their values in urea,
i.e. 0.2480 eVꢁ1 and 0.1240 eVꢁ1 respectively. These results
indicate that the synthesized dye NA4 have high NLO property
than urea.
2.5.4. Theoretical investigations of the optical nonlinear (NLO)
properties
Nonlinear optical properties of the NA4 compound were inves-
tigated theoretically by the calculation of some quantum chemical
descriptors, QCDs, using the DFT/B3LYP method with a 6-31G(d,p)
basis set in comparison with urea as a standard. The urea is gener-
ally used as a reference in the investigations of NLO properties [75],
therefore, QCDs, of urea are calculated at the same method and
level.
NLO properties of any compound increases according to
increasing of EHOMO, softness means (S) and optical softness
(So). The decreasing of ELUMO, energy gap, ionization potential
3. Result and discussion
3.1. Diffraction ring patterns
Fig. 9 represents the dependence of the ring patterns on the
input power of the laser beam at wavelength 473 nm traversed
the NA4 compound solution in the 1 mm thickness glass cell.
Based on the Fig. 9, the number of diffraction rings increase with
the increase of input power since absorbed energy increases and
more heat resulted. At the same time the ring patterns appears
IE and Hardness (
g) means increasing of NLO properties. The
results are summarized in Tables 3. The LUMO energy, Egap
8

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
circular symmetric at low input power when the conduction cur-
rent that occurs horizontally equals to the vertical convection
current. At higher input power vertical convection current
exceeds the conduction current that leads to asymmetries of
the ring patterns i.e., the upper part of the patterns grew in
low ratio compare to lower part where the upper hot layer
moves upward and replaced by a cool one i.e. refractive index
change is lower than the lower part layer. As the input power
increase so does the area of each pattern also the outer most
rings in each pattern appear intense compare to the inner ones
as a result of self-defocusing. The dependence of type of ring
patterns on the laser beam wave front, convergent and diver-
gent, when the sample was 1 cm before and 1 cm after the lens
focal point respectively are shown in Fig. 10. The temporal evo-
lution of a chosen ring pattern are shown in Fig. 11, where it can
be seen that the ring patterns evolve temporally i.e., appear
small and circular at zero sec time then its area increases, the
number of rings increases with time and each pattern appear
asymmetric as time laps.
3.2. Modeling the diffraction ring patterns:
To qualitatively and quantitatively calculate the diffraction ring
patterns obtained in Figs. 9–11, suppose a CW laser beam with
Gaussian distribution propagate horizontally along the z- direction
and its field vary in the x-y plane from peak power, P, to zero away
ꢀ
ꢁ
1=2
from the z-direction by a distance r = x2 þ y2
where the beam
radius
x
= rwhen the beam intensity, I, reduced from Io to Io=e2. Let
R be the beam wavefront radius, k ¼ 2
p=k, is the laser beam wave
vector and k is the beam wavelength, the laser beam complex field
amplitude, Uðx; y; t; z ¼ 0Þ, at the entrance of the nonlinear med-
ium can be written as follows [55,76]:
ꢂ
ꢃ
ꢂ
ꢃ
1=2
2P
p
r2
x2
r2
2R
Uðx; y; t; z ¼ 0Þ ¼
exp
ꢁ
expðꢁik
Þ
ð3Þ
x2
As the beam traverses the nonlinear medium, part of it’s energy
is absorbed and heat appear as a result of the nonradiative transi-
tions and conduction current appear horizontally in the shape of
Fig. 12. Simulation results (from left to right columns) of diffraction ring patterns in NA4 compound solution (1st), spatial distributions of laser beam phase (2nd), intensity
distributions of laser beam in one dimension (x-3rd) and (y-4th) at power input (mW): (a) 10 (b) 30 (c) 44 (d) 59.
9

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
Gaussian distribution. The ring patterns shown in Fig. 9 loses sym-
metry in the vertical direction suggesting a convection occur in
that direction. The asymmetries in the ring patterns increase as
time laps and as input power increases too. This supposing a con-
vective velocity, vx, which can be written as follows [76]:
The characteristic heat diffusion timetc ꢃ
x
2=4D:
The light field complex amplitude, Uðx; y; t; z ¼ 0Þ, at the exit
plane of the nonlinear medium cell can be rewritten as follows
[76]:
ꢂ
ꢃ
1
ꢂ
ꢃ
2
2p
a
d
x2 þ y2
Tꢂmaxph2
Uðx; y; t; z ¼ 0Þ ¼
expðꢁ Þ: exp ꢁik
bg½
D
16
p
x2
2
x2
vx
¼
ð4Þ
l
ꢂ
ꢃ
x2 þ y2
: exp
ꢁ
expði
D
u
ðx; y; tÞÞ
ð9Þ
b is the medium thermal expansion, g is the gravity acceleration, h
is the distance from the center of the beam to a position at which
convection still occur, [DT]max is the maximum change in the non-
2R
ꢀ
ꢁ
The intensity distribution of laser beam, I x0 ; y0 ; t , on the screen
in the far field with respect to a distance F away from the sample
cell exist plane where the spatial coordinates are rewritten as
linear medium temperature and
be written as follows [76]:
l
is the medium viscosity.DT can
ꢀ
ꢁ
x0 ; y0 , using the Fresnel-Kirchhoff theory and Franuhofer approx-
Z
t
ꢀ
ꢁ
a
pqCp
p
dt0
2
expðꢁ2½ x ꢁ v0x
imation can be written as follows [76]:
D
Tðx; y; tÞ ¼
f
8Dt0 þ x2
0
ꢂ
ꢃ
1
2
ꢂ
ꢃ
Z
þ y2ꢂ=½8Dt0 þ x2ꢂÞg
ð5Þ
2P
i
p
kF
x2
ad
1
ꢀ
ꢁ
I x0 ; y0 ; t ¼ j
exp ðikFÞ exp
ꢁ
dx
p
x2
2
ꢁ1
with D ꢃ K=
qcp is the medium thermal diffusivity and K, q, cp are
ꢂ
ꢃ
ꢂ
ꢃ
Z
1
x2 þ y2
x2 þ y2
its thermal conductivity, density and specific heat respectively.
The temperature variation lead to variation of the medium refrac-
tive index, nðx; y; tÞ, can be written as follows [76]:
ꢄ
dy: exp
ꢁ
:exp½i ꢁk
xx0 þ yy0
x2
2R
ꢁ1
ꢂ
ꢃ
2
þ
D
u
ðx; y; tÞꢂ: exp ꢁik
j
ð10Þ
F
dn
dT
nðx; y; tÞ ¼ n0 þ
D
Tðx; y; tÞ
ð6Þ
Eq. (10) was solved numerically using the MATLAB system.
Figs. 12–14 are the simulation results based on the solution of
Eq. (10). Results of Fig. 12 can be well compared with those given
in Fig. 9 for the diffraction ring pattern evolution as input power
increase. Fig. 13 shows the type of ring patterns dependence on
the the laser beam wave front type which can be compared with
those shown in Fig. 10. Fig. 14 shows the temporal evolution of a
chosen ring pattern which can be compared with those given in
Fig. 11. The overall simulation results agree well with those
measured.
n0 is the NA4 compound solution linear refractive index and
dn=dTis its thermoptic coefficient. The change in the medium index
of refraction, nðx; y; tÞ, leads to a phase change or shift,
D
uðx; y; tÞ,
can be written as follows [76]:
2
p
D
uðx; y; tÞ ¼
d½nðx; y; tÞ ꢁ nð0; 0; tÞꢂ
k
ð7Þ
Using the definitions previously introduced, the phase shift (Eq.
(7)) can be written as follows:
ꢀ
ꢁ
Z
ꢂ
dt0
2
dn
dT
t
ꢀ
ꢁ
a
PL
0
ꢄ
ꢅ
D
uðx; y; tÞ ¼
fexpðꢁ2½ x ꢁ vxt
2t0
tc
3.3. Diffraction ring pattern:
2kktc
0
1 þ
ꢃ
ꢂ
ꢃ
2t0
tc
2t0
tc
ꢀ
ꢁ
The estimation of the induced total change in the NA4 com-
pound solution index of refraction,
the geometrical optics. When a single ring resulted post the prop-
agation of the laser beam in the NA4 compound solution an indica-
þ y2ꢂ=½ 1 þ
x2ꢂÞ ꢁ expðꢁ2 vxt0 2=½ 1 þ
x2
ꢂ
Dn, can be carried based on
ð8Þ
Fig. 13. Simulation results (from left to right columns) diffraction ring patterns in NA4 compound solution (1st), laser beam phase spatial distributions (2nd), 1 dimensional
intensity distributions of laser beam (x-3rd) and (y-4th) where the laser beam wave front is convergent (upper row) and divergent (lower row) at input power 59 mW.
10

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
Fig. 14. Simulation results of temporal development (from left to right columns) of the chosen diffraction ring pattern in NA4 compound solution (1st), spatial distributions of
the laser beam phase (2nd), 1 dimensional intensity distributions (x-rd) and (y-4th) at input power of 59 mW: (a) 100 msec (b) 200 msec (c) 300 msec (d) 400 msec (e) 500
msec (f) 600 msec (g) 700 msec (h) 800 msec (i) 1000 msec.
Nk
d
tion of a phase change in the laser beam of 2
rings a total phase change in the NA4 compound solution,
N radians can be written as [77]
p
radians. For total N
D
n ¼
ð13Þ
ð14Þ
Du, of
2p
k is the laser beam wavelength, and
D
u
¼ 2p
N
ð11Þ
D
n
n2 ¼
D
u
can be related to the sample thickness, d, the laser beam wave
I
vector, k ¼ 2
¼ kd
So that
p
=k, and n as follows:
D
2P
whereI is the laser beam intensity (¼
).
x2
p
D
u
D
n
ð12Þ
For number of rings N, 3, for NA4 compound solution,
d = 0.1 cm, beam spot size, , of 19.228 m, k = 473 nm, laser beam
x
l
11

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
Fig. 14 (continued)
intensity = 7408 W/cm2 so that
D
n is equal to 1.419 ꢄ 10ꢁ3 and n2
We obtained a straight line when conducting an OA Z-scan,
which indicates that the NA4 compound solution does not have a
nonlinear absorption coefficient. This is expected because the mea-
surements were made using a non-resonant wavelength, and at
this wavelength a reverse saturation absorption (RSA) or two-
photon absorption (TPA) must be obtained when using a pulsed
laser, and since a CW beam was used, neither RSA nor TPA can
be obtained.
Since the nonlinearity origin exhibited by the sample is thermal,
therefore the Cuppo et al., model [78] can be used, so that the non-
linear index of refraction, n2, can be determined based on the rela-
tion [79]
equals 1.915 ꢄ 10ꢁ7 cm2/W.
3.4. Z-scan
In the current study, both types of Z-scans measurements were
performed viz., the closed and open aperture Z-scans. Fig. 15 shows
the results of the CA Z-scan to the NA4 compound solution. From
the Fig. 15, we can conclude that the self-defocusing has occurred
to laser beam, which means that the NA4 compound solution has a
negative nonlinear index of refraction, because the curve shows a
peak followed by a valley. The nonlinearity shown by the NA4
compound solution is thermal due to the use of a CW laser beam,
and it results in the formation of a thermal divergence lens due to
the energy absorption from the laser beam by the NA4 compound
solution, which leads to its heating. This lens induces a phase shift
D
4
T
p
pꢁvk
Id
Tpꢁv is the difference between the peak and valley transmittances.
n2 ¼
ð15Þ
D
From Fig. 15 and using the value of Tpꢁv in Eq. (15) with the laser
beam intensity = 1721 W/cm2, we can determine the value of the
nonlinear index of refraction of NA4 compound solution and find
it is equal to 1.075 ꢄ 10ꢁ8 cm2/W.
in the laser beam; when the amount of shift is less than 2
p
radians,
self-defocusing set’s in, and when the phase shift is ꢅ 2
p radians a
diffraction ring patterns appears.
12

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
high nonlinear optical properties represented by the high nonlin-
ear refractive index, which encouraged us to study the properties
of the optical limiting of the NA4 compound solution since it pos-
sesses high nonlinear optical properties, therefore it is expected to
possess the properties of the optical limiting. Fig. 16a depicts the
properties of the optical limiting of the NA4 compound solution,
where the variation in output power is plotted as a function of
input power. As expected, the NA4 compound solution possessed
properties of the optical limiting. From Fig. 16a it is noticed that,
as the input power is low the output power changes linearly, while
at high input power the relation is nonlinear, as the increase of the
input power, the output power becomes constant.
After the NA4 compound solution has proved that it possesses
the properties of the optical limiting, this is not sufficient for the
NA4 compound solution to be used as an optical limiter. To deter-
mine the use of the NA4 compound solution as an optical limiter,
the limiting threshold, TH, must be obtained, which represents
the value of the input power for which transmittance through
the sample is reduced to halve. Plotting the transmittance as a
function of the input power is shown in Fig. 16b, from which we
find that the value of TH of NA4 compound solution is 12.4 mW.
Fig. 15. Experimental results of CA Z-scan measurement of the NA4 compound
solution.
3.6. Comparative study
When comparing the nonlinear index of refraction value of a
NA4 compound solution computed by the diffraction ring patterns
and Z-scan methods, we find that its value calculated by the former
method is greater than the latter one for the NA4 compound solu-
tion. The reason for this is that the refractive index depends on the
incident intensity, and the intensity used in the diffraction ring
patterns method is greater than the intensity used in the Z-scan
method. Therefore, the value of the nonlinear index of refraction
by the former method is greater than its value calculated by the
latter method.
Post comparing the nonlinear index of refraction value of the
NA4 compound solution computed by two methods, we will in this
paragraph compare the nonlinear index of refraction value of the
NA4 compound solution computed by Z-scan with its values of
other materials [80–83], and it is worth noting here that in these
studies [80–83], the Z-scan method and cw laser were used. From
comparison, we find that the value of the nonlinear index of refrac-
tion of the materials mentioned in these studies [80–83], are less
than that of the NA4 compound solution, which confirms that
the NA4 compound solution can be used in optical applications.
Now we will compare the threshold value of a NA4 compound
solution with its values for the materials mentioned in Refs. [84–
87] as these materials were known to have threshold values suit-
able for being candidates for use as optical limiters. It must be
pointed out again that a cw laser beam was used when studying
the properties of the optical limiting for the materials mentioned
in Refs. [84–87]. As a result of this comparison, we can conclude
that the value of the threshold limiting for the materials men-
tioned in Refs. [84–87] are greater than the value of the NA4 com-
pound solution, which indicates that the NA4 compound solution
is more efficient than those materials when it is used as an optical
limiter.
4. Conclusions
Fig. 16. (a) Experimental results of the optical limiting (b) variation of the
Azo compounds are of widespread interest and applications, so
the azo compound 4-((1,3-dioxo-1-phenylbutan-2-yl)diazenyl)ben
zenesulfonamide was prepared by the coupling reaction of dizo-
nium salt of sulfanilamide with benzoylacetone. The passage of
laser beam of low power continuous wave through the azo com-
pound have led to the generation of diffraction ring patterns. Based
normalized transmittance against input power of the NA4 compound solution.
3.5. Optical limiting
After studying the nonlinear optical properties of the NA4 com-
pound solution, it was found that the NA4 compound solution has
13

H.A. Sultan, Adil Muala Dhumad, Qusay M.A. Hassan et al.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 251 (2021) 119487
[22] Rita S. Elias, Qusay M.A. Hassan, H.A. Sultan, Ahmed S. Al-Asadi, Bahjat A.
Saeed, C.A. Emshary, Thermal nonlinearities for three curcuminoids measured
by diffraction ring patterns and Z-scan under visible CW laser illumination,
Opt. Las. Tech. 107 (2018) 131–141.
[23] H.A. Sultan, Qusay M.A. Hassan, H. Bakr, Ahmed S. Al-Asadi, D.H. Hashim, C.A.
Emshary, Thermal-induced nonlinearities in rose, linseed and chamomile oils
using CW visible laser beam, Can. J. Phys. 96 (2018) 157–164.
[24] Amjad F. Abdulkader, Qusay M. Ali Hassan, Ahmed S. Al-Asadi, H. Bakr, H.A.
Sultan, C.A. Emshary, Linear, nonlinear and optical limiting properties of
carbon black in epoxy resin, Optik 160 (2018) 100–108.
[25] Qusay M.A. Hassan, H.A. Sultan, Ahmed S. Al-Asad, Ayat Jawdat Kadhim, Nazar
A. Hussein, C.A. Emshary, Synthesis, characterization, and study of the
nonlinear optical properties of two new organic compounds, Synth. Met. 257
(2019), 116158 (14 pp).
[26] Faeza A. Almashal, Mohammed Q. Mohammed, M.A. Qusay, C.A. Hassan, H.A.
Sultan Emshary, Adil M. Dhumad, Spectroscopic and thermal nonlinearity
study of a Schiff base compound, Opt. Mat. 100 (2020), 109703 (12 pp).
[27] Qusay M.A. Hassan, H.A. Sultan, Ahmed S. Al-Asadi, H. Bakr, D.H. Hashim, C.A.
Emshary, Diffraction ring patterns and Z-scan measurements of nonlinear
refractive index of khoba vegetable oil, J. Bas. Res. Sci. 44 (2018) 47–63.
[28] Ayat J. Kadhum, Nazar A. Hussein, Qusay M.A. Hassan, H.A. Sultan, Ahmed S.
Al-Asadi, C.A. Emshary, Investigating the nonlinear behavior of cobalt (II)
phthalocyanine using visible CW laser beam, Optik 157 (2018) 540–550.
[29] Qusay M.A. Hassan, H.A. Sultan, H. Bakr, Isra M. Ali, R.M. Hassan, C.A. Emshary,
Estimating the nonlinear refractive index of 10W30 oil using visible low power
laser beam, Res. 10 (2018) 46–51.
[30] C.A. Emshary, H.A. Sultan, Qusay M.A. Hassan, H. Bakr, Nonlinearities of a
brake fluid using low visible laser beam, Int. J. Phys. Appl. Sci. 6 (2019) 42–53.
[31] Qusay M.A. Hassan, H. Bakr, H.A. Sultan, Raed M. Hassan, C.A. Emshary,
Evolution of far-filed diffraction patterns and nonlinear optical properties of
SAE 70 oil, Int. J. Appl. Nat. Sci. 6 (2017) 181–188.
[32] Qusay M.A. Hassan, H. Bakr, C.A. Emshary, H.A. Sultan, Studying the surface
morphology, optical and nonlinear optical properties of epoxy resin doped
nickel nitrate film, Optik 213 (2020), 164771 (9 pp).
[33] Ahmed Majeed Jassem, Qusay M.A. Hassan, C.A. Emshary, H.A. Sultan, Faeza
Abdulkareem Almashal, Wisam Abdulhassan Radhi, Synthesis and optical
nonlinear properties performance of azonaphthol dye, Phys. Scr. 96 (2021),
025503 (20 pp).
on ring patterns and the Z-scan techniques the nonlinear refractive
index of the prepared azo compound has been calculated. The use
of the Fresnel-Kirchhoff theory and Mat Lab numerical system,
have led to the simulation result that agree well with experimen-
tally observed ring patterns. Optical limiting threshold of 12.4 m of
the azo dye have been calculated at the 473 nm wavelength. The
aim of the current study is achieved by finding a new material that
could be a good candidate to be used as optical limiter for CW laser
beams in low power regime.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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