Chemical Physics Letters 648 (2016) 91–96

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Chemical Physics Letters

journal homepage: www.elsevier.com/locate/cplett

Second- and third-order nonlinear optical properties of unsubstituted

and mono-substituted chalcones
Luis M.G. Abegão a , Ruben D. Fonseca b , Francisco A. Santos a , Gabriela B. Souza c ,
André Luis B.S. Barreiros c , Marizeth L. Barreiros c , M.A.R.C. Alencar a , Cleber R. Mendonça b
, Daniel L. Silva d , Leonardo De Boni b , J.J. Rodrigues Jr. a,∗
a
Departamento de Física, Universidade Federal de Sergipe, 49100-000 São Cristovão, SE, Brazil
b
Instituto de Física de São Carlos, Universidade de São Paulo, CP 369, 13560-970 São Carlos, SP, Brazil
c
Departamento de Química, Universidade Federal de Sergipe, 49100-000 São Cristovão, SE, Brazil
d
Departamento de Ciências da Natureza, Matemática e Educação, Universidade Federal de São Carlos, Rod. Anhanguera – Km 174, 13600-970 Araras, SP,
Brazil

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

Article history: This work describes the second and third orders of nonlinear optics properties of unsubstituted chalcone
Received 19 November 2015 (C15 H12 O) and mono-substituted chalcone (C16 H14 O2 ) in solution, using hyper-Rayleigh scattering and Z-
In final form 2 February 2016 Scan techniques to determine the first molecular hyperpolarizability (ˇ) and the two-photon absorption
Available online 8 February 2016
(2PA) cross section respectively. ˇ Values of 25.4 × 10−30 esu and 31.6 × 10−30 esu, for unsubstituted and
mono-substituted chalcone, respectively, dissolved in methanol have been obtained. The highest values
of 2PA cross-sections obtained were 9 GM and 14 GM for unsubstituted and mono-substituted chalcone,
respectively. The experimental 2PA cross sections obtained for each chalcone are in good agreement with
theoretical results.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction chalcone-based [8], consequently, the latter became naturally more

The most recent developments in the field of nonlinear optics
(NLO) have driven second- and third-order nonlinear optical mate-
rials (NLOM) into practical applications and devices [1], such as
photodynamic therapy [2], optical-limiting [3], optical data storage
[4], 3D micro-fabrication [5] and two-photon excited fluorescence
microscopy [6]. In most of these applications, the exploited nonlin-
ear phenomena are related to the molecular structure of the organic
material, in particular to the presence of de-localized ␲-electrons
within the molecule’s chain, donor–acceptor intermolecular inter-
action, and the crystalline symmetry of natural or synthesized
organic crystals [7].
Among the multitude of the investigated NLOM, some organic
molecules (OM) have optical and electronic properties that can
be engineered with changes in their molecular structure, making
them extremely interesting and very attractive for NLO applications
[7]. Two examples of these OM are nitroaniline-based deriva-
tives and chalcone-based derivatives. The compounds made of
nitroaniline-based derivatives have inferior blue transparency than
∗ Corresponding author.
E-mail address: joatan@ufs.br (J.J. Rodrigues Jr.).
interesting for future optoelectronic devices [9].
Chalcones (1,3-diaryl-2-propen-1-ones) and substituted chal-
cones, also known as chalconoids [10], are open chain flavonoids
that are widely biosynthesized in plants [11], but it is possible
to synthesize them with a low-cost procedure in the laboratory
[12]. Chalcones have a large spectral application in biological chem-
istry activities [13,14] and, in the recent years, studies have shown
that chalcones derivatives are molecules with very interesting NLO
properties including high absorption extinction coefficients in the
ultraviolet (UV) region [15] and relevant second- and third-order
NLO responses [16–18].
Owing to the undesirable degradation or bleaching experienced
by most of OM when excited by high-energy optical beams, some
studies proposed the use of chalcones within a polymeric matrix
[19,20]. Using this strategy, it was possible to enhance the NLO
response of the polymer and avoid any damage to the employed
chalconoids.
In this work, first molecular hyperpolarizability and two-
photon absorption (2PA) from C15 H12 O unsubstituted chalcone
and C16 H14 O2 mono-substituted chalcone dissolved in methanol
were characterized using hyper-Rayleigh scattering (HRS) [21] and
Z-Scan techniques [22] respectively. To further understand the non-
linear optical properties of these molecules the sum-over state

http://dx.doi.org/10.1016/j.cplett.2016.02.009
0009-2614/© 2016 Elsevier B.V. All rights reserved.
92 L.M.G. Abegão et al. / Chemical Physics Letters 648 (2016) 91–96
Figure 1. The molecular structure of trans-chalcone.
(SOS) method and quantum-chemical calculations carried out at
the density functional theory (DFT) level of theory were employed.
2. Experimental
The studied samples are shown in Figure 1 and were denomi-
nated henceforth in this letter as C-1 (C15 H12 O) and C-2 (C16 H14 O2 ),
C-1 is the unsubstituted chalcone and C-2 the mono-substituted
chalcone. The chalcones were synthesized by Claisen–Schmidt con-
densation using the following method: a solution of 2.2 g NaOH
was prepared and dissolved in 32 ml water/ethanol (2:1), then
added 5.2 g of acetophenone and 4.6 g of the corresponding alde-
hyde, which was kept stirring for 5 min in an ice bath. The reaction
mixture was removed from the bath and held stirring at room tem-
perature for 3 h. Thus, the mixture was cooled in the freezer for
12 h and then filtered in vacuum. The aldehydes used were ben-
zaldehyde for C-1 and anisaldehyde for C-2.
The obtained product was purified by column chromatogra-
phy using silica gel 60 eluting with hexane and ethyl acetate and
characterized by nuclear magnetic resonance (Varian INOVA 500)
with the following parameters: 1 H, 13 C and DEPT 90◦ and 135◦ . All
chemicals reagents were analytical grade and used without further
purification. The spectra revealed by nuclear magnetic resonance at
500 MHz for 1 H and 125 MHz for 13 C, in CDCl3 , with tetramethyl-
silane as internal reference.
Figure 2. HRS illustration scheme to measure the 1st hyperpolarizability.
Figure 3. Z-Scan illustration scheme to measure the 2PA.
All photophysical experiments were performed in a fused quartz
cuvettes with 1 mm long optical path, except HRS technique, which
used a 10 mm. The linear absorption spectra were obtained by a
UV–VIS spectrophotometer system (Shimadzu, Model UV-1800).
HRS technique was carried out in a very similar way as the one
presented by Clays and Persoons [23], but with variations intro-
duced by Franzen et al. [24]. The experimental setup is depicted in
Figure 2. Briefly, a Q-switched, mode-locked Nd:YAG laser, which
delivered pulse trains of 100 ps modulated by approximately 300 ns
Q-switched envelope at 1064 nm, was employed as the excitation
source. After collimation (L1 and L2), the laser beam is focused
into the sample by L3 . The SHG signal was collected by lens L4 and
focused onto the window of a photomultiplier tube (PMT) by lens
L5 . In order to improve the signal-to-noise ratio, a spherical mir-
ror (M) collects the signal scattered in the opposite direction of the
PMT. The high-pass (HPF) and the 532 nm narrow-band (BPF) filters
were used in order to eliminate visible light emitted by the laser
flash lamp and to avoid the incidence of the excitation light onto the
PMT respectively. It must be emphasized that the response time of
the employed PMT was fast enough in order to separate signals from
distinct pulses. Computer software controls the acquisition system,
which marks each peak position in the pulse train and measures the
HRS signal generated by each individual pulse.
First order molecular hyperpolarizability values were obtained
using the following equation:
 n 

I2ω = G Ni ˇi2 2
Iω (1)
i=1
in which I2ω is the intensity of the HRS radiation with an wave-
length corresponding at 532 nm, G is a constant determined by the
scattering geometry, local field factors at ω and 2ω, as well other
optical and instrument quantities, N is the concentration of the
used samples and ˇ is the first molecular hyperpolarizability. Using
 L.M.G. Abegão et al. / Chemical Physics Letters 648 (2016) 91–96
Figure 4. The symbols represent the Z-Scan experimental signatures for four dis-
tinct excitation wavelength. Solid lines are the fittings obtained with Eq. (2).
nitroanliline (PNA) dissolved in methanol as a reference sample
[23], the values of the investigated chalcones were determined.
Two-photon absorption spectra were obtained using Z-Scan
technique with the open-aperture configuration [25] (see Figure 3).
An optical parametric oscillator (OPO) (Quantronix, model TOPAS),
pumped by single pulses of 150 fs from a 1 kHz MXR-CLARK laser
was employed as a tunable light source. The optical beam was
tuned from 480 up to 790 nm and presents a Gaussian profile due
to the spatial filter used before the Z-Scan setup [26]. The beam
was focused by a convergent lens of 15 cm focal length. The sample
was placed on a motorized translation stage, and its position varied
along the beam path. The transmitted light intensity was mea-
sured at different sample positions, passing through the lens focal
plane.
Some Z-Scan signatures (symbols) are depicted in Figure 4 for
C-2 in four different wavelengths. The solid lines are the fittings of
the normalized transmittance T(z) obtained by Eq. (2):
 +∞
1 2
T (z) = √ ln[1 + q0 (z, 0)e−t ]dt (2)
q0 (z, 0) −∞
−1
in which q0 (z, 0) = ˛2PA I0 L(1 + z 2 /z02 ) , I0 is the intensity of the
pulse, L is the optical path, z0 is the Rayleigh length, and z is the
sample position.
The 2PA absorption cross-sections values,
expressed in Göppert–Mayer [27] (GM) units
(1 GM = 10−50 cm4 s molecule−1 photon−1 ), were evaluated using
 2PA = (h/N)˛2PA , in which, h is the excitation energy, and N is
the concentration.
3. Theoretical section
Assuming the two-photon resonant condition, ωgf = 2ω, and that
the normalized line-shape of the excited states is represented by
the Lorentzian function, the 2PA cross-section ( gf ) of the degen-
erate process is written as [28,29]:
163 ˛a50 (ω)2
gf (ω) = ıgf  (3)
c (f /2)
in which ˛ is the fine structure constant, c is the speed of light,
a0 is the Bohr’s radium, ω is the photon energy, and ıgf  is the
two-photon transition probability for the transition from the
ground (g) state to a final (f) excited state.  f is the damping
93
constant describing the full width at half-maximum of
the final state line width. In Eq. (3), one has to use
a0 = 5.291772108 × 10−9 cm, c = 2.99792458 × 1010 cm/s and
the values of ω,  f and ıgf  in atomic units.
The degenerate two-photon transition probability in an
isotropic medium using a linearly polarized laser beam is given
by [30,31]:
1  gf gf ∗ gf gf ∗
ıgf = 2S˛˛ (Sˇˇ ) + 4S˛ˇ (S˛ˇ ) (4)
30
˛,ˇ
in which the subscripts ˛ and ˇ represent the Cartesian coordinates
gf
and S˛ˇ is the two-photon matrix element, which for a single beam
2PA experiment is defined as [31,32]:
 
gf 1  g|ê · 
ˆ ˛ |kk|ê · 
ˆ ˇ |f  g|ê · 
ˆ ˇ |kk|ê · 
ˆ ˛ |f 
S˛ˇ = + (5)
2 ωgk − ω ωgk − ω
k
In the HRS experiment, the 90◦ angle geometry is used. Assum-
ing such geometry and adopting the laboratory coordinate system
of reference (X, Y, Z) and the molecular coordinate system of refer-
ence (x, y, z), if the fundamental light beam is propagating in the
X-direction and vertically polarized in the Z-direction, then ˇHRS 
can be written as [32,33]:

ˇHRS  = 2  + ˇ2 
ˇZZZ (6)
XZZ
in which ˇZZZ 2  and ˇ2  are macroscopic averages in which the
XZZ
first subscript (X or Z) refers to the polarization state of the fre-
quency doubled light (laboratory system of reference) and it was
assumed that both polarization states are detected with equal
sensitivity. In Eq. (6), the macroscopic averages can be written
as a function of the molecular first-order hyperpolarizability ten-
sor components (molecular system of reference), as can be found
somewhere else [34]. In this work, we focused on the electronic
contribution to the first hyperpolarizability and neglect the pure
vibrational and zero-point vibrational average contributions.
All quantum-chemical calculations were carried out at the den-
sity functional theory (DFT) level [35,36]. The gaussian 09 package
was used to determine the equilibrium geometry of the molecules
with the aid of the hybrid B3LYP functional [37,38] and the 6-
311G(d,p) basis set. To determine the effect of the methanol solvent
on the equilibrium molecular geometry of the molecules, geom-
etry optimization calculations were performed in gas-phase and
also employing a polarizable continuum model (PCM) to take into
account the solvent environment. The PCM using the integral equa-
tion formalism variant (IEF-PCM) [39], as implemented in gaussian
09 package, was employed for this purpose. For the molecules
investigated, it was not observed any important change between
the molecular equilibrium geometries as determined by the gas-
phase and IEF-PCM calculations.
To determine and characterize the linear and nonlinear optical
properties of the molecules investigated, the response function for-
malism [40], within the DFT framework, was used as implemented
in the dalton program. In this approach, the oscillator strengths
and two-photon transition probabilities are calculated analytically
as single residues of the linear and quadratic response functions
of the molecular electronic density, respectively. The quadratic
response function connected with the second-harmonic generation
(ˇ(− 2ω ; ω, ω)) is used to compute the components of the static
(ω = 0 a . u .) and dynamic (ω = 0.04282 a . u .) first-order hyperpo-
larizability tensor (ˇijk ). The response function calculations were
performed in gas-phase and in solvent environment, by employing
the PCM solvation method as implemented in the dalton program,
[41] and using the CAM-B3LYP/6-311++G(d,p) approach [42]. For
consistency reason, the van der Waals surface used in the response
94 L.M.G. Abegão et al. / Chemical Physics Letters 648 (2016) 91–96
Figure 5. HRS as a function of the fundamental beam irradiance. The inset shows the
HRS normalized to the square of the fundamental beam as a function of the samples
concentration. The PNA was used as the reference sample (squares) to compare
the values of the chalcones samples (C-1: circles and C-2: triangles). The solid lines
represent the linear and parabolic fittings.
function calculations was defined by adopting the set of van der
Waals radius and atomic centers determined at the geometry opti-
mization stage using the gaussian 09 package.
4. Results and discussion
Previous studies [43–45] showed that organic molecules that
possesses strong electron donors substituents and any acceptor
group at either ends of a long ␲-conjugation have a recognized large
ˇ, and the cause for this NLO effect is the charge distribution asym-
metry that is also associated to the excited charge-transfer state,
promoting an increase of the electron delocalization in the molec-
ular structure [46]. The samples studied here do not present a long
␲-conjugation, thus one should not expect large values of ˇ. It was
confirmed by our HRS experiment, in which ˇ for C-1 was evalu-
ated to be 25.4 × 10−30 esu while for C-2 it was 31.6 × 10−30 esu.
The same order of magnitude of PNA/Methanol, 24.3 × 10−30 esu
[24]. Figure 5 shows that chalcone C-2 reveals an higher response
of the HRS radiation than chalcone C-1, which occurs due to the
stronger electron donation of the methoxy substituent. The inset
of Figure 5 shows a higher angular coefficient for C-2 to the HRS
normalized to the square of the fundamental beam as a function of
the concentration.
Linear absorption (1PA) revealed that chalcone C-1 has two
energy bands with its maximum absorption corresponding to the
excitation wavelength of 226 and 308 nm, while chalcone C-2
presents a bathochromic shift for both bands, changing the absorp-
tion peaks for 243 and 343 nm respectively, as can be seeing in
Figure 6 (dashed dotted lines). The bathochromic shift is occasioned
by the methoxyl (OCH3 ) in the aromatic ring B, that reduces the
energy difference from the chromophores in the highest occupied
molecular orbital to the lowest unoccupied molecular orbital.
In Figure 6, the symbols represent the degenerate 2PA spectra
measured using the Z-scan technique from 480 nm to 790 nm. A 2PA
band is observed around 610 and 670 nm for C-1 and C-2 respec-
tively, in which is approximate the twice the peak wavelength of
1PA. This is possible due to the relaxation of selection rules for
asymmetrical molecules, in which states allowed by 1PA are also
0.5
allowed by 2PA for noncentrosymmetric molecules [47]. The 2PA
spectra show, for wavelength shorter than 560 nm, a monotonic
increase of the 2PA cross-sections for both molecules, probably
Figure 6. Absorbance (dashed dotted lines) and 2PA experimental (symbols) spectra
of chalcones. The solid lines represent the theoretical fitting obtained with SOS.
related to the resonance enhancement of the 2PA as the one-photon
transition is approached. The results presented in Figure 6, shown
that a slight molecular modification from the original chalcone
structure C-1 to C-2, exhibit an increase of the 2PA cross-section
value by 50%.
As can be seen in Figure 6, sample C-2 is the molecule with higher
2PA cross-sections values around 490 and 800 nm if compared with
C-1. ChalconeC-2 has a radical methoxyl attached to the aromatic
ring B, that donates a pair of free electrons by resonance to the
system, and those free electrons can move from the B aromatic
ring up to the carbonyl that is connected to the aromatic ring A [48].
This electron movement increases the natural delocalization of the
aromatic rings, promoting an enhancement of 2PA cross section
relatively to C-1.
To analysis the 2PA spectra of both chalcones, we used the sum-
over-states (SOS) equation, given by [49]:

4 (2)4 2 |01 |2 201 01
2PA () =
5 (ch)2 (01 − )2 +  2 (01 − 2)2 + 01
2
01

|12 |2 |01 |2 02
+ (7)
(02 − 2)2 + 02
2
in which  is the frequency of the laser, c is the speed of light
and h is the Planck constant. In this expression, 0n ,  0n and 0n
corresponds to the frequency transition, damping constant and
transition dipole moments, respectively, of the 0 → n transition
(n = 1, 2). The factor 01 represents the difference between per-
manent dipole moments of the molecule at excited and ground
states. In Eq. (7), the terms inside brackets represent the 2PA
line-shapes, in which both molecules corresponds the two-photon
transition from ground to excited states ( → *).
In Figure 6, the solid lines represent the theoretical fittings
obtained using Eq. (7). Most of the spectroscopy parameters,
in Eq. (7), were obtained from the linear absorption spec-
tra. For C-1, the frequency values were v01 = 9.69 × 1014 Hz
and 02 = 1.31 × 1015 Hz and the coefficient damping were
 01 = 8.10 × 1013 Hz and  02 = 1.05 × 1014 Hz respectively. For
C-2, the values were v01 = 8.73 × 1014 Hz, 02 = 1.24 × 1015 Hz,
 01 = 6.41 × 1013 Hz and  02 = 1.61 × 1014 Hz. The transition dipole
moment (01 ) between the ground and the first excited state can
be determined by:
3 ch 1
(8)01 = ˛()d in which N is the number of
83 N 01
molecules is the absorption coefficient in cm−1 . The
per cm3 , ˛
only adjustable parameters in the SOS fitting were 12 and 01 .
 L.M.G. Abegão et al. / Chemical Physics Letters 648 (2016) 91–96 95

Table 1
Theoretical results for the 1PA and 2PA transitions of the investigated molecules. f is the oscillator strength of the 1PA transition to the nth excited state, ı is the two-photon
transition probability to the nth excited state and  2PA is the related 2PA cross-section.

Molecule n In vacuum In methanol

E f ı  2PA E f ı  2PA
(nm) (a.u) (GM) (nm) (a.u) (GM)

1 346 0.000 0.895E+01 0 329 0.003 0.781E+02 0

2 292 0.736 0.204E+04 6 312 0.846 0.442E+04 12
C-1 3 256 0.006 0.105E+03 0 262 0.036 0.777E+02 0
4 255 0.032 0.613E+02 0 262 0.018 0.222E+03 1
5 246 0.117 0.321E+04 18 254 0.162 0.785E+04 42
1 343 0.001 0.337E+02 0 337 0.958 0.135E+05 20
2 312 0.845 0.621E+04 11 326 0.019 0.100E+03 0
C-2 3 258 0.010 0.370E+03 2 261 0.003 0.395E+03 1
4 253 0.027 0.467E+02 0 260 0.032 0.671E+02 0
5 244 0.128 0.389E+04 28 252 0.186 0.109E+05 72

Table 2
Theoretical results for the static and dynamic first-order hyperpolarizabilities of the investigated molecules. ˇ in 10−30 esu and
␻ = 1064 nm.

Molecule In vacuum In methanol Experimental

ˇ(0 ; 0, 0) ˇ(− 2ω ; ω, ω) ˇ(0 ; 0, 0) ˇ(− 2ω ; ω, ω) ˇ(− 2ω ; ω, ω)

C-1 5.3 9.1 17.2 18.5 25.4

C-2 13.6 24.4 42.4 50.1 31.6

The experimental and theoretical values, expressed in Debyes (D),
relative to the transitions dipole moments for the chalcone C-
exp exp exp
1 are: ␮01 = 6.24; ␮12 = 5.69; ␮01 = 3.93; ␮th 01
= 2.54,
exp exp exp
and for the chalcone C-2 are: ␮01 = 3.38; ␮12 = 7.62; ␮01 =
8.80; ␮th = 7.87.
01
The quantum-chemical calculations for the 1PA and 2PA tran-
sitions of the investigated molecules are shown in Table 1. The
2PA cross-section of the two 2PA allowed excited-states of C-1 and
C-2 identified in the UV–vis region were computed using damp-
ing constants ( f ) as estimated through the SOS fitting. The 2PA
cross-section of the remaining lowest-energy excited-states was
computed adopting a reasonable value (0.4 eV) for the damping
constants.
The quantum-chemical calculations confirmed the existence of
two strongly (f > 0.1) allowed 1PA transitions along the UV–vis
region of the linear absorption spectrum of both investigated
molecules. The transition wavelengths (transition energy) deter-
mined by the calculations for such transitions (254 nm and 312 nm)
of C-1 are in good agreement with the spectral position of the two
bands observed in the linear spectrum (226 and 308 nm). Simi-
larly, for C-2 (252 nm and 337 nm) are also in good agreement
with the experimental linear spectrum (243 and 343 nm). Compar-
ing the theoretical results in gas-phase and solvent environment,
one can observe that for both C-1 and C-2 such transitions suffer a
bathochromic shift in methanol.
Concerning the 2PA, the results of the quantum-chemical cal-
culations showed the existence of two strongly allowed 2PA
transitions along the UV–vis region for both molecules. Such tran-
sition involves the same excited states allowed via 1PA. Therefore,
these results confirm the relaxation of selection rules for the elec-
tronic transitions in both molecules.
A good agreement between theoretical results and experimen-
tal values, taken into account the experimental error, for the 2PA
cross-section of the excited state associated with the lowest energy
absorption band of both C-1 and C-2 is observed. From a compar-
ison of the theoretical results obtained in gas-phase and solvent
environment, one can conclude that the solvent effects significantly
affect he 2PA cross-section of both molecules. The 2PA cross-section
of the excited state associated with the lowest energy absorption
band is doubled due to solvent effects.
Table 2 summarizes the results of the quantum-chemical cal-
culations for the static (ˇ(0 ; 0, 0)) and dynamic (ˇ(− 2ω ; ω, ω))
first-hyperpolarizability of the molecules. From a comparison of the
theoretical results obtained in gas-phase and solvent environment,
it is verified that the solvent effects also significantly affect this non-
linear property. For both C-1 and C-2 the solvent effects basically
doubled the dynamic first-order hyperpolarizability. Comparing
the static and dynamic hyperpolarizabilities, it is possible to con-
clude that the dispersion effects play a minor role on the dynamic
first-order hyperpolarizability of the molecules investigated.
Taken into account the experimental error of the HRS tech-
nique, about 30%, one can conclude that a good agreement between
the theoretical result and experimental value for the dynamic
first-order hyperpolarizability of C-1 molecule. However, it seems
that the quantum-chemical calculation overestimated the dynamic
first-order hyperpolarizability of C-2 molecule.
Comparing C-1 and C-2 with commercial molecules Dibenzoyl-
methane (DBM) and 2,5-diphenyloxazole (PPO), one can have an
idea about the order of magnitude expected for small ␲-conjugated
chain length. DBM molecular structure is similar to the chalcones
synthesized in this work, but it presents one more carbonyl group
between the two aromatic rings than C-1 and C-2. DBM maximum
value for the 2PA cross section is 37 GM, that is higher but in the
same order of magnitude of C-2, while the value of the first hyper-
polarizability (8.8 × 10−30 esu) [45] is lower than C-1 and C-2. PPO
molecular structure presents also two aromatic rings in the edges,
but its core is an oxazole. PPO presented a maximum value for the
2PA cross section of 27 GM [50], which is in between the maximum
value of DBM and C-2.
Therefore, although the investigated chalcones do not exhibit
a very large 2PA cross section and first hyperpolarizability, the
measured values are of the same order of other compounds
with different molecular structures but with approximately the
same ␲-conjugated chain length. Moreover, in the present work,
these quantities were measured with the molecules in solution
and no degradation was detected within the employed experi-
mental conditions. Hence, our results indicate that these simple
chalcones molecules can be employed as a start point for the engi-
neering of organic compounds with improved nonlinear optical
properties.
96 L.M.G. Abegão et al. / Chemical Physics Letters 648 (2016) 91–96

5. Conclusions [12] B.K. Sarojini, et al., J. Cryst. Growth 295 (1) (2006) 54.
[13] N.J. Lawrence, A.T. Mcgown, Curr. Pharm. Des. 11 (13) (2005) 1679.
[14] Z. Nowakowska, Eur. J. Med. Chem. 42 (2) (2007) 125.
We determined the 2PA cross-section spectra, from 480 to [15] Dong Hoon Choi, et al., Thin Solid Films 360 (1) (2000) 213.
790 nm, and the first hyperpolarizability of two chalcones C-1 and [16] M.S. Kiran, et al., J. Photochem. Photobiol. A: Chem. 290 (2014) 38.
C-2 in methanol solution. The value of maximum 2PA cross-section [17] V. Ramkumar, et al., CrystEngComm 15 (13) (2013) 2438.
[18] A. Jayarama, et al., J. Mol. Struct. 1051 (2013) 285.
was estimated to be 9 and 14 GM, while the first hyperpolarizabil- [19] S. Shettigar, et al., Opt. Mater. 30 (8) (2008) 1297.
ity were 25 × 10−30 and 32 × 10−30 esu for C-1 and C-2 respectively. [20] P. Poornesh, et al., Opt. Mater. 31 (6) (2009) 854.
Theoretical calculations, within the Density Functional Theory [21] K. Clays, A. Persoons, Phys. Rev. Lett. 66 (23) (1991) 2980.
[22] E.W. Van stryland, M. Sheik-bahae, Characterization Techniques and Tabula-
model, yielded one- and two-photon transition properties in accor-
tions for Organic Nonlinear Materials, 1998, pp. 655.
dance with the experimental results and identified the set of active [23] F.L. Huyskens, P.L. Huyskens, A.P. Persoons, J. Chem. Phys. 108 (19) (1998) 8161.
electronic states along the spectral region investigated. It is impor- [24] P.L. Franzen, L. Misoguti, S.C. Zilio, Appl. Opt. 47 (10) (2008) 1443.
[25] M. Sheik-Bahae, et al., Quantum Electron. IEEE J. 26 (4) (1990) 760.
tant to mention here that for the same conjugation length, the
[26] L. De Boni, et al., Chem. Phys. Lett. 361 (3) (2002) 209.
radical methoxyl attached to the aromatic ring B was responsible [27] M. Göppert-Mayer, Ann. Phys. 18 (7–8) (2009) 466.
for the increase in the 2PA and HRS of the C-2 molecule. To the best [28] K. Ohta, K. Kamada, J. Chem. Phys. 124 (12) (2006) 124303.
of our knowledge, no work of the nonlinear optics characterizations [29] D.L. Silva, et al., J. Chem. Phys. 131 (24) (2009) 244516.
[30] P.R. Monson, W.M. Mcclain, J. Chem. Phys. 53 (1) (1970) 29.
of chalcones molecules in solution has been done. [31] W.M. Mcclain, J. Chem. Phys. 55 (6) (1971) 2789.
[32] R. Bersohn, Yoh-Han Pao, H.L. Frisch, J. Chem. Phys. 45 (9) (1966) 3184.
Acknowledgments [33] F. Castet, et al., J. Chem. Phys. 136 (2) (2012) 024506.
[34] D.L. Silva, et al., J. Chem. Phys. 142 (6) (2015) 064312.
[35] P. Hohenberg, W. Kohn, Phys. Rev. 136 (1964) B864.
The authors acknowledge the financial support from CAPES, [36] W. Kohn, L.J. Sham, Phys. Rev. 140 (1965) A1133.
CNPq/MCT, FAPITEC, Nanofoton Network and INCT-FOTÔNICA. [37] A.D. Becke, J. Chem. Phys. 98 (7) (1993) 5648.
[38] Chengteh Lee, Weitao Yang, R.G. Parr, Phys. Rev. B 37 (2) (1988) 785.
[39] J. Tomasi, B. Mennucci, E. Cances, J. Mol. Struct.: Theochem. 464 (1) (1999)
References 211.
[40] P. Sałek, et al., Chem. Phys. Lett. 374 (5) (2003) 446.
[1] S. Suresh, D. Arivuoli, Rev. Adv. Mater. Sci. 30 (2012) 243. [41] L. Frediani, Z. Rinkevicius, H. Ågren, J. Chem. Phys. 122 (24) (2005) 244104.
[2] F.Z. Henari, et al., Chem. Phys. Lett. 552 (2012) 126. [42] Takeshi Yanai, D.P. Tew, N.C. Handy, Chem. Phys. Lett. 393 (1) (2004) 51.
[3] C.P. Singh, et al., Chem. Phys. Lett. 616 (2014) 189. [43] M.C. Flipse, et al., Chem. Phys. Lett. 245 (2) (1995) 297.
[4] P.-O. Åstrand, et al., Chem. Phys. Lett. 325 (1) (2000) 115. [44] P.J.A. Kenis, et al., Eur. J. Org. Chem. 1998 (6) (1998) 1089.
[5] K.D. Belfield, et al., J. Phys. Org. Chem. 13 (12) (2000) 837. [45] Y. Dwivedi, et al., Opt. Commun. 293 (2013) 119.
[6] H. Ftouni, F. Bolze, J.-F. Nicoud, Dyes Pigment. 97 (1) (2013) 77. [46] D.S. Chemla (Ed.), Nonlinear Optical Properties of Organic Molecules and Crys-
[7] Ch. Bosshard, et al., Organic Nonlinear Optical Materials, CRC Press, 2001. tals, Elsevier, 2012.
[8] M.C. Gupta, J. Ballato (Eds.), The Handbook of Photonics, CRC Press, 2006. [47] K. Kamada, et al., Chem. Phys. Lett. 372 (3) (2003) 386.
[9] N.S.K. Reddy, et al., Chem. Phys. Lett. 616 (2014) 142. [48] P.Y. Bruice, Org. Chem., 2006, pp. 2006.
[10] G. Nelson, et al., Med. Chem. Res. 22 (10) (2013) 4610. [49] U.M. Neves, et al., Chem. Phys. Lett. 441 (4) (2007) 221.
[11] D.I. Batovska, I.T. Todorova, Curr. Clin. Pharmacol. 5 (1) (2010) 1. [50] D.L. Silva, et al., Opt. Mater. 34 (7) (2012) 1013.