An analysis of structural and spectroscopic signatures, the reactivity study of synthetized 4,6-dichloro-2-(methylsulfonyl)pyrimidine: A potential third-order nonlinear optical material

Article abstract of DOI:10.1016/j.molstruc.2019.03.021

In this work the 4,6-dichloro-2-(methylsulfonyl)pyrimidine (DCMSP) has been synthesized from 4,6-dichloro-2-(methylthio)pyrimidine, its molecular and electronic structure was authenticated by detailed spectroscopic signature studies (via SCXRD, FT-Raman, FT-IR and (¹H & ¹³C) NMR), Hirshfeld surface analysis and DFT calculations. The solid-state crystal structure of DCMSP corroborated by the single crystal X-ray diffraction studies, features C[sbnd]H?O and π···π interactions. Quantum chemical calculations of DCMSP have been performed at DFT/B3LYP/6-311++G (d,p) level of theory. The detailed assignment of each the vibrational mode was done on the basis of potential energy distribution (PED) by using the VEDA4 program and these results have been correlated with the experimental data. We calculated the linear and nonlinear optical properties of the title compound to understand the linear and nonlinear optical behavior in both static and dynamic fields using an iterative electrostatic embedding scheme and density functional theory (DFT) methods with standard and long-range corrected functionals. We also performed a study of the linear refractive index and nonlinear optical susceptibility χ⁽³⁾ of the crystal as a function of frequency. An estimate of linear and nonlinear macroscopic quantities confirms their suitability for nonlinear optical devices such as optical limiting and optical switching. Investigation of local and global reactivity parameters of DCMSP was carried out by the calculation of molecular electrostatic potential (MEP), average local ionization energies (ALIE) surfaces and atomic Fukui indices in the gas phase. Stability in water and sensitivity towards autoxidation process has been investigated by radial distribution function (RDF) and bond dissociation energies (BDE) calculation after molecular dynamic simulations.

Full text of DOI:10.1016/j.molstruc.2019.03.021

Accepted Manuscript
An analysis of structural and spectroscopic signatures, the reactivity study of
synthetized 4,6-dichloro-2-(methylsulfonyl)pyrimidine: A potential third-order nonlinear
optical material
P. Krishna Murthy, Clodoaldo Valverde, V. Suneetha, Stevan Armaković, Sanja J.
Armaković, N. Usha Rani, N. Venkatasubba Naidu
PII:
S0022-2860(19)30282-0
DOI:
https://doi.org/10.1016/j.molstruc.2019.03.021
MOLSTR 26290
Reference:
To appear in: Journal of Molecular Structure
Received Date: 1 September 2018
Revised Date: 19 February 2019
Accepted Date: 6 March 2019
Please cite this article as: P.K. Murthy, C. Valverde, V. Suneetha, S. Armaković, S.J. Armaković,
N.U. Rani, N.V. Naidu, An analysis of structural and spectroscopic signatures, the reactivity study of
synthetized 4,6-dichloro-2-(methylsulfonyl)pyrimidine: A potential third-order nonlinear optical material,
Journal of Molecular Structure (2019), doi: https://doi.org/10.1016/j.molstruc.2019.03.021.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
An analysis of structural and spectroscopic signatures, the reactivity study of synthetized 4,6-
dichloro-2-(methylsulfonyl)pyrimidine: A potential third-order nonlinear optical material
a*
b,c
a,d
e
P. Krishna Murthy , Clodoaldo Valverde , V. Suneetha , Stevan Armaković , Sanja J.
f
g
h
Armaković , N. Usha Rani , N. Venkatasubba Naidu
a
Department of Chemistry, Bapatla Engineering College (Autonomous), Acharya Nagarjuna
University Post Graduate Research Centre, Bapatla-522 102, A.P., India.
b
Laboratório de Modelagem Molecular Aplicada e Simulação (LaMMAS), Campus de
Ciências Exatas e Tecnológicas, Universidade Estadual de Goiás, 75001-970, Anápolis, GO,
Brazil.
c
Universidade Paulista, 74845-090, Goiânia, GO, Brazil; Centro Universitário de Anápolis,
7
5083-515, Anápolis, GO, Brazil.
d
Department of Chemistry, Bapatla College of Arts and Sciences, Baptla-522 101, A.P.,
India.
e
University of Novi Sad, Faculty of Sciences, Department of Physics, Trg D. Obradovića 4,
2
1000 Novi Sad, Serbia.
f
University of Novi Sad, Faculty of Sciences, Department of Chemistry, Biochemistry and
Environmental Protection, Trg D. Obradovića 3, 21000 Novi Sad, Serbia.
g
Department of Freshman Engineering, P.V.P. Siddhartha Institute of Technology,
Vijayawada-520 007.
h
Department of Chemistry, Sri Venkateswara University, Tirupati -517 512, A.P., India.
*
Corresponding author: krishnamurthypotla@gmail.com
Abstract
In this work the 4,6-dichloro-2-(methylsulfonyl)pyrimidine (DCMSP) has been synthesized
from 4,6-dichloro-2-(methylthio)pyrimidine, its molecular and electronic structure was
authenticated by detailed spectroscopic signature studies (via SCXRD, FT-Raman, FT-IR and
1
13
(
H & C) NMR), Hirshfeld surface analysis and DFT calculations. The solid-state crystal
structure of DCMSP corroborated by the single crystal X-ray diffraction studies, features C-
H···O and π···π interactions. Quantum chemical calculations of DCMSP have been
performed at DFT/B3LYP/6-311++G(d,p) level of theory. The detailed assignment of each
the vibrational mode was done on the basis of potential energy distribution (PED) by using
the VEDA4 program and these results have been correlated with the experimental data. We
calculated the linear and nonlinear optical properties of the title compound to understand the
1

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linear and nonlinear optical behavior in both static and dynamic fields using an iterative
electrostatic embedding scheme and density functional theory (DFT) methods with standard
and long-range corrected functionals. We also performed a study of the linear refractive index
(3)
and nonlinear optical susceptibility χ of the crystal as a function of frequency. An estimate
of linear and nonlinear macroscopic quantities confirms their suitability for nonlinear optical
devices such as optical limiting and optical switching. Investigation of local and global
reactivity parameters of DCMSP was carried out by the calculation of molecular electrostatic
potential (MEP), average local ionization energies (ALIE) surfaces and atomic Fukui indices
in the gas phase. Stability in water and sensitivity towards autoxidation process has been
investigated by radial distribution function (RDF) and bond dissociation energies (BDE)
calculation after molecular dynamic simulations.
Keywords: Pyrimidine; NLO properties; ALIE; BDE; RDF; Fukui functions.
1
. Introduction
Historically, inorganic crystals are main materials applied for nonlinear optical field with
current applications [1-3], but the last few years, the use of organic crystals as non-linear
optical (NLO) materials has been growing motivated by to the easy manipulation of these
crystals, which allow control the material NLO properties [4]. Studies of non-linear optical
processes contribute significantly to the development of photonics [5, 6], spectroscopy [7, 8],
fiber optic lines [7], optical switches [9], frequency converters [1], electro-optic modulators
[
10], and still with thermal application [11]. Third-order nonlinear materials with inefficient
nonlinear absorption and strong nonlinear refraction have received considerable attention
from researchers because of their potential uses in optical signal processing devices [12,13].
Organic crystals with good third-order nonlinear optical properties have attracted attention
because such compounds were possessing good trade-off between optical transparency and
optical power limiting performance [12–17].
Computational molecular modeling techniques have become indispensable tools for studying
fundamental reactive properties of various molecular structures [18-23]. The ab-initio
calculations have proven to be especially useful for the understanding of the local reactivity
of molecules. In this work, we endeavor synthesis, spectroscopic investigations (via SCXRD,
1
13
FT-Raman, FT-IR and ( H & C) NMR), and Hirshfeld surface analysis of 4,6-dichloro-2-
methylsulfonyl)pyrimidine (DCMSP). We apply ab-initio methods in conjunction with a
(
supermolecule approach which includes the Møller-Plesset Perturbation Theory (MP2) and
the Density Functional Theory (DFT) at the CAM-B3LYP level to determine the linear
2

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refractive index and the third-order nonlinear susceptibility of the crystal (DCMSP). The
local reactivity properties of DCMSP molecule have been investigated by calculating the
molecular electrostatic potential (MEP), average local ionization energy (ALIE), atomic
Fukui indices, bond dissociation energies (BDE) and bond dissociation energies for hydrogen
abstraction (H-BDE). The influence of water and identification of DCMSP’s atoms with
pronounced interactions with water molecules have been assessed by molecular dynamics
(MD) simulations and radial distribution functions (RDF).
2
2
. Methodology
.1. General remarks
All chemicals and reagents were purchased from a commercial source and used as such
without further purification. The synthesis was performed under anaerobic conditions. The
Fourier transform infra spectrum was recorded using the KBr disc on ATR module ALPHA-
-1
-1
T Bruker FT-IR spectrometer in the range 4000-400 cm with resolution ±2cm (Figure 1).
The Fourier transform Raman spectrum was recorded on Bruker RFS 100/s, Germany (laser
-1
source: Nd:YAG, excitation wavelength: 1064 nm, spectral resolution ± 2cm ) for the solid
-1
1
13
sample in the range 50-4000 cm (Figure 2). H and C-NMR chemical shift values
measured in ppm on Bruker 400 MHz FT-NMR spectrometer using TMS as internal standard
and the sample was dissolved in a DMSO-d solvent.
6
2
4
.2. Synthesis of 4,6-dichloro-2-(methylsulfonyl)pyrimidine
,6-dichloro-2-(methylthio)pyrimidine (0.7g, 3.608 mmol) was dissolved in dichloromethane
o
(
15 mL), cooled to 0 C and meta-Chloroperoxybenzoic acid (m-CPBA) was added (1.55g,
9
.011 mmol) portion wise to the reaction mixture at the same temperature. After addition, the
reaction mixture was allowed to stir for 4 hours at room temperature. Then the reaction mass
was quenched with an aqueous solution of sodium thiosulphate (11 mL) and extracted with
dichloromethane (2 x 10 mL). Combined organic layer was washed with saturated aqueous
NaHCO solution (15 mL), brine solution (7 mL), dried over anhydrous MgSO , filtered and
3
4
the filtrate was evaporated under reduced pressure to afford 4,6-dichloro-2-
methylsulfonyl)pyrimidine (0.65 g, 80.20%) as off-white solid (Scheme -1).
.3. X-ray crystallography
(
2
A suitable block shape crystal with dimension 0.12×0.16×0.18 mm was selected and mounted
on a Bruker Smart APEX-II diffractometer using graphite monochromated MoKα (λ =
0
.71073 Å) radiation and detector (CCD). The crystal was kept at 296 K during data
collection. The structure was solved using SHELXS-97 [24] structure solution program then
refined with the ShelXL [24] refinement package using Least Squares minimization. All the
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geometrical calculations were carried out using the program PLATON [25] associated the
WinGX suite [26]. The molecular and packing diagrams in solid state were generated using
the software MERCURY [27].
2
.4. Computational details
Ab-initio and DFT calculations on DCMSP have been performed with the Gaussian 09W
computational package [28] and Schrödinger Materials Science Suite 2018-1 [29]. The
starting molecular geometry of DCMSP was taken from experimental X-ray crystal structure.
The full geometry optimization, analytic harmonic frequency calculations, HOMO-LUMO
energies (FMO orbitals), global reactivity parameters, NBO analysis, Mullikan charges and
molecular electrostatic potential (MEP) were carried out by the DFT approach with B3LYP
(
Becke three-parameter Lee-Yang-Parr) functional [30] using 6-311++G(d,p) basis set. The
assignment of each vibrational frequency was done by PED analysis using VEDA4 program
31]. The calculated wavenumbers were scaled by a scaling factor 0.9613 for better
agreement with experimental values [32]. Chemical shift values were computed by GIAO
Gauge-Independent Atomic Orbital) method [33] and electronic spectra were calculated by
[
(
the TD-DFT method [34].
In order to study the linear and nonlinear optical (NLO) properties of the DCMSP crystal, we
used the supermolecule (SM) approach to simulate the polarization of the crystalline
environment in a single DCMSP molecule. This approach consists of building a bulk formed
by a set of unit cells arranged in a 13×13×13 configuration. Each unit cell has 4 molecules
and each molecule has 16 atoms, thus creating a bulk with 140,576 atoms, as shown in Figure
S1. We will call this bulk an embedded molecule or crystal DCMSP. This isolated molecule
has a blue highlight in the centre of the bulk. The atoms that are around the structure in blue
were considered as punctual charges. Thus, the effects of intermolecular interactions make it
possible to estimate the values of crystal properties, taking as a starting point the results
obtained from the isolated molecule DCMSP.
The iterative process of the SM approach is performed in several steps: step 0, the partial
atomic charge of the atoms of the isolated molecule is determined, via a ChelpG fit, by the
MP2 method using the 6-311++G(d,p) basis set; then each atom of the bulk is replaced by its
partial atomic charge previously obtained via fit Chelpg. At this moment, the static electric
properties are calculated, dipole moment (ꢀ), linear polarizability (α) and second
hyperpolarizability (γ). In step 1, the partial atomic charges of the atoms of the isolated
molecule are determined again and then we replace the value of these atomic charges in each
atom of the bulk and then the electrical properties are again calculated. This iterative process
4

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continues until the convergence of the electric dipole moment is obtained, which is treated as
the electrostatic equilibrium between the isolated and neighbouring molecules [35], see
Figure S2.
In each iterative process, the linear and non-linear electrical properties were calculated for
both the static and dynamic cases of the embedded molecule. In the calculations of dipole
moment and linear polarizability, we used the MP2 method and for the calculation of the
second hyperpolarizability, we used the Density Functional Theory (CAM-B3LYP) method;
in both cases, we used the 6-311++G(d,p) basis set. This choice was due to the satisfactory
results obtained previously for similar systems, as demonstrated in [36].
Fonseca et al. [37] used the SM approach for the calculation of the dipole moment and the
first hyper-polarizability and those results compared with experimental values, show mutual
agreement. In another study, Santos et al. [38] used the SM approach for the calculation of
linear ꢀ(ꢁ) and nonlinear second-order ꢀ(ꢂ) susceptibilities of urea and thiourea, theoretical
results were very close to the experiment’s reports. A recent literature shows [36] the SM
(
ꢁ)
(ꢂ)
approach was successfully used to calculateꢀ , ꢀ for 3-methyl-4-nitropyridine-1-oxide
molecule and again the results are good in agreement with the experimental reports. In recent
years, the SM approach has been successfully applied in several studies [39-49].
The electrical parameters of the crystal DCMSP were calculated using the following
expressions, the total dipole moment,
ꢁ/ꢂ
ꢂ
ꢂ
ꢂ
(1)
ꢃ = ꢄꢃ + ꢃ + ꢃ ꢈ
,
ꢅ
ꢆ
ꢇ
the average of the linear polarizability,
1
(2)
ꢉꢊ = ꢄꢉ + ꢉꢆꢆ + ꢉ ꢈ,
ꢅꢅ
ꢇꢇ
3
and the average of the second hyperpolarizability, in Kleinmann's [50] symmetry,
(3)
1
ꢋ̅
= ꢌꢋ
+ ꢋꢆꢆꢆꢆ + ꢋꢇꢇꢇꢇ + 2ꢄꢋꢅꢅꢆꢆ + ꢋꢅꢅꢇꢇ + ꢋꢆꢆꢇꢇꢈꢍ.
ꢅꢅꢅꢅ
5
The average linear polarizability and the average second hyperpolarizability can be related
with the linear refractive index (n ) of the crystal by the Clausius-Mossotti relation, and with
o
(
ꢎ)
the third-order electric susceptibility (ꢀ ), through the expressions,
ꢂ
ꢏ − 1 4ꢑꢒ
(4)
(5)
ꢐ
=
〈ꢉ〉,
ꢂ
ꢏ + 2
3
ꢐ
and
ꢕ
ꢔ ꢒꢋ
̅
ꢀ(
ꢎ)
=ꢓ
,
ꢖ ꢗ
ꢐ
5

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where N is the number of molecules (Z) per unit cell volume (V) and f is the Lorentz local
field correction factor given by,
ꢂ
(
ꢏ + 2)
(6)
ꢐ
ꢔ =
.
3
DFT calculations and molecular dynamics (MD) simulations were also performed by Jaguar
51-53] and Desmond [53-56] programs, respectively. Input files and the visualization of
[
results have been achieved by Maestro GUI [57]. Jaguar, Desmond and Maestro programs
were used as incorporated in Schrödinger Materials Science Suite 2018-1 [29]. For DFT
calculations, a B3LYP exchange-correlation functional was used. Calculations of MEP, ALIE
and atomic Fukui indices were done with 6-311++G(d,p) basis set. BDE and H-BDE values
have been obtained with 6-311G(d,p) basis set. MD simulation was performed with OPLS3
[
54, 58-60], together with simulation time set to 10 ns, while the cut off radius was set to 12
Å. The temperature was set to 300 K and the pressure to 1.0325 bar. The MD system was
modeled as one DCMSP molecule surrounded by ~2500 water molecules, all placed in a
cubic box. The system was considered as an NPT ensemble type. The solvent was described
by a simple point charge (SPC) model [61].
3
3
. Results & analysis
.1. Crystal structure description
ꢊ
The title compound DCMSP (C H Cl N O S), crystallizes in a triclinic P1 space group with
5
4
2
2
2
two symmetrically independent molecules in the asymmetric unit. The crystallographic data
and refinement parameters are listed DCMSP are listed in Table 1 and geometric parameters
o
for hydrogen bonding and other intermolecular contacts (Å, ) operating in the crystal
structure of DCMSP in Table 2. The crystal structure description of DCMSP was included in
supplementary information.
3
3
.2. Hirshfeld surface analysis
D-Hirshfeld surfaces [62-64] associated 2D-finger print analysis [65-67] was performed
using a powerful graphical tool CrystalExplorer3.1 suite [68], which accept CIF as the input
file. The 3D-Hirshfeld surfaces and 2D-finger print plots of present investigated compound
depicted in Figure 3. The surfaces title compound have been mapped over dnorm(1), shape
index (2) and curvedness (3) in the range of –0.356 (red) to 1.191 Å au (blue), –1.0 (concave)
to 1.0 Å au (convex) and –4.0 (flat) to 0.4 Å au (singular), respectively (Figure 3A). In dnorm
surface, strong hydrogen bonds result in bright-red spots near the hydrogen bonding acceptor
and donor atoms, while other interactions result in faint-red spots. The dnorm mapped surfaces
of the present investigated compound exhibit two interactions; the first interaction between
6

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the oxygen atom of the sulfonyl group (S=O) and with the hydrogen atom of pyrimidine ring,
which can be visualized as bright red spot and labeled as (i). The second interaction between
the oxygen atom of sulfonyl group (S=O) and with the hydrogen atom of a methyl group
(
CH ), which can be visualized as bright red spots and labeled as (ii) (Figure 3A and 3B).
3
From the decomposition of fingerprint plots of the title compound represents the major
contributors contacts on the surface of Hirshfeld namely O···H/H···O and H···H contacts.
The intermolecular hydrogen bonds contacts O···H /H···O have the greatest contribution to
the surface of Hirshfeld (21.9%), they are represented by two sharp symmetric spikes in the
two-dimensional fingerprint maps (Figure 3.C (a)). The H···H contacts appear in the middle
of the scattered points in the two dimensional fingerprint maps; they comprise 6% of the
entire surface of Hirshfeld (Figure 3.C (b)).
3
.3. Optimization of geometry
The geometry optimization of DCMSP was carried out for an isolated molecule in the gas
phase utilizing DFT calculations with the B3LYP correlation functional and 6-311++G (d,p)
basis set using the Gaussian 09W software and those results are included in the
supplementary data (supplementary data).
3
.4. Vibrational Analysis
The calculated (scaled) wavenumbers, observed IR, Raman bands and assignments are given
in Table 3. The methyl group stretching modes (asymmetric and symmetric) are expected in
-1
-1
the region 3100-2900 cm [69, 70]. Wherein these modes are observed at 3058 cm in the IR
-1
-1
spectrum, 3060 cm in the Raman spectrum and 3064, 3043 cm theoretically (asymmetric
-1
-1
stretching modes); at 2946 cm in the Raman spectrum and 2949 cm theoretically
(symmetric stretching modes) as expected [71]. In this work, the methyl group deformations
-1
-1
bands have been observed at 1400 cm in the IR spectrum, 1399 cm in the Raman spectrum
-1
-1
and 1395, 1392 cm (DFT) (asymmetric deformation), 1297 cm in the IR spectrum, 1298
-1
-1
cm in Raman spectrum and 1301 cm (DFT) (symmetric deformation) as expected [69].
-1
Pyrimidine ring C-H stretching mode are calculated at 3114 cm (DFT), while it has been
-1
observed experimentally at 3101 cm in both IR and Raman spectrum and expected in the
-1
range 3000-3100 cm [71]. This mode (mode number 1) is pure and PED is exactly 100%
with IR intensity of 4.60 and Raman activity of 77.79. The in-plane and out-plane C-H
-1
deformation modes of the heteroaromatic ring are expected in the region 1300-1000 cm and
-
1
-1
1
1
000-600 cm respectively [71]. These bands are assigned at 1082 cm (IR spectrum), 1357,
-1
-1
-1
083 cm (Raman spectrum), 1356, 1084 cm (DFT) (in-plane deformation) and 612 cm
-1
-1
(
IR spectrum), 611 cm (Raman spectrum), 605 cm (DFT) (out-of-plane deformation).
7

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-1
The C=N stretching modes are assigned at 1363, 1255, 1198, 1082 cm in the IR spectrum,
-1
-1
1
357, 1258, 1214, 1083 cm in the Raman spectrum and in the range 1356-1084 cm
theoretically, which are in agreement with reported values [72]. The modes observed at 1509,
-1
-1
-1
1
499 cm theoretically, at 1512 cm in the IR spectrum and at 1511 cm in the Raman
spectrum are assigned as the pyrimidine ring C=C stretching modes, which are in agreement
with the literature values [73].
-1
-1
The C-Cl stretching vibrational modes are assigned at 800 cm in the IR spectrum, 802 cm
-1
in the Raman spectrum and computationally at 804, 789 cm , with high IR intensity and low
-1
Raman activity, which are expected in the region 750-880 cm [69] and in agreement with
-1
-1
reported values at 800 cm (IR) and 843, 818 (DFT) cm [71].
The stretching vibrational modes of the SO group observed at 1250 cm (IR spectrum),
-1
2
-1
-1
-1
1
246 cm (Raman spectrum) and at 1245 cm (DFT) (anti symmetric) and 1066 cm (Raman
-1
spectrum), 1063 cm (DFT) (symmetric) in agreement with reported values [74].
.5. Frontier orbital analysis, Global reactivity parameters and electronic spectral analysis
3
Reactivity is an inherent property of the molecular system which reflects on the feasibility of
chemical modification. The stability and reactivity of the molecular system are addressed
through global reactivity parameters such as chemical potential, global hardness and
electrophilicity index. Frontier molecular orbitals of the DCMSP are visualized in Figure 4
and the energy gap between the highest occupied molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO) is calculated using the DFT/B3LYP/6-311++G(d,p)
level of theory. HOMO (molecular orbital number 57 with energy of –8.49 eV) is confined
over the methylsulfonyl group, partially on pyrimidine ring, whereas the LUMO (molecular
orbital number 58 with energy of –2.67 eV) is confined over the pyrimidine ring partially on
sulfonyl group. This supports that eventual charge transfer occurs within the present
investigated compound from methylsulfonyl group to pyrimidine ring, while the energy gap
between frontier orbitals is 5.82 eV. The global reactivity parameters for present investigated
molecule are: ionization potential (I) is equal to –EHOMO = 8.49 eV, electron affinity (A)
ELUMO = 2.67 eV, electronegativity χ = (I+A)/2 = 5.58 eV, global hardness η = (I–A)/2 = 2.91
eV, chemical potential (µ) equals to –(I+A)/2 = –5.58 eV, chemical softness (ν) equals to 1/ η
2
=
0.34 eV and electrophilicity index (ω) = µ /2η = 5.34 eV [75, 76]. The maximum
absorption wavelengths λ [nm], excitation energies E [eV] and oscillator strengths (f) of the
title compound are computed using TD-DFT/B3LYP/6-311++G(d,p) method [33] (Table 4).
The simulated UV-Visible spectrum in the gas phase is shown in Figure S3. The electronic
8

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absorption spectra of title compound show an electronic absorption band with maxima at λmax
=
254 nm, which is good in agreement with theoretical value (λmax at 253 nm).
3
.6. NBO analysis
Natural bonding orbital analysis (NBO analysis) calculations were done with the help of
NBO 3.1 program [77], as is implemented in a Gaussian 09W suite, at the DFT/B3LYP/6-
3
11++G(d,p) level of theory. Second-order interactions obtained by NBO analysis are listed
in Table 5 and Table 6. The important intermolecular hyper conjugative interactions are:
C12-S9 from O11 of n2(O11)→ σ*(C12-S9),C12-S9 from O10 of n2(O10)→ σ*(C12-S9),
N6-C1 from N2 of n1(N2) → σ*(N6-C1), N2-C1 from N6 of n1(N6) → σ*(N2-C1), with
electrons densities 0.17263, 0.17263, 0.03712, 0.04159e and stabilization energies 17.58,
1
7.58, 12.49, 13.01 kJ/mol. Almost 100% p-character was observed as lone pairs of n2O11
99.85) and n2O10 (99.85).
.7. Nonlinear optical properties
(
3
The SM approach was used in the calculations of the electrical properties of the embedded
molecule DCMSP, as is indicated in Table 7. The ꢃ component of the dipole moment was
ꢆ
the one with the highest contribution to the total dipole moment, whereas the ꢃ component
ꢅ
contributed the least. The value of the total dipole moment (ꢀ) due to the effect of the
ambient polarization was 5.71 D. The calculated linear polarizability in the case static for the
crystalline phase DCMSP was 17.34 × 10ꢘꢂꢕ esu and the component that contributed mostly
to the value of the average polarizability was ꢉ , while the one that contributed the least was
ꢇꢇ
ꢉꢆꢇ. The values of the second hyperpolarizability can be seen in Table 7 for the embedded
molecule DCMSP. The tensor components ꢋꢅꢅꢅꢅ and ꢋꢇꢇꢇꢇ showed a greater participation in
the calculation of the average of the second hyperpolarizability ꢋ
̅.
From Eq. (4) the static linear refractive index estimated for DCMSP crystal is n = 1.58 and
o
(3)
the Eq. (5) was used to calculate the third order χ electric susceptibility of the DCMSP
(3)
-22
crystal and value found for χ in the static case for the DCMSP crystal was 34.02×10
2
(
m/V) . However, in order to make a proper comparison between the DFT predictions and
(3)
the experimental value of χ measured by the single Z-scan technique [14], we have find a
first estimate of the frequency-dependent second hyperpolarizability (〈ꢋ(−ꢙ; ꢙ, ꢙ, −ꢙ)〉)
associated with a nonlinear optical process [78] of the intensity-dependent refractive index
(
IDRI) of the dc-K results. According to previous work [79], for small frequencies [80],
〈ꢋ(−ꢙ; ꢙ, ꢙ, −ꢙ)〉 can be written as 〈ꢋ(−ꢙ; ꢙ, ꢙ, −ꢙ)〉 ≅ 2〈ꢋ(−ꢙ; ꢙ, 0,0)〉 −
(
〈
ꢋ(0; 0,0,0)〉 details in Table 8. The linear refractive index dispersion curves and the third-
9

ACCEPTED MANUSCRIPT
(3)
order nonlinear optical susceptibility χ for the DCMSP crystal are shown in Figure 5. In
(3)
both figures the linear refractive index and the χ show similar behavior as a function of
frequency. Table 9 presents the DFT prediction and the experimental results of the
macroscopic quantities studied. The value of DCMSP crystal is therefore 24.67, 28.51, and
2
3.94 times higher respectively than the values found experimentally by D'silva et al. [14],
see Table 9.
.8. MEP and ALIE surfaces, atomic Fukui indices
3
The identification of reactive molecular sites of DCMSP molecule in this work has been done
firstly by a combination of MEP and ALIE quantum molecular descriptors. Both of these
descriptors are widely used for the determination of molecular areas which are sensitive
towards electrophilic and nucleophilic attacks [81-86]. Although MEP descriptor is used
somewhat more frequently, ALIE descriptor might better perform when it comes to the
identification of sites prone to electrophilic attacks [87-90]. Both MEP and ALIE descriptors
are most frequently visualized by a mapping of their values to the electron density surface,
which is the method adopted in this work as well. DCMSP molecule’s MEP and ALIE
surfaces have been provided in Figure 6.
According to the provided MEP surface of DCMSP molecule, the oxygen atoms are
recognized as sensitive towards electrophilic attacks, due to the fact that MEP has the lowest
values precisely at these locations. Maximal MEP values are located in near vicinities of
hydrogen atoms and above chlorine atoms, designating these locations as possibly sensitive
towards nucleophilic attacks. On the other side, ALIE descriptor identifies the near vicinity of
nitrogen atom N6 as possibly sensitive towards the electrophilic attacks. Similarly, as in the
case of the MEP descriptor, maximal ALIE values are located in near vicinities of hydrogen
atoms and above chlorine atoms.
The concept of Fukui functions is very frequently employed for the further assessment of
local reactive properties of molecular structures. Besides Fukui functions, Fukui indices are
also frequently used. Sometimes, this descriptor is called condensed-to-atom Fukui function.
In Jaguar program for DFT calculations, Fukui indices are calculated according to
HOMO
methodologies explained in references [91, 92]. In this particular work we have used fNN
LUMO
and fNN
indices for further understanding of local reactive properties of DCMSP
molecule. Fukui indices have been summarized for DCMSP molecule in Figure 7.
In Figure 7, the very low (and therefore irrelevant) values of Fukui indices haven’t been
HOMO
visualized for the sake of clarity. The high values of fNN
index indicate that certain atom
1
0

ACCEPTED MANUSCRIPT
might donate electrons, thanks to which it can be stated that it is prone to electrophilic
HOMO
attacks. According to Figure 7a, the highest positive values of the fNN
index have been
calculated for oxygen atoms. These results are in agreement with the conclusions of MEP
LUMO
surfaces. On the other side, the high values of fNN
index indicate that atom might receive
electrons and therefore might be sensitive towards the nucleophilic attacks. According to
LUMO
Figure 7b, the highest values of the fNN
index have been calculated for carbon atoms C1
and C4, designating them as possibly vulnerable to nucleophilic attacks.
.9. Sensitivity towards autoxidation and water
3
Taking into account that autoxidation mechanism belongs to a group of very important
reactions from the industrial aspects [18, 83, 85, 93-95], we have calculated BDE and H-BDE
values for all single acyclic bonds of DCMSP molecule. Concretely, H-BDE values reflect
the sensitivity of molecule towards the autoxidation mechanism and this fact is very
important because experimental measurements of BDE are very difficult and time-consuming
[
20, 96]. For instance, if the H-BDE value is calculated to be in the range between 70 and 85
kcal/mol, then there is a high possibility that the observed molecule is sensitive towards the
autoxidation mechanism [96]. H-BDE values from 85 kcal/mol up to 90 kcal/mol might also
be important, but they have to be taken into account with caution [97]. BDE values for the
remaining single acyclic bonds don’t have particular importance for a prediction of sensitivity
towards autoxidation mechanism, but they might serve for the comparison of bond strengths
within the molecule. BDEs and H-BDEs for DCMSP molecule have been summarized in
Figure 8.
According to the H-BDE values calculated for DCMSP molecule, it can be stated that this
molecule is highly stable towards the autoxidation mechanism due to the fact that all of the
H-BDE values are much higher than the upper border level of 90 kcal/mol. This indicates a
high stability of DCMSP in the presence of oxygen, difficult degradation and therefore long
shelf life of formulations based on it. On the other side, the lowest BDE value has been
calculated for the single bond connecting the sulphur atom and the five-membered ring,
indicating that degradation of DCMSP molecule might start by breaking this bond.
MD simulation has been performed and radial distribution functions (RDF) have been
calculated for all atoms in order to identify the atoms with the pronounced interactions with
water molecules. RDFs have been calculated with respect to the distance between the
observed atom and oxygen atom of water molecules. Representative RDFs with respect to
their profile have been presented in Figure 9.
1
1

ACCEPTED MANUSCRIPT
According to results related to RDFs, DCMSP molecule has significant stability in water
since there are no hydrogen atoms with their maximal g(r) values located at distances below 2
Å. The highest g(r) values have been calculated for both chlorine atoms, with distances of
about 3.5 Å. High maximal g(r) values have also been calculated for sulphur atom and carbon
atom C12, however, their maximal g(r) values are also located at high distances, especially in
the case of case of the sulphur atom with a distance of 4 Å. These results indicate a very low
possibility for DCMSP’s degradation to be triggered by natural environmental conditions.
3
.10. NMR spectroscopy analysis
Nuclear magnetic resonance spectroscopy (NMR spectroscopy) is one of the powerful
spectroscopic techniques for the identification of structure as well as functional groups of
1
13
chemical species. For title compound, H and C-NMR chemical shift values were recorded
in a DMSO-d solvent and TMS as internal standard on Bruker FT-NMR spectrometer
6
operating at 400 MHz (Figure S4) and theoretically calculated by GIAO method [32] using
DFT/6-311++G(d,p) basic set, which is performed after full geometry optimization. The
chemical shift values of the proton spectra were observed in two regions; the first signal
observed at 8.4/7.7 ppm (experimental/DFT) for aromatic proton and another signal observed
1
3
for methyl proton at 3.4/3.1 ppm (experimental/DFT). Chemical shift values of C-NMR of
typical organic molecule usually ˃100 ppm [98, 99], for title compound aromatic carbons
were observed in the range (experimental/DFT) 125-164/130-177 ppm. The chemical shift
value for both C3 and C5 is 162/177 (experimental/DFT) were found to be significantly high
due to the impact of the electronegative chlorine atom. For the methyl group, carbon (C12)
signal is observed at the upfield region (experimental/DFT) at 40/45 ppm (Table S1).
3
.11. Mulliken atomic charge analysis
The calculation and analysis of Mulliken atomic charges have an important role for the
determination of reactive properties of the studied molecular systems. Atomic charge affects
the dipole moment, polarizability, electronic structure and other molecular properties of the
system [100]. The Mulliken atomic charges of DCMSP are obtained by means of Mulliken
population analysis and those results are tabulated in Table S2. The charges at the sites of the
C atoms attached to the electronegative atoms N, S and Cl atoms are positive because of the
electron-withdrawing nature of N, S and Cl atoms. Thus, C , C and C atoms accommodate
1
3
5
positive charge and become more acidic. Other C atoms are in negative charge. Moreover,
Mulliken atomic charges also indicate that all of the hydrogen atoms have a net positive
charge, but the H and H atoms accommodate more positive atomic charges 0.162 and
1
3
14
0
.183 e, than the other hydrogen atoms and therefore are considered as acidic. The calculated
1
2

ACCEPTED MANUSCRIPT
Mulliken charges of O and O , H , H , C and C atoms are –0.480, –0.480, 0.162, 0.183,
1
0
11
13
14
4
12
–
0.002 and –0.432 e, respectively, and these values confirm the existence of C-H···O
intermolecular hydrogen bond in solid forms.
Conclusions
The title compound DCMSP was synthetized and characterized by SCXRD, FT-IR, FT-
4
.
1
13
Raman, H and C-NMR spectroscopic signature studies. DFT calculation and MD
simulation studies were used for to predict reactive properties and stability of title compound.
The experimental geometrical parameters were good in agreement with predicted geometrical
parameters. The DCMSP crystal macroscopic quantities such as the linear refractive index (n
=
1.613)
and
the
third-order
nonlinear
susceptibility
(ꢎ)
ꢘꢂꢂ
ꢂ
ꢂ
(
χ (−ꢙ; ꢙ, ꢙ, −ꢙ) = 56.74×10
m ⁄V )ꢓ were calculated from the Clausius-Mossoti
equation. This χ( value is twenty eight times greater than the reported values for others
chalcone derivatives (see Table 9), qualifying the DCMSP crystal as a potential candidate for
application in nonlinear optical devices. The SM approach was successfully used to estimate
the third-order nonlinear susceptibility and the linear refractive index in Ref. [101] with
results close to the experimental ones. MEP surfaces showed that oxygen atoms might be
sensitive towards electrophilic attacks. On the other side, ALIE surfaces also indicated
ꢎ)
HOMO
nitrogen atom N6 to be possibly sensitive towards electrophilic attacks. The results of fNN
atomic Fukui index are in agreement with the findings of MEP surfaces regarding the
LUMO
sensitivity of oxygen atoms towards electrophilic attacks, while fNN
atomic Fukui index
highlighted two carbon atoms of five membered ring to be possible prone to nucleophilic
attacks. H-BDE values indicated stability towards the autoxidation mechanism, while BDE
values indicated that degradation of DCMSP might start by breaking of C1–S9 bond. MD
simulation and RDFs showed that DCMSP is stable in water as well, with all representative
atoms having maximal g(r) values at distances beyond 3 Å.
Acknowledgment
The author C. Valverde thank the Brazilian funding agencies CAPES, CNPq, and FAPEG for
financial support and the PrP/UEG for the research developed with the support of the UEG
High Performance Computing Nucleus. Part of this study was conducted within the projects
supported by the Ministry of Education, Science and Technological Development of Serbia,
grant numbers III41017. Part of this work has been performed thanks to the support received
from Schrödinger Inc.
1
3

ACCEPTED MANUSCRIPT
Supplementary Material
The cif file of the title compound have been assigned CCDC number 1863699 and can be
obtained free of cost on application to CCDC 12 Union Road, Cambridge CB21 EZ, UK.
(Fax: (+44) 1223 336-033: e-mail: data_request@ccdc.cam.ac.uk).
References
[
[
[
1]
2]
3]
G. Shi, Y. Wang, F. Zhang, B. Zhang, Z. Yang, X. Hou, S. Pan, K.R. Poeppelmeier,
Finding the Next Deep-Ultraviolet Nonlinear Optical Material: NH B O F, J. Am.
4
4
6
Chem. Soc. 139 (2017) 10645–10648.
B. Zhang, G. Shi, Z. Yang, F. Zhang, S. Pan, Fluorooxoborates: Beryllium-Free
Deep-Ultraviolet Nonlinear Optical Materials without Layered Growth, Angew.
Chemie Int. Ed. 56 (2017) 3916–3919.
M. Mutailipu, M. Zhang, B. Zhang, L. Wang, Z. Yang, X. Zhou, S. Pan, SrB O F
7 3
5
6
−
Functionalized with [B O F ] Chromophores: Accelerating the Rational Design of
5
9 3
Deep-Ultraviolet Nonlinear Optical Materials, Angew. Chemie Int. Ed. 57 (2018)
095–6099.
6
[
[
4]
5]
E. Timurdogan, C. V Poulton, M.J. Byrd, M.R. Watts, Electric field-induced second-
order nonlinear optical effects in silicon waveguides, Nat. Photonics. 11 (2017) 200-
2
006.
L. Lu, Z. Liang, L. Wu, Y. Chen, Y. Song, S.C. Dhanabalan, J.S. Ponraj, B. Dong, Y.
Xiang, Few-layer Bismuthene: Sonochemical Exfoliation, Nonlinear Optics and
Applications for Ultrafast Photonics with Enhanced Stability, Laser & Photonics
Reviews, 12 (2018) 1700221.
[
[
6]
7]
R. Salvi, C. Cerqueira-coutinho, E. Ricci-junior, N. Santos, S.R. Pinto, E.S.
Bernardes, P. Lopes, B. De Araujo, R. Santos-oliveira, Diagnosing lung cancer using
99m
etoposide microparticles labeled with
2018) 341-345.
Tc, Artif Cells Nanomed Biotechnol. 46(2)
(
M. Luo, F. Liang, Y. Song, D. Zhao, F. Xu, N. Ye, Z. Lin, M. Luo, F. Liang, Y. Song,
D. Zhao, F. Xu, N. Ye, Z. Lin, M B O F ( M = Ca, Sr): Two Noncentrosymmetric
2
10 14 6
Alkaline Earth Fluorooxoborates as Promising Next-Generation Deep-Ultraviolet
Nonlinear Optical Materials, J Am Chem Soc. 140 (11) (2018) 3884-3887.
H. Zhao, S. Han, R. Hui, Nonlinear Optical Spectroscopy of Two-Dimensional
Materials Qiannan Cui, (2017).
[
[
8]
9]
M. Nakano, Open-Shell-Character-Based Molecular Design Principlesꢁ: Applications
to Nonlinear Optics and Singlet Fission, Chem Rec. 17 (2017) 27-62.
1
4

ACCEPTED MANUSCRIPT
[
[
10] R. Mallah, M.C. Sreenath, S. Chitrambalam, I.H. Joe, N. Sekar, Excitation energy
transfer processes in BODIPY based donor-acceptor system - Synthesis,
photophysics, NLO and DFT study, Opt. Mater. 84 (2018) 795–806.
+
3
11] M. Anis, G.G. Muley, V.G. Pahurkar, M.I. Baig, S.R. Dagdale, Influence of Nd on
zinc tris-thioureasulphate single crystalꢁ: A comparative crystal growth, structural ,
linear – nonlinear optical and dielectric study to explore NLO device applications,
Materials Research Innovations, DOI: 10.1080/14328917.2016.1264848.
12] Joel M. Hales, Shijun Zheng, Stephen Barlow, A. Seth R. Marder, J.W. Perry,
Bisdioxaborine Polymethines with Large Third-Order Nonlinearities for All-Optical
Signal Processing, (2006). doi:10.1021/JA063535M.
[
[
[
[
[
[
[
[
[
13] S.R. Marder, B. Kippelen, A.K.-Y. Jen, N. Peyghambarian, Design and synthesis of
chromophores and polymers for electro-optic and photorefractive applications,
Nature. 388 (1997) 845–851. doi:10.1038/42190.
14] E.D. D’silva, G.K. Podagatlapalli, S. VenugopalRao, S.M. Dharmaprakash, Study on
third-order nonlinear optical properties of 4-methylsulfanyl chalcone derivatives using
picosecond pulses, Mater. Res. Bull. 47 (2012) 3552–3557.
15] S. Shettigar, G. Umesh, K. Chandrasekharan, B.K. Sarojini, B. Narayana, Studies on
third-order nonlinear optical properties of chalcone derivatives in polymer host, Opt.
Mater. 30 (2008) 1297–1303.
16] A. John Kiran, A. Mithun, B. ShivaramaHolla, H.D. Shashikala, G. Umesh, K.
Chandrasekharan, Nonlinear optical studies of 1-3-diaryl-propenones containing 4-
methylthiophenyl moieties, Opt. Commun. 269 (2007) 235–240.
17] A.N. Prabhu, V. Upadhyaya, A. Jayarama, K.S. Bhat, Third-order NLO property of
thienylchalcone derivative: Physicochemical analysis and crystal structure
determination, Mol. Cryst. Liq. Cryst. 637 (2016) 76–86.
18] S. Armaković, S.J. Armaković, B.F. Abramović, Theoretical investigation of
loratadine reactivity in order to understand its degradation properties: DFT and MD
study, Journal of molecular modelling, 22(10) (2016) 240.
19] E.I. Izgorodina, Z.L. Seeger, D.L. Scarborough, S.Y. Tan, Quantum Chemical
Methods for the Prediction of Energetic, Physical, and Spectroscopic Properties of
Ionic Liquids. (2017).
20] P. Lienard, J. Gavartin, G. Boccardi, M. Meunier, Predicting drug substances
autoxidation, Pharmaceutical research, 32(1) (2015) 300-310.
1
5

ACCEPTED MANUSCRIPT
[
[
[
21] A. Reisi-Vanani, M. Safipoor, Investigation of carbon monoxide adsorption onto
+
sumanene (C21H12) decorated with Li ions toward its elimination, Current Applied
Physics, 17(11) (2017)1382-1395.
+
22] A. Reisi-Vanani, Z. Shabani, Evaluation of the hydrogen adsorption onto Li and Li
decorated circumtrindene (C36H12): A theoretical study, International Journal of
Hydrogen Energy, 42(36) (2017) 22973-22986.
23] S. Armaković, S.J. Armaković, S. Koziel, Optoelectronic properties of curved carbon
systems, Carbon, 111 (2017) 371-379.
[
[
24] G.M. Sheldrick, A short history of SHELX, Acta Cryst. A64 (2008) 112-122.
25] A.L. Spek, Structure validation in chemical crystallography, ActaCrystallogr., D 65
(2009) 148-155.
[
[
26] L.J. Farrugia, WinGX suite for small-molecule single-crystal crystallography, J. Appl.
Crsystallogr. 32 (1999) 837-838.
27] C.F. Macrae, I.J. Bruno, J.A. Chisholm, P.R. Edgington, P. McCabe, E. Pidcock, L.
Rodriguez-Monge, R. Taylor, J. van de Streek, P.A. Wood, Mercury CSD 2.0 - New
Features for the Visualization and Investigation of Crystal Structures, J. Appl. Cryst.,
4
1 (2008) 466-470.
[
28] Gaussian 09, Revision B.01, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria,
M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson,
H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng,
J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida,
T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E.
Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N.
Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C.
Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E.
Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann,
O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K.
Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich,
A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox,
Gaussian, Inc., Wallingford CT, 2010.
[
[
29] Materials Science Suite 2018-1, Schrödinger, LLC, New York, NY. 2018.
30] A.D. Becke, Density‐functional thermochemistry. III. The role of exact exchange, The
Journal of Chemical Physics, 98(7) (1993) 5648-5652.
1
6

ACCEPTED MANUSCRIPT
[
[
[
[
[
31] Michal. H. Jamroz, Vibrational Energy Distribution Analysis VEDA4, Warsaw, 2004-
2
010.
32] J.B. Foresman, Pittsburg, PA, in: E. Frisch (Ed.), Exploring Chemistry with
Electronic Structure Methods: a Guide to Using Gaussian, 1996.
33] R. Ditchfield, Molecular orbital theory of magnetic shielding and magnetic
susceptibility, J. Chem. Phys. 56 (1972) 5688–5691.
34] F. Furche, R. Ahlrichs, Adiabatic time dependent density functional methods for
excited states properties, J. Chem. Phys. 117 (2002) 7433-7447.
35] M.A. Spackman, P. Munshi, D. Jayatilaka, The use of dipole lattice sums to estimate
electric fields and dipole moment enhancement in molecular crystals, Chem. Phys.
Lett. 443 (2007) 87–91.
[
36] O.L. Santos, J.R. Sabino, H.C. Georg, T.L. Fonseca, M.A. Castro, Electric properties
of the 3-methyl-4-nitropyridine-1-oxyde (POM) molecules in solid phase: A
theoretical study including environment polarization effect, Chem. Phys. Lett. 669
(2017) 176–180.
[
[
[
37] T.L. Fonseca, J.R. Sabino, M.A. Castro, H.C. Georg, A theoretical investigation of
electric properties of <scp>L</scp> -arginine phosphate monohydrate including
environment polarization effects, J. Chem. Phys. 133 (2010) 144103.
38] O.L. Santos, T.L. Fonseca, J.R. Sabino, H.C. Georg, M.A. Castro, Polarization effects
on the electric properties of urea and thiourea molecules in solid phase, J. Chem. Phys.
1
43 (2015) 234503.
39] J.M.F. Custodio, F.G. Santos, W.F. Vaz, C.E.P. Cunha, R.G. Silveira, M.M. Anjos,
C.E.M. Campos, G.R. Oliveira, F.T. Martins, C.C. da Silva, C. Valverde, B. Baseia,
H.B. Napolitano, Molecular structure of hybrid imino-chalcone in the solid state: X-
ray diffraction, spectroscopy study and third-order nonlinear optical properties, J. Mol.
Struct. 1157 (2018).
[
40] C. Valverde, W.F. Vaz, J.M.F. Custodio, V.S. Duarte, P.S. Carvalho-Jr, A.S.
Figueredo, G.L.B. de Aquino, B. Baseia, H.B. Napolitano, The solid state structure and
environmental polarization effect of a novel asymmetric azine, New J. Chem. 41
(2017) 11361–11371.
[
[
41] B. Baseia, F. Osório, L. Lima, C. Valverde, Effects of Changing Substituents on the
Non-Linear Optical Properties of Two Coumarin Derivatives, Crystals. 7 (2017) 158.
42] A.N. Castro, F.A.P. Osório, R.R. Ternavisk, H.B. Napolitano, C. Valverde, B. Baseia,
Theoretical investigations of nonlinear optical properties of two crystalline acetamides
1
7

ACCEPTED MANUSCRIPT
structures including polarization effects of their environment, Chem. Phys. Lett. 681
(2017) 110–123.
[
[
[
43] R.F.N. Rodrigues, L.R. Almeida, F.G. dos Santos, P.S. Carvalho Jr, W.C. de Souza,
K.S. Moreira, G.L.B. de Aquino, C. Valverde, H.B. Napolitano, B. Baseia, Solid state
characterization and theoretical study of non-linear optical properties of a Fluoro-N-
Acylhydrazide derivative, PLoS One. 12 (2017) e0175859.
44] W.F. Vaz, J.M.F. Custodio, R.G. Silveira, A.N. Castro, C.E.M. Campos, M.M. Anjos,
G.R. Oliveira, C. Valverde, B. Baseia, H.B. Napolitano, Synthesis, characterization,
and third-order nonlinear optical properties of a new neolignane analogue, RSC Adv. 6
(2016) 79215–79227.
45] L.R. Almeida, M.M. Anjos, G.C. Ribeiro, C. Valverde, D.F.S. Machado, G.R.
Oliveira, H.B. Napolitano, H.C.B. de Oliveira, Synthesis, structural characterization
and computational study of a novel amino chalcone: a potential nonlinear optical
material, New J. Chem. 41 (2017) 1744–1754.
[
[
[
[
46] J. Custodio, C. Moreira, C. Valverde, G. de Aquino, B. Baseia, H. Napolitano,
Hirshfeld Surfaces and Nonlinear Optics on Two Conformers of a Heterocyclic
Chalcone, J. Braz. Chem. Soc. (2017) 168–179.
47] C. Valverde, R.F.N. Rodrigues, D.F.S. Machado, B. Baseia, H.C.B. de Oliveira, Effect
of the crystalline environment on the third-order nonlinear optical properties of L-
arginine phosphate monohydrate: a theoretical study, J. Mol. Model. 23 (2017) 122.
48] G.C. Ribeiro, L.R. Almeida, H.B. Napolitano, C. Valverde, B. Baseia, Polarization
effects on the third-order nonlinear optical properties of two polymorphs of enamine
derivative, Theor. Chem. Acc. 135 (2016) 244.
49] A.N. Castro, L.R. Almeida, M.M. Anjos, G.R. Oliveira, H.B. Napolitano, C. Valverde,
B. Baseia, Theoretical study on the third-order nonlinear optical properties and
structural characterization of 3-Acetyl-6-Bromocoumarin, Chem. Phys. Lett. 653
(
2016) 122–130.
50] D.A. Kleinman, Nonlinear Dielectric Polarization in Optical Media, Phys. Rev. 126
1962) 1977–1979.
[
[
(
51] A.D.Bochevarov, E. Harder, T.F. Hughes, J.R. Greenwood, D.A. Braden, D.M.
Philipp, D. Rinaldo, M.D. Halls, J. Zhang, R.A. Friesner, Jaguar: A high‐performance
quantum chemistry software program with strengths in life and materials sciences,
International Journal of Quantum Chemistry, 113(18) (2013) 2110-2142.
1
8

ACCEPTED MANUSCRIPT
[
[
52] Schrödinger Release 2017-4: Jaguar, Schrödinger, LLC, New York, NY, 2017. 2017.
53] L.D. Jacobson, A.D. Bochevarov, M.A. Watson, T.F. Hughes, D. Rinaldo, S. Ehrlich,
T.B. Steinbrecher, S. Vaitheeswaran, D.M. Philipp, M.D. Halls, Automated Transition
State Search and Its Application to Diverse Types of Organic Reactions, Journal of
chemical theory and computation, 13(11) (2017) 5780-5797.
[
54] D. Shivakumar, J. Williams, Y. Wu, W. Damm, J. Shelley, W. Sherman, Prediction of
absolute solvation free energies using molecular dynamics free energy perturbation
and the OPLS force field, Journal of chemical theory and computation, 6(5) (2010)
1
509-1519.
[
[
55] Z. Guo,U. Mohanty, J. Noehre, T.K. Sawyer, W. Sherman, G. Krilov, Probing the α‐
helical structural stability of stapled p53 peptides: molecular dynamics simulations
and analysis, Chemical biology & drug design, 75(4) (2010) 348-359.
56] K.J.Bowers, E. Chow, H. Xu, R.O. Dror, M.P. Eastwood, B.A. Gregersen, J.L.
Klepeis, I. Kolossvary, M.A. Moraes, F.D. Sacerdoti, Scalable algorithms for
molecular dynamics simulations on commodity clusters, in Proceedings of the 2006
ACM/IEEE conference on Supercomputing, 2006, ACM.
[
[
57] Materials Science Suite 2017-2, Schrödinger, LLC, New York, NY, 2017.
58] E.Harder, W. Damm, J. Maple, C. Wu, M. Reboul, J.Y. Xiang, L. Wang, D. Lupyan,
M.K. Dahlgren, J.L. Knight, OPLS3: a force field providing broad coverage of drug-
like small molecules and proteins, Journal of Chemical Theory and Computation,
1
2(1) (2015) 281-296.
[
[
59] W.L.Jorgensen,D.S. Maxwell, J. Tirado-Rives, Development and testing of the OPLS
all-atom force field on conformational energetics and properties of organic liquids,
Journal of the American Chemical Society, 118(45) (1996) 11225-11236.
60] W.L. Jorgensen, J. Tirado-Rives, The OPLS [optimized potentials for liquid
simulations] potential functions for proteins, energy minimizations for crystals of
cyclic peptides and crambin, Journal of the American Chemical Society, 110(6)
(1988) 1657-1666.
[
61] H.J. Berendsen, J.P. Postma, W.F. van Gunsteren, J. Hermans, Interaction models for
water in relation to protein hydration, in Intermolecular forces, Springer,1981, pp.
3
31-342.
1
9

ACCEPTED MANUSCRIPT
[
[
[
62] M.A. Spackman, D. Jayatilaka, Hirshfeld surface analysis, CrystEngComm. 11 (2009)
1
9-32.
63] F.L. Hirshfeld, Bonded-Atom Fragments for Describing Molecular Charge Densities,
Theor. Chim.Acta 44 (1977) 129-138.
64] H.F. Clausen, M.S. Chevallier, M.A. Spackman, B.B. Iversen, Three new co-crystals
of hydroquinone: crystal structures and Hirshfeld surface analysis of intermolecular
interactions, New J. Chem. 34 (2010) 193-199.
[
[
65] A.L. Rohl, M. Moret, W. Kaminsky, K. Claborn, J.J. McKinnon, B. Kahr, Hirshfeld
surfaces identify inadequacies in computations of intermolecular interactions in
crystals: pentamorphic 1, 8-dihydroxyanthraquinone, Cryst. Growth Des. 8 (2008)
4
517-4525.
66] A. Parkin, G. Barr, W. Dong, C.J. Gilmore, D. Jayatilaka, J.J. McKinnon, M.A.
Spackman, C.C. Wilson, Comparing entire crystal structures: structural genetic
fingerprinting, CrystEngComm. 9 (2007) 648-652.
[
[
[
[
[
67] M.A. Spackman, J.J. McKinnon, Fingerprinting intermolecular interactions in
molecular crystals, CrystEngComm. 4 (2002) 378-392.
68] S.K. Wolff, D.J. Grimwood, J.J. McKinnon, D. Jayatilaka, M.A. Spackman, Crystal
Explorer 2.0; University of Western Australia, Australia, 2012.
69] N.P.G. Roeges, A Guide to the Complete Interpretation of Infrared Spectra of Organic
Structures, John Wiley and Sons Inc., New York, 1994.
70]
R.M. Silverestein, G.C. Bassler, T.C. Morril, Spectroscopic Identification of Organic
Compounds, fifth ed., John Wiley and Sons Inc., Singapore, 1991.
71] V. Balachandran, A. Lakshmi, A. Janaki, vibrational spectroscopic studies and natural
bond orbital analysis of 4,6-dichloro-2-(methylthio)-pyrimidine on density functional
theory, SpectrochimicaActa Part A 81 (2011) 1-7.
[
72] N.G. Haress, A.A. El-Emam, O.A. Al-Deeb, C.Y. Panicker, A.A. Al-Saadi, C. Van
Alsenoy, J.A. War, S.K. Srivastava, Vibrational spectroscopic and molecular docking
study
carbonitrile, a potential chemotherapeutic agent, SpectrochemActa A, 137 (2015)
69-80.
of
2-Benzylsulfanyl-4-[(4-methylphenyl)-sulfanyl]-6-pentylpyrimidine-5-
5
[
[
73] S. Gunasekaran, S.R. Varadhan, K. Manoharan, Asian J.Phys. 12 (1993) 119-121.
74] P. Krishna Murthy, V. Suneetha, Stevan Armaković, Sanja J. Armaković, P.A.
Suchetan, L. Giri, R. Sreenivasa Rao, Synthesis, characterization and computational
2
0

ACCEPTED MANUSCRIPT
study of the newly synthetized sulfonamide molecule, Journal of Molecular Structure,
1
153 (2018) 212-229.
[
[
[
75] T.A. Koopmans, Uber die zuordnung von wellenfunktionen und eigenwertenzu den
einzelnenelektroneneines atoms, Physica 1 (1993) 104-113.
76] R.J. Parr, L.V. Szentpaly, S. Liu, Electrophilicity index, J. Am. Chem. Soc. 121
(1999) 1922-1924.
77] E.D. Glendening A.E. Reed, J.E. Carpenter, F. Weinhold, NBO Version 3.1, Gaussian
Inc., Pittsburgh, PA, 2003.
[
78] M. Maldonado, H.T.M.C.M. Baltar, A.S.L. Gomes, R. Vaia, K. Park, J. Che, M.
Hsiao, C.B. de Araújo, A. Baev, P.N. Prasad, Coupled-plasmon induced optical
nonlinearities in anisotropic arrays of gold nanorod clusters supported in a polymeric
film, J. Appl. Phys. 121 (2017) 143103.
[
79] S. Marques, M.A. Castro, S.A. Leão, T.L. Fonseca, Second hyperpolarizability of the
calcium-doped lithium salt of pyridazine Li–H C N ⋯ Ca, Chem. Phys. Lett. 659
3
4
2
(2016) 76–79.
[
[
80] D.M. Bishop, D.W. De Kee, The frequency dependence of nonlinear optical
processes, J. Chem. Phys. 104 (1996) 9876–9887.
81] S. Armaković, S.J. Armaković, J.P. Šetrajčić, I.J. Šetrajčić, Active components of
frequently used β-blockers from the aspect of computational study, Journal of
molecular modeling, 18(9) (2012) 4491-4501.
[
82] N. Okulik, A.H. Jubert, Theoretical study on the structure and reactive sites of three
non-steroidal anti-inflammatory drugs: Ibuprofen, Naproxen and Tolmetin acids,
Journal of Molecular Structure: THEOCHEM, 769(1) (2006) 135-141.
[
[
83] P. Politzer, J.S. Murray, The fundamental nature and role of the electrostatic potential
in atoms and molecules, Theoretical Chemistry Accounts, 108(3) (2002) 134-142.
84] Y.S. Mary, V. Aswathy, C.Y. Panicker, A. Bielenica, P. Brzózka, O. Savczenko, S.
Armaković, S.J. Armaković, C. Van Alsenoy, Spectroscopic, single crystal XRD
structure, DFT and molecular dynamics investigation of 1-(3-chloro-4-fluorophenyl)-
3
1
-[3-(trifluoromethyl) phenyl] thiourea, RSC Advances, 6(113) (2016) 111997-
12015.
[
85] B. Sureshkumar, Y.S. Mary, C.Y. Panicker, S. Suma, S. Armaković, S.J. Armaković,
C. Van Alsenoy, B. Narayana, Quinoline derivatives as possible lead compounds for
2
1

ACCEPTED MANUSCRIPT
anti-malarial drugs: Spectroscopic, DFT and MD study, Arabian Journal of
Chemistry, 2017.
[
86] J.A. War, K. Jalaja, Y.S. Mary, C.Y. Panicker, S. Armaković, S.J. Armaković, S.K.
Srivastava, C. Van Alsenoy, Spectroscopic characterization of 1-[3-(1H-imidazol-1-
yl) propyl]-3-phenylthiourea and assessment of reactive and optoelectronic properties
employing DFT calculations and molecular dynamics simulations, Journal of
Molecular Structure, 1129 (2017) 72-85.
[
[
[
87] J.S. Murray, J.M. Seminario, P. Politzer, P. Sjoberg, Average local ionization energies
computed on the surfaces of some strained molecules, International Journal of
Quantum Chemistry, 38(S24) (1990) 645-653.
88] P. Politzer, F. Abu‐Awwad, J.S. Murray, Comparison of density functional and
Hartree–Fock average local ionization energies on molecular surfaces, International
journal of quantum chemistry, 69(4) (1998) 607-613.
89] F.A. Bulat, A. Toro-Labbé, T. Brinck, J.S. Murray, P. Politzer, Quantitative analysis
of molecular surfaces: areas, volumes, electrostatic potentials and average local
ionization energies, Journal of molecular modeling, 16(11) (2010) 1679-1691.
90] P. Politzer, J.S. Murray, F.A. Bulat, Average local ionization energy: a review.
Journal of molecular modeling, 16(11) (2010) 1731-1742.
[
[
[
91] R.R. Contreras, P. Fuentealba, M. Galván, P. Pérez, A direct evaluation of regional
Fukui functions in molecules, Chemical physics letters, 304(5) (1999) 405-413.
92] E. Chamorro, P. Pérez, Condensed-to-atoms electronic Fukui functions within the
framework of spin-polarized density-functional theory, The Journal of chemical
physics, 123(11) (2005) 114107.
[
[
[
93] S. Armaković, S. Armaković, N. Finčur, F. Šibul, D. Vione, J. Šetrajčić, B.
Abramović,
Influence
of
electron
acceptors
on
the
kinetics
of
metoprololphotocatalytic degradation in TiO2 suspension, A combined experimental
and theoretical study, RSC Advances, 5(67) (2015) 54589-54604.
94] S.J. Armaković, M. Grujić-Brojčin, M. Šćepanović, S. Armaković, A. Golubović, B.
Babić, B.F. Abramović, Efficiency of La-doped TiO2 calcined at different
temperatures in photocatalytic degradation of β-blockers, Arabian Journal of
Chemistry, 2017.
95] S.J. Armaković, S. Armaković, D.D. Četojević-Simin, F. Šibul, B.F. Abramović,
Photocatalytic degradation of 4-amino-6-chlorobenzene-1, 3-disulfonamide stable
2
2

ACCEPTED MANUSCRIPT
hydrolysis product of hydrochlorothiazide: Detection of intermediates and their
toxicity, Environmental Pollution, 233 (2018) 916-924.
[
[
96] T. Andersson, A. Broo, E. Evertsson, Prediction of Drug Candidates' Sensitivity
Toward Autoxidation: Computational Estimation of C-H Dissociation Energies of
Carbon‐Centered Radicals, Journal of pharmaceutical sciences, 103(7) (2014) 1949-
1
955.
97] G. Gryn'ova, J.L. Hodgson, M.L. Coote, Revising the mechanism of polymer
autooxidation, Organic & biomolecular chemistry, 9(2) (2011) 480-490.
[
[
[
98] H.O. Kalinowski, S. Brawn, Carbon13 NMR Spectroscopy, John Wiley and Sons,
Chichester, 1988.
99] K. Pinlajer, E. Kleinpeter (Eds.), Carbon13 Chemical Shifts in Structure and
Spectrochemical Analysis, VCH publishers, Deerfield Beach, 1994.
100] R.S. Mulliken, Electronic population analysis on LCAO-MO molecular wave
functions, J. Chem. Phys. 23 (1955) 1833-1840.
[
101] C. Valverde, F.A.P. Osório, T.L. Fonseca, B. Baseia, DFT study fo third-order
nonlinear susceptibility of a chalcone crystal, Chem. Phys. Letters 706 (2018) 170–
1
74.
Figures
Scheme -1: Synthetic scheme for 4,6-dichloro-2-(methylsulfonyl)pyrimidine.
Figure 1. Fourier transform Infra-Red spectrum of DCMSP.
Figure 2. Fourier transform Raman spectrum of DCMSP.
Figure 3. Analysis of 3D-Hirshfeld surfaces and 2D-finger print plots of DCMSP.
Figure 4. HOMO-LUMO plots of DCMSP.
Figure 5. Dynamic evolution of the studied values (a) of the linear refractive index and (b)
third-order nonlinear optical susceptibility χ (inꢓ10ꢘꢂꢂ m ⁄V ) of the DCMSP crystal with
(
3)
ꢂ
ꢂ
respective values of frequencies.
Figure 6. MEP and ALIE surfaces of DCMSP.
HOMO
LUMO
Figure 7. Fukui indices for DCMSP molecule a) f NN
and b) fNN
indices.
Figure 8. H-BDE (red color) and BDE (blue color) values for DCMSP molecule.
Figure 9. Representative RDFs of DCMSP molecule.
2
3

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Tables
Table 1. Crystallographic data and structure refinement of DCMSP.
Table 2. Hydrogen bond geometry (°, Å) in the DCMSP.
Table 3. Simulated wavenumbers (scaled), experimental IR, Raman bands and assignments
for DCMSP.
Table 4. Theoretical electronic absorption spectra of title compound (absorption wavelength λ
(nm), excitation energies E (eV) and oscillator strengths (f)) using TD-DFT/ B3LYP/
6
311++G(d,p) method.
Table 5. Second-order perturbation theory analysis of Fock matrix in NBO basis
corresponding to the intramolecular bonds of the title compound.
Table 6. NBO results showing the formation of Lewis and non-Lewis orbitals.
Table 7. The values of the dipole moment (in D) and the linear polarizability (in 10ꢘꢂꢕ esu)
were calculated using MP2/6 − 311 + +G(d, p)
and for values of the second
hyperpolarizability in (in 10ꢘꢎꢚ esu) we used CAM − B3LYP/6 − 311 + +G(d, p) for
DCMSP embedded molecule in the case static.
Table 8. The values of the linear polarizability (in 10ꢘꢂꢕ esu) were calculated CAM −
B3LYP/6 − 311 + +G(d, p) and for values of the second hyperpolarizability in (in 10ꢘꢎꢚ
esu) we used CAM − B3LYP/6 − 311 + +G(d, p) for DCMSP embedded molecule
(ωꢓinꢓa. u.).
Table 9. DFT/CAM-B3LYP/ 6-311++G(d,p) results for the linear refractive index and third-
order nonlinear susceptibility (10ꢘꢂꢂ m ⁄V ) for the case dynamic (ω = 0.085 a.u.) of the
ꢂ
ꢂ
DCMSP crystal.
2
4

ACCEPTED MANUSCRIPT
Table 1.
Crystallographic data and structure refinement of DCMSP.
Formula
C5 H4 Cl2 N2 O2 S
227.06
Formula Weight
Crystal System
Space group
a, b, c [Å]
triclinic
ꢀ
P1
7.9208(4) 8.6194(5) 14.3769(8)
α, β, γ [°]
V [Å ]
Z
85.404(3) 88.336(3) 63.205(3)
873.31(9)
4
3
3
ρcalcd [g/cm ]
1.727
µ [ /mm ]
0.940
F(000)
456
Crystal Size [mm]
Temperature (K)
λ [ Å ]
0.12 x 0.16 x 0.18
296
0.71073
2.8, 29.1
Theta Min-Max [°]
-10 ≤ h ≤ 10
-11 ≤ k ≤ 11
-19 ≤ l ≤ 19
Index ranges
Rflns.Total.
16835
Unique rflns
4645
Rint
0.029
Observed Data [I > 2.0 sigma(I)]
N , N
R
wR2
Max. and Av. Shift/Error
Min. and Max. Resd. Dens. [e/ Å ] -0.53, 0.70
3895
4677, 258
0.0414
0.1173
0.00, 0.00
ref
par
3

ACCEPTED MANUSCRIPT
Table 2.
Hydrogen bond geometry (°, Å) in the DCMSP
A—H
Å)
H···B
(Å)
A—H···B
(Å)
A—H···B
(°)
A—H···B
(
C4—H13···O10
C12—H14···O11
0.93
0.96
2.29
2.40
3.201(3)
3.216(7)
166
143

ACCEPTED MANUSCRIPT
Table 3
Simulated wavenumbers (scaled), experimental IR, Raman bands and assignments for
DCMSP.
B3LYP/6-311++G(d,p)
ν(IR)
(cm )
ν(Raman)
(cm )
Scaled
Raman
activity
77.7954
34.2458
Assignment (%)
-1
-1
IR activity
-
1
(cm )
3
3
114
064
4.6075
3.00E-04
3101
3058
3101
3060
νCH(100)
ν CH (50)
asy
3
ν CH (54)
asy
3
3
043
949
0.023
70.6943
161.083
-
-
-
ν CH (23)
asy
3
ν CH (46)
sy
3
2
0.2021
2946
ν CH (27)
sy
3
νCN(13)
νCC(39)
νCN(33)
1
1
509
499
385.678
313.329
7.9379
1512
-
1511
-
17.2595
δ CH (53)
asy
3
1
1
395
392
13.0804
7.4147
2.966
1400
-
1399
-
δ CH (11)
asy 3
γHCSC(11)
δ CH (36)
asy
3
7.5257
δ CH (17)
asy 3
γHCSC(17)
νCN(19)
1
1
356
301
105.52
1.0988
1.3296
1363
1297
1357
1298
δCHI(35)
δ CH (32)
sy
3
11.3561
δ CH (27)
sy
3
δNCN(26)
νCN(22)
1
267
105.715
2.4962
1255
1258
νCC(12)
1
1
245
201
223.053
10.3479
12.3783
5.7275
1250
1198
1246
1214
ν SO (48)
νCN(39)
νCC(15)
as
2
δNCN(20)
δCNC(20)
δCHI(52)
δCCN(13)
νCC(10)
1
176
101.403
107.469
3.4799
1.6009
-
1174
1083
1
1
084
063
1082
142.063
6.6406
32.5791
36.646
-
1066
972
ν SO (42)
s
2
9
63
970
δNCN(10)
δCH (16)
γHCSC(30)
3
9
48
29.7999
2.0631
-
946
δCH (14)
3
9
41
0.3273
2.3708
-
941
γHCSC(39)
γHCSC(13)

ACCEPTED MANUSCRIPT
8
8
36
04
16.878
0.0838
0.5473
-
835
802
γHCPh(77)
νSC(20)
νClC(25)
18.7522
800
νClC(30)
νClC(10)
7
89
145.096
0.0477
-
-
τNCNC(16)
τCNCN(24)
νSC(65)
γCHI(10)
γOCCS(12)
γClCNC(34)
νSC(10)
7
6
6
5
48
94
05
82
0.0523
107.481
0.0016
0.0044
0.0022
15.2176
0.5517
0.0426
743
692
612
-
741
694
611
585
5
4
4
02
84
20
96.1014
10.5672
17.802
3.274
4.2465
4.0764
-
-
-
503
501
420
δSO scissoring (11),
2
γOCOS(47)
νSC(13)
δCCl(11),
δSO wagging(29)
2
δCSC(10)
νClC(22)
νClC(18)
δSO twisting (17)
2
δCCl(22)
4
3
3
13
98
24
6.2385
12.0064
3.3673
0.6764
8.0636
1.4614
-
-
-
-
383
-
δSO (26)
2
νClC(27)
νClC(25)
δOSC(23)
γOCCS(54)
OCOC(11)
2
68
0.4623
9.2941
-
272
δSO rocking (11)
2
δOSC(11)
δOSC(56)
γOCCS(10)
δCSC(66)
τCH3(24)
γHCSC(29)
γHCSC(24)
γCCl(15)
δClCN(35)
γCCl(12)
γOCCS(15)
δCSCN(93)
2
2
53
39
3.3337
4.9607
0.5337
4.2871
-
-
253
223
1
90
0.0398
0.0849
-
192
1
1
1
8
1
88
73
39
7
7
0
0.0735
4.2074
0.9527
1.7198
0.4828
-
-
-
-
-
-
0.0156
2.427
0.0108
5.3392
163
129
75
-
a
υ-stretching; δ-in-plane deformation; γ-out-plane deformation; τ-torsion; potential energy
distribution is given in brackets (%) in the assignment column.