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SPECTRAL INVESTIGATIONS AND A
TD-DFT STUDY ON THE SINGLET AND
TRIPLET EXCITED-STATES UV-VIS
ANALYSES OF HETEROCYCLIC 5-
NITRO-1,3-BENZODIOXOLE
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10.1. INTRODUCTION
1,3-Benzodioxoles occur widely in plant products, some of which are known
to show potent antioxidant and antibacterial activities [205]. It has recently been
reported that 1,3-benzodioxole derivatives possess cytotoxic activity against several
human tumour cell lines including human colon carcinoma cells [206] and multidrug-
resistant nasopharyngeal carcinoma cells [207]. On this basis and in pursuing the
interest in the study of new anticancer agents [208-210], the spectroscopic
investigations have been done on a 1,3-benzodioxole derivative such as 5-nitro-1,3-
benzodioxole (NBD).
Recently, Yonggang He et al., [211] have performed cation vibrational energy
levels of 1,3-benzodioxole obtained via zero kinetic energy photoelectron spectroscopy.
Synthesis and characterization of asymmetric o- and m-nitrobenzoic acids with a
1,3-benzodioxole skeleton has been performed by Masaya Suzuki et al., [205]. A
computational study on reminiscence of benzene in the spectroscopy of 1,3-benzodioxole
has been reported by Emanuela Emanuele et al., [212]. So far, the vibrational spectra
and the theoretical calculations of 5-nitro-1,3-benzodioxole (NBD) have not been
reported except in this work. Therefore, we have studied the spectral investigations of
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NBD. The main objective of the present study is to investigate in detail vibrational
spectral analysis and electronic properties of NBD using ab initio/HF and
DFT/B3LYP computations.
10.2. EXPERIMENTAL SECTIONS
The pure 5-nitro-1,3-benzodioxole (NBD) was obtained from Lancaster
Company, USA that is of spectroscopic grade and hence used for recording the
spectra as such without any further purification. The FT-IR of NBD was measured in
the BRUKER IFS 66V spectrometer in the range 4000-400 cm-1
. The FT-Raman
spectrum of NBD was also recorded in BRUKER RFS 100/S instrument equipped
with Nd:YAG laser source operating at 1064 nm wavelength and 150 mW powers in
the range 3500-50 cm-1
.
10.3. QUANTUM CHEMICAL CALCULATIONS
The first task for the computational work was to determine the optimized
geometry of the compound using GAUSSIAN 09W [45] program package. It is well
known in the quantum chemical literature that the hybrid B3LYP [20,21] method
based on Becke’s three parameter functional of DFT yields a good description of
harmonic vibrational wavenumbers for small and medium sized molecules than HF
and flexible basis set 6-311++G level to perform accurate calculations on the title
compound were chosen. However, the frequency values computed at these levels
contain known systematic errors. In general theoretical calculations symmetrically
overestimate the vibrational wavenumbers. Hence, the vibrational frequencies
theoretically calculated are scaled down by using MOLVIB 7.0 version written by
Tom Sundius [55,44]. After scaling with a scaling factor, the deviation from the
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experiment is more reliable. Analytic frequency calculations at the optimized
geometry were done to confirm the optimized structure to be an energy minimum and
to obtain the theoretical vibrational spectra. Using above mentioned methods the
following analyses such as electronic properties, NBO, HOMO-LUMO, NMR, UV-
VIS and thermal properties were carried out. The first hyper polarizability was
calculated to study the NLO properties.
10.4. RESULT AND DISCUSSION
10.4.1. Molecular geometry
The numbering of the atoms in 5-nitro-1,3-benzodioxole (NBD) is depicted in
Fig 10.1. The optimized geometries of NBD with HF and B3LYP methods are listed
in Table 10.1. Previously reported structural parameters determined by microwave
spectroscopy [213] are also included for comparison in Table 10.1. The bond lengths
calculated at the HF level are obviously underestimated, whereas DFT level makes
them closer to the microwave data. The overall structural parameters at B3LYP level
represent definite improvements on the HF results.
10.4.2. Vibrational spectral analysis
The title compound, NBD, has C1 point group symmetry, consists of 17 atoms,
so it has 45 normal vibrational modes. The calculated vibrational wavenumbers using
different methods were compared with the experimentally observed values.
Comparison of the frequencies calculated at HF and DFT with the experimental
values (Table 10.2) reveal the overestimation of the calculated vibrational modes due
to neglect of anharmonicity in real system. To certain extend inclusion of electron
correlation in the density functional theory; reduce the values of the frequencies a
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Fig. 10.1: Molecular structure of 5-nitro-1,3-benzodioxole�
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little. Although basis sets are sensitive, the computed harmonic vibrations are only
marginal as observed in the DFT values using 6-311++G. It is customary to scale
down the calculated harmonic frequencies in order to develop the agreement with the
experiment without affecting the level of calculations. The scaled calculated
frequencies minimize the root-mean square difference between calculated and
experimental frequencies for bands with definite identifications. The FT-IR and FT-
Raman spectra of CNA are shown in Figs 10.2 and 10.3 and they are interpreted as
follows.
10.4.2.1. C–H vibration
The aromatic structure shows the presence of C–H stretching vibration in the
region 3000–3100 cm-1
[62]. There are three stretching vibrations are identified for
C–H stretching at 3112, 3035 and 3000 cm-1
. The theoretically computed (scaled)
values for C–H vibrations using B3LYP/6-311++G method show a good agreement
with recorded spectrum. The bands due to the ring C–H in-plane bending are usually
observed in the region 1000–1300 cm-1
. In the title compound, these vibrations are
observed at 1225, 1065 and 1055 cm-1
. The C–H out-of plane bending vibrations are
usually observed between 750 and 1000 cm-1
[214]. In the present compound, these
vibrations are observed at 850, 808, and 730 cm-1
.
10.4.2.2. CH2 vibrations
The ethyl group of the title compound gives rise to four stretching modes and
the couple of scissoring, wagging, rocking and twisting modes. The band observed at
2966 cm-1
in FT-IR is assigned to asymmetric stretching mode of the ethyl group of
NBD. The band at 2920 cm-1
is designated as symmetric stretching modes. One of the
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Fig
. 10.
2: F
T-I
R s
pec
tru
m o
f 5-
nit
ro-1
,3-b
enzo
dio
xole
.
Fig
. 10.
3: F
T-R
aman
sp
ectr
um
of
5-n
itro
-1,3
-ben
zod
ioxo
le.
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CH2 deformation modes called CH2 scissoring generates band at 1515 in FT-IR and
1505 in FT-Raman spectra, respectively. The band at 1410 cm-1
in FT-IR and 1430
cm-1
in FT-Raman are attributed to CH2 wagging vibrations. The peak at 1160 cm-1
in
FTIR is ascribed to ethyl twisting vibrations. The title compound display the peak at
1070 cm-1
in FT-IR spectrum has been ethyl rocking vibration. All these ethyl
vibrations are agreed well with the literature [215].
10.4.2.3. Nitro group vibrations
Aromatic nitro compounds have strong absorptions due to asymmetric and
symmetric stretching vibrations of the NO2 group at 1570–1485 and 1370–1320 cm-1,
respectively. Hydrogen bonding has a little effect on NO2 asymmetric stretching
vibrations [65]. In NBD, two FTIR bands at 1540 and 1350 cm-1
have been assigned
to asymmetric and symmetric stretching modes of NO2. Aromatic nitro compounds
have a band of weak to medium intensity in the region 590–500 cm-1
[62] due to the
out of plane bending deformations mode of NO2 group. This is observed in NBD at
505 cm-1
. The in-plane NO2 deformations vibrations have a week to medium
absorption in the region 775–660 cm-1
[216]. In NBD, NO2 deformations are found at
780 and 710 cm-1
and NO2 twisting vibration is observed at 30 cm-1
. These vibrations
are not affected much by other modes. This is a unique occurrence of NO2.
10.4.2.4. C-N vibrations
NO2 group attached to ring carbon atom C5 of NBD gives rise to three
vibrational modes such as C-N stretching, C-N in-plane and out-of-plane bending. In
the present study, the band at 1110 cm-1
in FT-IR is assigned to νC-N mode which is
well agreed with the literature [217]. The assignments of in-plane and out-of-plane
C-N bending modes are made at 610 and 380cm-1
, respectively.
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10.4.2.5. Skeletal vibrations
The bands observed in the infrared spectrum of NBD at 1615, 1590, 1468,
1375, 1278 and 1250 cm-1
are ascribed to the benzene ring stretching modes and the
corresponding FT-Raman bands are appeared at 1620, 1610, 1460, 1378, 1288 cm-1
.
The ring2 stretching vibrations are observed at 1035, 910, 895, 678 cm-1
in FT-IR
spectrum and at 1030, 900 cm-1
in the FT-Raman spectrum. Also, the benzene ring
and ring2 in-plane vibrations are assigned to the observed frequencies at 580, 542 cm-1
and 525, 493, 402 cm-1
in FT-IR and FT-Raman spectra, respectively. The out-of-
plane bending vibrations are established at 345, 312, 210 155, 75 cm-1
in FT-Raman
spectrum. All these vibrations are agreed well with the literature [215].
10.5. HOMO-LUMO ANALYSIS
The orbital energy level analysis for NBD at the BLYP level shows EHOMO
(highest occupied molecular orbital) and ELUMO (lowest unoccupied molecular orbital)
values of -7.524 eV and -4.62 eV, respectively. The magnitude of the HOMO–LUMO
energy separation could indicate the reactivity pattern of the molecule. The charge
densities of the HOMO and LUMO are shown in Fig.10.4. The HOMO is located on
the C5–C6, C7–C8 and C9–C4 bonds of the benzene ring (C1–C6) as well as on the
oxygen atoms of nitro group with only minor population, O2 and O3 and CH2 group
of dioxole ring. The LUMO in NBD, however, populates on the carbon atoms (C4, C5
and C6) and the NH2 group of the benzene ring and O1 atom. The population of
LUMO on the bonding between C1–C2, C6–C8 and N1–C9 forms antibonding
orbitals. Minor population can be located on the oxygen atoms of the methoxy groups.
These population shows that the charge transfer is taking place from NO2 group to
rings. According to molecular orbital theory, HOMO and LUMO are two important
factors influencing the bioactivity.
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�
(a) HOMO Energy=-7.524 eV
�
�
�
�
�
�
�
�
�
(b) LUMO Energy= - 4.62 eV
�
Fig. 10.4: Charge densities of (a) HOMO and (b) LUMO of 5-nitro-1,3-benzodioxole.
�
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10.6. NBO ANALYSIS
NBO analysis has been performed on the compound at the B3LYP/6-311++G
level in order to elucidate the intramolecular, rehybridization and delocalization of
electron density within the compound.
The larger the E(2)
(energy of hyperconjugative interactions) value, the more
intensive is the interaction between electron donors and electron acceptors, i.e. the
more donating tendency from electron donors to electron acceptors the greater the
extent of conjugation of the whole system. Delocalization of electron density between
occupied Lewis-type (bond or lone pair) NBO orbitals and formally unoccupied (anti-
bond or Rydgberg) non-Lewis NBO orbitals correspond to a stabilizing donor–
acceptor interaction.
The intramolecular interactions are formed by the orbital overlap between
�(C- C), �*(C-C), �(C-C), �*(C-C) bond orbital which results intramolecular charge
transfer (ICT) causing stabilization of the system. These interactions are observed as
increase in electron density (ED) in C-C anti-bonding orbital that weakens the
respective bonds. These intramolecular charge transfer (���*, ���*) can induce
large nonlinearity of the compound.
The strong intramolecular hyper conjugation interaction of the � and �
electrons of C-C, C-H, C-N and C-Cl to the anti C-C, C-H and C-N bond leads to
stabilization of some part of the ring as evident from Table 10.3. The intramolecular
interactions are formed by the orbital overlap between bonding (C-C) and (C-C)
antibond orbital which results intramolecular charge transfer (ICT) causing
stabilization of the system. These interactions are observed as increase in electron
density (ED) in C-C anti-bonding orbital that weakens the respective bonds. The
� ����
strong intramolecular hyper conjugative interaction of the � electron of (C4- C9)
distribute to �*(C5-C6) and �*(C7-C8) of the ring which leads to strong
delocalization of 74.6844 and 89.7468 kJ/mol, respectively. The �(C5-C6) bond is
interacting with �*(C4–C9) and �*(C8-C9) with the energies 84.6423, and 69.0778
KJ/mol for NBD. The same �(C5-C6) bond interacts with �*(N15-O17) with the
highest energy 143.679 KJ/mol resulting the strong stabilization of NBD. The
electrons of LP(3) O16 can be redistributed into �*(N15–O17) with the potential of
744.3754 kJ/mol with external perturbations, then, the redistributed electrons of the
�* (N15–O17) can be easily transported to its neighbouring anti-bond of �*(C5 –C6)
with the higher interaction energies of 66.7348 kJ/mol. Thus, the electrons of NO2
group are transported into ring of the compound.
10.7. UV-VIS ANALYSIS
10.7.1. Singlet excited states and absorption spectra
Calculated absorption spectrum with their oscillator strengths, assignment,
configurations, excitation energies, excitations with maximum coefficients and the
experimental values are summarized in Table 10.4. The corresponding simulated UV–
VIS absorption spectrum of NBD, presented as oscillator strength against wavelength,
are presented in Fig.10.5. In order to explain the electronic transition characteristics,
the relative frontier molecular orbital compositions of NBD in acetonitrile are
provided in Table 10.4. Fig. 10.5 shows that the lowest lying distinguishable
singlet�singlet first absorption band, originating from excited state 5, was at 239.40
nm. This absorption band was assigned as a HOMO – LUMO+1 transition with the
excitation energy of 5.1789 eV. The lowest lying absorption peak of 2, at 315.39 nm,
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is best described as a HOMO-1->LUMO transition with the oscillator strength of
0.1490. For band 3, it appeared that the HOMO-LUMO transition originating from
excited state 1, located at 401.69 nm.
10.7.2. Triplet excited states and emission properties
The triplet excited states of NBD were computed, using acetonitrile as a
medium, based on their lowest lying triplet state geometry. The corresponding triplet
excited state emission spectrum of NBD is presented in Fig. 10.6. The energies of the
triplet excited states are provided relative to the singlet ground state in the lowest
lying triplet state-optimized geometry. In NBD, only one emission band at 475.80 nm
has been observed with the excitation energy of 2.6058 eV.
10.8. NMR SPECTRAL ANALYSIS
Full geometry optimization of NBD was performed at the gradient corrected
DFT using the hybrid B3LYP method based on Becke’s three parameters functional
of DFT. Then, gauge-including atomic orbital (GIAO)1H,
13C
15N and
17O NMR
chemical shift calculations of the compound have been made by same method. The
computed and experimental 1H,
13C
15N and
17O NMR chemical shifts are tabulated in
Table 10.5. Atom positions were numbered according to the Fig. 10.1. Aromatic
carbons give signals in overlapped areas of the spectrum with chemical shift values
from 100 to 150 ppm [79,80]. In our present investigation, the chemical shift values
of aromatic carbons are in the range 104.3849–119.8578 ppm. The nitro group which
is an electronegative functional group polarizes the electron distribution; therefore the
calculated 13
C NMR chemical shift value of C5 bonded to nitro group is high
compared to other carbons, observed at 146.8189 ppm. Similarly, C8 and C9 atoms
�
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�
�
�
�
�
�
�
�
�
Fig. 10.5: Singlet excited state absorption spectrum of 5-nitro-1,3-benzodioxole. �
�
�
��
�
�
�
� �
�
�
�
�
�
�
�
�
�
�
Fig. 10.6: Triplet excited state emission spectrum of 5-nitro-1,3-benzodioxole
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have larger 13
C NMR chemical shifts (152.6968 and 147.1116 ppm, respectively) than
the other ring carbon atoms. The signals for aromatic protons in the rings were
observed at 5.8818 - 7.1165 ppm. The chemical shift of 15
N ranges from 0 to 900 ppm
[155]. Since in our investigation, the peak at 428.5877 ppm is assigned to N15 of
nitro group.17
O has a very wide chemical shift range which for small molecules
partially compensates for its broad signals. The chemical shift of 17
O ranges from -40
to 1120 ppm [156]. In the title compound, the peaks at 793.4796 and 792.1667 ppm
are assigned to nitro group oxygens, O17 and O16, respectively. Correspondingly the
dioxole ring oxygen’s chemical shifts (O1 and O3) are obtained at 158.0709 and
143.8771 ppm. Obviously, the oxygen chemical shifts of nitro group are larger than
other oxygen due to the environment.
10.9. FIRST HYPERPOLARIZABILITY
The electronic and vibrational contributions to the first hyperpolarizability
have been studied theoretically for many organic and inorganic systems. The values
of the first hyperpolarizability were found to be quite large for the so-called push–pull
molecules, i.e. p-conjugated molecules with the electron donating and the electron
withdrawing substituents attached to a ring, compared to the monosubstituted systems
[24]. This type of functionalization of organic materials, with the purpose of
maximizing NLO properties, is still commonly followed route.
The first hyperpolarizability of title compound is calculated using B3LYP/6-
311++G method, based on the finite-field approach. In the presence of an applied
electric field, the energy of a system is a function of the electric field. First order
hyperpolarizability (�) is a third rank tensor that can be described by 3×3 ×3 matrices.
� ����
The components of are defined as the coefficients in the Taylor series expansion of
the energy in the external electric field. When the external electric field is weak and
homogeneous, this expansion becomes:
0
� � �� � � ��� � � �
1 1E = E -� F - � F F - � F F F +...
2 6
where E0 is the energy of the unperturbed molecule, F� is the field at the origin, and
��, ��� and ���� are the components of dipole moment, polarizability and the first order
hyperpolarizability, respectively. The total static dipole moment (�) and the mean first
hyperpolarizability (�) using the x, y, z components, they are defined as:
( )1
2 2 2 2
x y z� = � +� +�
( )1
2 2 2 2
x y z�= � +� +�
where
x xxx xyy xzz� =� +� +�
y yyy xxy yzz� =� +� +�
z zzz xxz yyz� =� +� +�
Since the value of hyperpolarizability (�) of the GAUSSIAN 09W output is
reported in atomic units (a.u.), the calculated values should have been converted into
electrostatic units (e.s.u) (1 a.u. = 8.639 × 10−33
e.s.u). The total molecular dipole
moment and first hyperpolarizability are 5.7519 Debye and 13.497 × 10−30
e.s.u,
respectively and are depicted in Table 10.6. Total dipole moment of title compound is
approximately four times greater than those of urea and first hyperpolarizability of
title compound is 36 times greater than those of urea (� and � of urea are 1.3732
Debye and 0.3728 × 10−30
esu obtained by HF/6-311G(d,p) method).
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10.10. THERMODYNAMIC PROPERTIES
On the basis of vibrational analysis, the statically thermodynamic functions
such as heat capacity (C0
p,m), entropy (S0
m ), and enthalpy changes (H0
m ) for NBD
were obtained from the theoretical harmonic frequencies and listed in Table 10.7.
From this table, it can be observed that these thermodynamic functions are increasing
with temperature ranging from 100 to 1000 K due to the fact that the molecular
vibrational intensities increase with temperature as shown Fig 10.7.
10.11. CONCLUSION
The vibrational wavenumbers of 5-nitro-1,3-benzodioxole were calculated and
the complete assignments were performed on the basis of the total energy distribution
(TED) of the vibrational modes. Results are compared with experimental observed
FT-IR and FT-Raman spectra. After scaling down, the calculated wavenumbers show
good agreement with experimental spectra. The NBO analysis of 5-nitro-1,3-
benzodioxole showed effective energy interaction between the nitrogen lone pair
LP(3) O16 and the sigma antibonding orbitals of the N15–O17 bond. The ground state
geometry and excited state geometry have been theoretically investigated on
absorption and emission properties of 5-nitro-1,3-benzodioxole. The positions of
hydrogen and carbon atoms of title compounds are determined with help of computed
1H and
13C NMR chemical shifts. The electronic properties were also discussed
theoretically. Non-linear optical behaviour of the examined molecule was investigated
by the determination of the hyperpolarizability. These results indicate that the 5-nitro-
1,3-benzodioxole is a good candidate of nonlinear optical materials.
�
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�
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�
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�
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�
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�
� �
� �
� � �
Fig. 10.7: Thermodynamic parameters of 5-nitro-1,3-benzodioxole at various temperature
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Tab
le 1
0.1:
O
pti
miz
ed p
aram
eter
s of
5-n
itro
-1,3
-ben
zod
ioxo
le b
y H
F a
nd
B3L
YP
met
hod
s u
sin
g 6-
311+
+G
bas
is s
et.
Val
ues
V
alu
es
Val
ues
HF
B
3LY
P
HF
B
3LY
P
HF
B
3LY
P
Bon
d
len
gth
(Å
) 6-
311+
+G�
6-31
1++
G�
Exp
. va
luea
Bon
d a
ngl
es (
o )
6-31
1++
G
6-31
1++
G
Exp
. va
luea
Dih
edra
l an
gles
(o )
6-31
1++
G
6-31
1++
G
O1
-C2
1
.47
92
1
.47
13
-
C2
-C1
-C8
106
.599
4
106
.605
8
- C
8-O
1-C
2-C
3
0.0
174
0
.00
61
O1
-C8
1
.39
38
1
.38
76
1
.36
8
O1
-C2
-O3
106
.414
5
106
.560
3
- C
8-O
1-C
2-H
13
-1
17
.98
46
-1
18
.068
2
C2
-O3
1
.47
2
1.4
648
1
.43
2
O1
-C2
-H1
3
109
.034
7
109
.047
- C
8-O
1-C
2-H
14
1
18
.020
4
118
.080
4
C2
-H1
3
1.0
855
1
.08
65
1
.09
4
O1
-C2
-H1
4
109
.035
6
109
.047
1
- C
2-O
1-C
8-C
7
179
.991
-1
80
.002
9
C2
-H1
4
1.0
855
1
.08
65
1
.09
4
O3
-C2
-H1
3
109
.486
2
109
.474
2
- C
2-O
1-C
8-C
9
-0.0
10
7
-0.0
03
8
O3
-C9
1
.40
25
1
.39
59
-
O3
-C2
-H1
4
109
.486
6
109
.474
1
- C
1-C
2-O
3-C
9
-0.0
17
7
-0.0
06
1
C4
-C5
1
.40
83
1
.40
53
1
.40
0
H1
3-C
2-H
14
1
13
.158
2
113
.030
1
- H
13
-C2
-O3
-C9
1
17
.685
8
117
.786
7
C4
-C9
1
.37
36
1
.37
14
1
.38
7
C2
-O3
-C9
106
.519
7
106
.514
5
- H
14
-C2
-O3
-C9
-1
17
.722
5
-11
7.7
99
C4
-H1
0
1.0
767
1
.07
78
1
.07
8
C5
-C4
-C9
115
.616
7
115
.569
- C
2-O
3-C
9-C
4
-179
.990
3
180
.003
C5
-C6
1
.39
61
1
.39
33
1
.40
0
C5
-C4
-H1
0
121
.186
5
121
.152
2
- C
2-O
3-C
9-C
8
0.0
117
0
.00
4
C5
-N1
5
1.4
592
1
.45
32
-
C9
-C4
-H1
0
123
.196
7
123
.278
8
- C
9-C
4-C
5-C
6
0.0
003
0
.00
01
C6
-C7
1
.40
21
1
.39
96
-
C4
-C5
-C6
123
.001
3
123
.058
4
- C
9-C
4-C
5-N
15
-1
79
.999
5
180
.000
2
C6
-H1
1
1.0
777
1
.07
89
-
C4
-C5
-N1
5
118
.141
7
118
.105
2
- H
10
-C4
-C5
-C6
-1
79
.999
5
180
.000
2
C7
-C8
1
.38
23
1
.38
-
C6
-C5
-N1
5
118
.857
1
18
.836
3
- H
10
-C4
-C5
-N1
5
0.0
008
0
.00
03
C7
-H1
2
1.0
785
1
.07
92
-
O1
6-N
15-O
17
1
23
.482
4
123
.600
7
- C
5-C
4-C
9-O
3
-179
.997
8
180
.001
C8
-C9
1
.39
62
1
.39
42
-
C5
-C6
-C7
119
.969
1
119
.997
7
12
0.5
C
5-C
4-C
9-C
8
-0.0
00
1
-0.0
00
1
N1
5-O
16
1
.26
85
1
.26
18
-
C5
-C6
-H1
1
119
.007
8
118
.951
5
- H
10
-C4
-C9
-O3
0
.00
2
0.0
009
N1
5-O
17
1
.26
87
1
.26
2
- C
7-C
6-H
11
121
.023
1
121
.050
8
- H
10
-C4
-C9
-C8
1
79
.999
7
-180
.000
2
C6
-C7
-C8
117
.062
3
117
.003
7
11
8.8
C
4-C
5-N
15
-O1
7
0.0
002
0
.0
C6
-C7
-H1
2
121
.684
1
121
.698
- C
6-C
5-N
15
-O1
6
0.0
005
0
.00
02
C8
-C7
-H1
2
121
.253
6
121
.298
4
- C
6-C
5-N
15
-O1
7
-179
.999
5
180
.000
2
O1
-C8
-C7
127
.553
2
127
.616
4
- C
5-C
6-C
7-C
8
-0.0
00
3
-0.0
00
1
O1
-C8
-C9
110
.325
6
110
.239
8
- C
5-H
6-C
7-H
12
1
79
.999
8
-180
.000
2
C7
-C8
-C9
122
.121
2
122
.143
8
12
0.7
H
11
-C6
-C7
-C8
1
79
.999
5
-180
.000
1
O3
-C9
-C4
127
.629
7
127
.692
9
- H
11
-H6
-H7
-H1
2
-0.0
00
4
-0.0
00
2
O3
-C9
-C8
110
.140
8
110
.079
7
- C
6-C
7-C
8-O
1
179
.998
6
-180
.000
8
C4
-C9
-C8
122
.229
4
122
.227
4
- C
6-C
7-C
8-C
9
0.0
005
0
.00
01
C5
-N1
5-O
16
1
18
.424
2
118
.372
1
- H
12
-C7
-C8
-O1
-0
.00
15
-0
.00
07
C5
-N1
5-O
17
1
18
.093
4
118
.027
2
- H
12
-H7
-C8
-C9
-1
79
.999
6
180
.000
2
�����
O1
-C8
-C9
-O3
-0
.00
07
-0
.00
01
O1
-C8
-C9
-C4
-1
79
.998
7
180
.000
8
C7
-C8
-C9
-O3
1
79
.997
8
-180
.000
9
C7
-C8
-C9
-C4
-0
.00
03
0
.0
C4
-C5
-C6
-C7
-0
.00
01
0
.0
C4
-C5
-C6
-C11
1
80
.000
1
18
0.0
N1
5-C
5-C
6-C
7
179
.999
7
179
.999
9
N1
5-C
5-C
6-C
11
-0.0
00
1
-0.0
00
1
C4
-C5
-N1
5-O
16
180
.000
3
18
0.0
a R
efer
the
refe
rence
[ 2
13]
�����
Tab
le 1
0.2:
V
ibra
tion
al a
ssig
nm
ents
of
exp
erim
enta
l fr
equ
enci
es o
f 5-
nit
ro-1
,3-b
enzo
dio
xole
alo
ng
wit
h c
alcu
late
d f
req
uen
cies
b
y H
F a
nd
B3L
YP
met
hod
s u
sin
g 6-
311+
+G
bas
is s
et.
Cal
cula
ted
fre
qu
ency
(cm
-1)
Exp
erim
enta
l fr
equ
ency
(c
m-1
) H
F/6
-311
++
G
B3L
YP
/6-3
11+
+G
S
.N
o F
T-I
R
FT
-Ram
an
Un
scal
ed
Sca
led
U
nsc
aled
S
cale
d
Ass
ign
men
ts w
ith
TE
D
(%)
1
31
12
-
32
73
31
29
3
25
2
31
18
ν
CH
(98
)
2
30
35
-
32
62
30
55
3
24
2
30
42
ν
CH
(89
)
3
30
00
-
32
43
30
11
3
22
2
30
08
ν
CH
(97
)
4
29
66
-
31
80
29
72
3
15
6
29
71
C
H2as
(88
)
5
29
20
-
30
99
29
45
3
08
0
29
31
C
H2ss
(90
)
6
16
15
1
62
0
16
63
16
35
1
65
6
16
22
B
enze
ne
rin
g
stre
tch
ing
(89
)
7
15
90
1
61
0
16
46
16
11
1
64
0
15
99
B
enze
ne
rin
g
stre
tch
ing
(91
)
8
15
40
-
15
58
15
65
1
56
2
15
49
N
O2 a
s
9
15
15
1
50
5
15
31
15
22
1
52
0
15
11
C
H2 s
cis
10
1
46
8
14
60
1
49
0
14
77
1
48
9
14
70
B
enze
ne
rin
g
stre
tch
ing
(90
)
11
1
41
0
14
30
1
45
5
14
22
1
45
0
14
19
C
H2
wag
12
1
37
5
13
78
1
41
5
13
79
1
41
7
13
78
B
enze
ne
rin
g
stre
tch
ing
(88
)
13
1
35
0
13
45
1
40
6
13
67
1
39
9
13
57
N
O2ss
14
1
27
8
12
88
1
29
9
12
89
1
30
3
12
81
B
enze
ne
rin
g
stre
tch
ing
(90
)
15
1
25
0
- 1
28
0
12
66
1
27
6
12
56
B
enze
ne
rin
g
stre
tch
ing
(92
)
�����
16
1
22
5
- 1
25
9
12
39
1
25
8
12
27
b
CH
(7
9)
17
1
16
0
- 1
17
2
11
67
1
17
5
11
62
C
H2 t
wis
t(7
4)
18
1
11
0
- 1
16
0
11
22
1
16
4
11
12
ν
CN
(89
)
19
1
07
0
- 1
14
0
10
65
1
14
3
10
68
C
H2 r
ock
(69
)
20
10
65
1
11
1
10
61
1
11
5
10
61
b
CH
(77
)
21
1
05
5
1
07
3
10
71
1
07
5
10
71
b
CH
(79
)
22
1
03
5
10
30
1
01
0
10
33
1
02
0
10
38
R
ing 2
str
etch
(90
)
23
9
10
9
00
9
86
92
1
99
3
91
1
Rin
g 2
str
etch
(89
)
24
8
95
-
92
0
90
8
92
7
90
3
Rin
g 2
str
etch
(91
)
25
8
50
-
91
9
86
6
91
9
85
6
�C
H(6
7)
26
8
08
-
87
8
81
9
87
3
81
9
�C
H(6
8)
27
7
80
-
85
3
79
2
85
8
78
6
NO
2sc
is(6
5)
28
7
30
8
05
8
09
74
9
80
9
73
9
�C
H(6
6)
29
7
10
7
15
7
94
72
8
79
1
71
7
NO
2 r
ock
(68
)
30
6
78
-
71
9
69
1
71
8
68
2
Rin
g 2
stre
tch
(88
)
31
6
10
-
71
9
62
2
70
7
61
1
bC
-N(6
9)
32
5
80
-
70
3
59
9
69
9
55
9
Ben
zen
e ri
ng b
end
(68
)
33
5
42
5
38
6
85
55
5
68
5
54
3
Ben
zen
e ri
ng b
end
(69
)
34
-
52
5
58
9
53
0
59
1
52
8
Ben
zen
e ri
ng b
end
(71
)
35
-
50
5
57
1
51
1
56
6
50
9
NO
2 w
ag(6
4)
36
-
49
3
54
8
50
4
54
6
49
2
Rin
g2
ben
d(6
5)
37
-
40
2
44
2
41
1
43
8
40
9
Rin
g2
ben
d(6
6)
�����
38
-
38
0
40
1
39
9
39
7
38
8
�C
N(6
7)
39
-
34
5
35
2
35
5
35
3
34
9
Ben
zen
e ri
ng o
ut
of
pla
ne
ben
din
g(6
2)
40
-
31
2
33
5
32
1
32
6
31
9
Ben
zen
e ri
ng o
ut
of
pla
ne
ben
din
g(6
6)
41
-
21
0
23
8
21
8
23
2
21
5
Rin
g2
ben
d t
ors
ion
(55
)
42
-
15
5
21
0
16
6
20
4
15
9
Ben
zen
e ri
ng o
ut
of
pla
ne
ben
din
g(5
8)
43
-
14
0
14
8
14
5
12
7
14
3
Bu
tter
fly(5
5)
44
-
75
9
3
82
7
0
80
R
ing2
ben
d t
ors
ion
(54
)
45
-
30
9
0
45
6
0
40
N
O2 t
wis
t(5
8)
Ab
bre
viat
ion
s:
ν –
str
etch
ing;
b –
ben
din
g;
sym
d –
sym
met
ric
defo
rmat
ion;
asym
d –
as
ym
metr
ic d
eform
ati
on;
trig
d-
trig
onal
def
orm
atio
n; �-o
ut
of
pla
ne
ben
din
g;
t –
tors
ion;
twis
t –
tw
isti
ng
; ss
– s
ym
met
ric
stre
tchin
g;
ass
- as
ym
met
ric
stre
tchin
g;
ipr
– i
n p
lane
rock
ing;
opr
– o
ut
of
pla
ne
rock
ing;
scis
– s
ciss
ori
ng;
rock –
rock
ing;
wag
– w
aggin
g.
� ����
Table 10.3: Selected second order perturbation energies E(2) associated with i->j delocalization in gas phase using B3LYP/6-311++G method and basis set.
Donor (i)
Type Acceptor
(j) Type
E(2)
(kJ mol-1) �j – �i
a
(a.u.) F(i,j)b
(a.u)
C5 - C6 �* 74.6844 0.29 0.066 C4 -C9 �
C7 - C8 �* 89.7468 0.29 0.072
C4 - C9 �* 84.6423 0.28 0.068
C8 - C9 �* 69.0778 0.28 0.061 C5 - C6 �
N15 - O17 �* 143.679 0.13 0.065
C4 - C9 �* 80.9186 0.29 0.067 C7 - C8 �
C5 - C6 �* 91.253 0.29 0.072
LP(2) O1 n2 C7 - C8 �* 120.374 0.33 0.093
LP(2) O3 n2 C4 - C9 �* 111.796 0.34 0.089
LP(2) O17 n2 C5 – N15 �* 44.3922 0.58 0.070
LP(2) O17 n2 N15 - O16 �* 79.0776 0.63 0.098
LP(2) O16 n2 C5 - N15 �* 44.9362 0.58 0.071
LP(2) O16 n2 N15 - O17 �* 79.3705 0.63 0.099
LP(3) O16 n3 N15 - O17 �* 744.3754 0.11 0.130
N15-O17 �* C5 - C6 �* 66.7348 0.16 0.061
� ����
Table 10.4: Singlet computed excitation energies, oscillator strength, electronic transition configuration wavelength of 5-nitro-1,3-benzodioxole using TD-DFT/B3LYP/6-311++G method and basis set inacetonitrile .
Excited States
EE (eV)
Oscillator strength
f Configuration
CI expansion coefficient
Wave length (nm)
1 3.0866 0.1415 42 → 44 0.14448
43 → 44 0.69077 401.69
2 3.4395 0.0000 41 → 44 0.70247 360.47
3 3.9312 0.1490 42 →44 0.68133
43 →44 -0.14350
43 → 45 -0.10942
315.39
4 3.9801 0.0001 39 → 44 0.70238 311.51
5 5.1789 0.1461 38 → 44 -0.12336
42 → 46 -0.20418
43 →45 0.64533
239.40
6 5.6293 0.0390 38 → 44 0.66297
40 →44 -0.12883
43 → 46 -0.16108
220.25
����
Tab
le 1
0.5:
C
alcu
late
d 13
C, 1
H, 1
5 N a
nd
17O
N
MR
iso
trop
ic c
hem
ical
sh
ifts
(al
l va
lues
in
pp
m)
of 4
-nit
ro-1
,3-b
enzo
dio
xole
usi
ng
DF
T/B
3LY
P/6
-311
++
G m
eth
od a
nd
bas
is s
et
Ato
ms
Ch
emic
al
shie
ldin
g
Ch
emic
al
shif
t A
tom
s C
hem
ical
shie
ldin
g
Ch
emic
al
shif
t A
tom
s C
hem
ical
shie
ldin
g
Ch
emic
al
shif
t
C8
2
9.7
68
8
15
2.6
96
8
H1
1
24
.76
56
7
.11
65
N
15
-1
70
.18
77
42
8.5
87
7
C9
3
5.3
54
14
7.1
11
6
H1
0
25
.01
41
6
.86
8
O1
7
-47
3.4
79
6
79
3.4
79
6
C5
3
5.6
46
7
14
6.8
18
9
H1
2
26
.00
03
5
.88
18
O
16
-4
72
.16
67
79
2.1
66
7
C6
6
2.6
07
8
11
9.8
57
8
H1
4
26
.36
88
5
.51
33
O
1
16
1.9
29
1
15
8.0
70
9
C2
7
5.6
10
7
10
6.8
54
9
H1
3
26
.36
91
5
.51
3
O3
1
76
.12
29
14
3.8
77
1
C7
7
5.8
14
3
10
6.6
51
3
C4
7
8.0
80
7
10
4.3
84
9
� ���
Table 10.6: Theoretical first hyperpolarizability of 5-nitro-1,3-benzodioxole using DFT/B3LYP/6-311++G method and basis set.
Parameters Values(a.u)
�xxx 1582.9896125
�xxy -297.6044822
�xyy 26.5978724
�yyy 111.5558416
�xxz -0.3246258
�yyz 0.0042833
�xzz -58.7957849
�yzz -4.2255076
�zzz -0.0090297
� 13.497×10−30
e.s.u
� ����
Table 10.7: Calculated specific heat capacity (C0p,m), entropy (S0
m), and
enthalpy (�H0m) at various temperature of 5-nitro-1,3-
benzodioxole using B3LYP/6-311++G method and basis set.
T (K) C0
p,m S0
m H0
m
100.00 290.71 67.97 4.95
200.00 349.63 108.02 13.68
298.15 401.06 152.73 26.46
300.00 402.00 153.57 26.75
400.00 452.18 196.29 44.29
500.00 499.94 231.79 65.76
600.00 544.79 259.95 90.40
700.00 586.59 282.16 117.55
800.00 625.47 299.88 146.68
900.00 661.65 314.26 177.42
1000.00 695.39 326.08 209.45
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