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9973
ISSN 2286-4822
www.euacademic.org
EUROPEAN ACADEMIC RESEARCH
Vol. III, Issue 9/ December 2015
Impact Factor: 3.4546 (UIF)
DRJI Value: 5.9 (B+)
Molecular Structure, Vibrational Spectroscopic and
HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
KHULOOD O. KAZAR
Chemistry Department, College of Science
Kerbala University, Kerbala, Iraq
MOHAMMED ALAA ABDUL ZAHRA
Chemistry Department, College of Education of Pure Sciences
Kerbala University, Kerbala, Iraq
NASEER K. SHREEF
Chemistry Department, College of Science
Kerbala University, Kerbala, Iraq
LOAY G. ABD ALI
Chemistry Department, College of Science
Kerbala University, Kerbala, Iraq
MANAL ABED MOHAMMED
Chemistry Department, College of Education of Pure Sciences
Kerbala University, Kerbala, Iraq
KHLOWD M. JASEM
Chemistry Department, College of Science
Kerbala University, Kerbala, Iraq
Abstract:
Quantum chemical calculations of energies, geometries and
vibrational wave numbers of m-bromoacetophenone were carried out
by DFT levels of theory using CEP-121G basis set. The study is
extended to calculate the HOMO- LUMO energy gap, ionization
potential, electron affinity, global hardness, chemical potential, global
electrophilicity, polarizability and thermodynamic properties of m-
bromoacetophenone. A complete vibrational assignment aided by the
theoretical harmonic frequency analysis has been proposed. The
calculated HOMO and LUMO energies show the charge transfer occurs
in the molecule. The harmonic vibrational frequencies calculated have
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9974
been compared with experimental FTIR spectra. The observed and the
calculated frequencies are found to be in good agreement.
Key words: DFT, Ionization potential, electron affinity, energy gap,
and IR spectrum.
Introduction
Aromatic ketones such as acetophenone, propiophenone and
their derivatives have great analytical and pharmaceutical
applications. m-bromoacetophenone is used as an intermediate
product for the preparation of fenoprofen which is an anti-
inflammatory, analgesic and antipyretic drug [1,2]. Chemically
it is called as 1-(3-bromophenyl)-ethanone. Alzheimer’s disease
(progressive form of percentile dementia) is treated with the
drug which was invented from 3-bromoacetophenonone [3]. It is
used as a reaction initiator with organopolysiloxane, which is
the base polymer to prepare silicone rubber [4]. It is also used
as a coupling partner in microwave accelerated cross- coupling
of a range of aryl boronic acids with aryl chlorides [5].
Substituted bromoacetophenone are used to synthesis
dicationic diarylpyridines which are used as nucleic acid
binding agents [6]. The title compound is used as an
antibacterial agent [7]. It is also used as a photo radical
polymerization initiator to provide a cross linkable silyl group
terminated vinyl polymer [ 8]. DFT calculations of vibrational
spectra of many organic systems [9,10], have shown promising
conformity with experimental results. Therefore, in these
present investigation DFT techniques is employed to study the
complete vibrational spectra of the title compound and to
identify the various normal modes with greater wave number
accuracy. Several other investigations have been carried out on
the title compound and its derivatives [11-15]. Literature
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9975
survey reveals that to the best of our knowledge no
DFT/B3LYP/CEP-121G frequency calculations of 3-
bromoacetophenone have been reported so far. It may be due to
difficulty in interpreting the spectra of these molecules because
of their complexity and low symmetry. Due to the absence of
vapour phase infrared spectra, a complete vibrational
assignment is not available in the literature. Hence the present
investigation was undertaken to study the vibrational spectra
of this molecule completely and to identify the various normal
modes with greater wave number accuracy. Assuming C1 point
group symmetry the band assignments have made.
Density Functional Theory (DFT) calculations have been
performed to support our wave number assignments. The
theoretically predicted IR intensities is well in agreement with
that of experimental spectral data.
2. Computational Details
The entire calculations conducted in the present work were
performed at B3LYP level included in the Gaussian 03W
package [16] program together with the CEP-121G basis set
function of the density functional theory (DFT) utilizing
gradient geometry optimization [17] . All the geometries were
optimized using CEP-121G basis sets using density functional
theory (DFT) [18] employing the Becke’s three-parameter
hybrid functional [19] combined with Lee-Yang-Parr correlation
[20] functional (B3LYP) method. The DFT partitions the
electronic energy as E = ET+EV+EJ+EXC, where ET, EV, and
EJ are the electronic kinetic energy, the electron nuclear
attraction and the electron-electron repulsion terms
respectively. The electron correlation is taken into account in
DFT via the exchange correlation term EXC, which includes the
exchange energy arising from the antisymmetric of the
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9976
quantum mechanical wave function and the dynamic
correlation in the motion of individual electrons [21].
The optimized structural parameters were used in the
vibrational frequency calculations at the DFT level to
characterize all stationary points as minima. Then vibrational
averaged nuclear positions of m-bromoacetophenone is used for
harmonic vibrational frequency calculations resulting in IR
frequencies together with intensities. The DFT hybrid B3LYP
functional also tends to overestimate the fundamental modes in
comparison to the other DFT methods; therefore, scaling factors
have to be used to obtain considerably better agreement with
experimental data. Thus according to the work of Rauhut and
Pulay [22], a scaling factor of 0.963 has been uniformly applied
to the B3LYP calculated wavenumbers.
Finally, calculated normal mode vibrational frequencies,
provide thermodynamic properties by way of statistical
mechanics. By combining the results of the Gaussview program
[23] with symmetry considerations, vibrational frequency
assignments were made with high degree of accuracy. There is
always some ambiguity in defining internal coordination.
However, the defined coordinate form complete set and matches
quite well with the motions observed using the Gaussview
program. To achieve a close agreement between observed and
calculated frequencies, the least square fit refinement
algorithm was used. For the plots of simulated IR and Raman
spectrum, pure Lorentzian band shapes were used with a
bandwidth of 10 cm-1. HOMO-LUMO energy gaps has been
computed and other related molecular properties are
calculated.
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9977
3. Results and Discussion
3.1. Molecular Geometry
The optimized structure parameters of m-bromoacetophenone
calculated by DFT-B3LYP level with the CEP-121G basis set
are listed in the Table 1 in accordance with the atom
numbering scheme given in Fig.1. The molecular structure,
XRD studies have been studied for the compound m-
chloroacetophenone and m-nitroacetophenone. Since the
compound chosen for the present study has close structural
relation with the above-mentioned compounds, the molecular
parameters have been taken from m-chloroacetophenone and
m-nitroacetophenone [24,25]. Table 1 compares the calculated
bond lengths and angles for m-bromoacetophenone with those
experimentally available from X-ray diffraction data [24, 25].
From the theoretical values, we can find that most of the
optimized bond angles are slightly larger than the experimental
values, due to the theoretical calculations belong to isolated
molecules in gaseous phase and the experimental results belong
to molecules in solid state. In spite of the differences, calculated
geometric parameters represent a good approximation and they
are the bases for calculating other parameters, such as
vibrational frequencies and thermodynamic properties.
3.2 Energies
Table 2 shows the values of the total energy and electronic
states for the analyzed structures and the energy gap of the m-
bromoacetophenone. The total energy for studied molecule as a
linear function of bromine substituted to the acetophenone
molecule. It is clear that from table 2, the total energy is
increase and depending on the atomic number of halogen atom,
and it is observed that substitution of bromine (electron-
accepting) causes decreasing the HOMO and LUMO energy, it
is known that the electron accepting substituents decreasing
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9978
the LUMO and HOMO energies [26], and energy gap decreased.
The frontier orbital (HOMO and LUMO) of the chemical species
are very important in defining its reactivity[27] The LUMO-
HOMO energy gaps of m-bromoacetophenone is small than that
of the original molecule, with decreasing energy gap, electrons
can be easily excited from the ground state. The table 2 shows
these energies of studied molecule, the molecule has C1
symmetry.
B3LYP functional used in this study has a high efficient
to calculate the electronic properties for the organic studied
molecules, such as ionization potentials (IP), electron affinities
(EA), chemical potential (K), absolute hardness (η), absolute
softness (S), electrophilic index (ω). The properties are
computed by the way that is based on the differences between
the HOMO and the LUMO energies of the neutral molecule and
is known as orbital-vertical (Koopmans’ theorem).The
calculated properties for each variable clearly reveal that the
ionization potential for the m-bromoacetophenone is higher
than that for the original molecule, this indicates that this
molecule needs high energy to become cation comparing with
the acetophenone. The strength of an acceptor is measured by
its electron affinity (EA) which the energy released when
adding one electron to LUMO. An acceptor must have a high
EA, adding the Br atom to acetophenone molecule leads to
increasing the ability of the electron affinity for the molecule, as
we see in table 4. The Koopmans’ theorem is a crude but useful
and fast approach [26,28]. The behavior of electronegativity,
softness and electrophilic index for the studied molecules shows
the magnitude larger than for the original molecule, adding the
Br atom gives the molecules more softness. The larger the
HOMO-LUMO orbital energy gap, the harder the molecule. The
hardness has been associated with the stability of the chemical
system[27]. In the present study, HOMO-LUMO gap and
hardness of the acetophenone molecule is larger than those for
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9979
m-bromoacetophenone as shown in table 2 and table 4, which
clearly indicates that the molecule is the most stable .
3.4 Molecular polarizability and the Dipole moment
One of the objectives of the present investigation is to study the
effect of the basis sets B3LYP/ CEP-121G levels on molecular
polarizability of acetophenone and its m-bromoacetophenone
derivative using the Gaussian03W program. In this study, the
computation of the molecular polarizability <a > was reported,
m-Bromoacetophenone molecule has polarizability larger than
that in acetophenone. The calculated dipole moment values
show that the acetophenone molecule is highly polar and more
than m-bromoacetophenone. The calculated dipole moment and
polarizabilities by DFT method are summarized in Table 3.
3.5 Thermodynamic properties
On the basis of vibrational analysis at B3LYP/ CEP-121G level,
several thermodynamic parameters are calculated and are
presented in Table 5. Table 5 showed that acetophenone
compound less entropy ∆Sᵒ and larger in the ∆Uᵒ, ∆Hᵒ, ∆Aᵒ and
∆Gᵒ properties than those of its m-bromoacetophenone
derivative, this because Br substituent effect.
3.6 Electronic densities
The electron densities for acetophenone molecule and its m-
bromoacetophenone derivative were listed in (Table 6) .
Electron densities are different between them because the Br
substituent effect .
3.7 Vibrational assignments
3.7.1 C-H Vibrations
The aromatic structure shows the presence of C-H stretching
vibrations in the region 3250 cm-1 - 2950 cm-1 which is
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9980
characteristic region for the ready identification of C-H
stretching vibrations and particularly the regions 3250 cm-1 -
3100 cm-1 for asymmetric stretching and 3100 cm-1 - 2950 cm-1
for symmetric stretching modes of vibration [29]. For most
cases, the aromatic compound C-H vibration absorption bands
are usually weak; in many cases it is too weak for detection. In
this region, the bands are not affected, appreciably by the
nature of substituents. In the present work, for the m-
bromoacetophenone, the FTIR bands observed at 3238 cm-1,
3220 cm-1 and 3197 cm-1 have been assigned to C-H stretching
vibration. The B3LYP level at CEP-121G gives slightly
different frequency values at 3211 cm-1, 3201 cm-1 and 3164 cm-1
as indicated in Table 7. In general the aromatic C-H stretching
vibrations calculated theoretically are in good agreement with
the experimentally reported values [30,31] for di substituted
benzene in the region 3200 - 2900 cm-1. The out of plane
bending mode of C-H vibration is found well in agreement with
the experimentally predicted in the region 1000-600 cm-1 [32].
At B3LYP/ CEP-121G , 982 and 834 cm-1 , is calculated . The
observed FTIR value of 996 cm-1 is in excellent agreement with
982 cm-1 of B3LYP/ CEP-121G results. The out of plane C-H
deformation vibrations of m-bromoacetophenone is
experimentally predicted in the region 636 and 996 cm-1
coincides satisfactorily with the calculated values in the same
region. The aromatic C-H in-plane bending modes of benzene
and its derivatives are observed in the region 1300-1000 cm-1
[33]. The C-H in plane bending vibrations assigned even though
found to be contaminated by C-CH3 stretch are found in
literature [34,35], while the experimentally observed values for
m-bromoacetophenone is at 1268 cm-1 . The C-H in-plane
bending vibration of m-bromoacetophenone coincides
satisfactorily with the experimentally observed values in this
region.
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9981
3.7.2 C-Br Vibrations
The compound under consideration m-bromoacetophenone has
a bromine substitution. The heavier mass of bromine obviously
makes the C-Br stretching mode to appear in longer
wavelength region. Bellamy has assigned the region 700-600
cm-1 for the C-Br stretching [36,37]. Based on this, the band
observed at 660 cm-1in FTIR is assigned to C-Br stretching. The
theoretically calculated value for m-bromoacetophenone 662
cm-1 is well agreed with the experimental value.
3.7.3 Methyl group Vibrations
The m-bromoacetophenone compound under consideration
possess a CH3 group in the side substitution chain. There are
nine fundamentals one can expect to a CH3 group, namely the
symmetrical stretching in CH3 (CH3 sym. stretch) and
asymmetrical stretching (in plane hydrogen stretching mode);
the symmetrical (CH3 sym. deform) and asymmetrical (CH3
asym. deform) deformation modes; in-plane rocking, out-of-
plane rocking, twisting and bending modes [38]. Each methyl
group has three stretching vibrations, one being symmetric and
other two asymmetric. The frequencies of asymmetric
vibrations are higher than the symmetric one [39].
The theoretically computed values 3016 cm-1 for CH3
symmetric stretching and 3091 cm-1, 3137 cm-1for CH3
asymmetric stretching shows an excellent agreement with the
range allotted by Williams and Fleming [40]. CH3 asymmetric
and symmetric in-plane bending are observed at 1470 and 1315
cm-1 in FTIR, respectively [41]. The torsion vibrations are not
observed in the FTIR because these appear at very low
frequency. The observations at 41 cm-1 in m-
bromoacetophenone is in agreement with theoretical results of
similar compounds, table 7.
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9982
3.7.4 C=O Vibrations
The C=O stretching vibration in acetophenone and m-
bromoacetophenone has a main contribution in the mode, with
B3LYP/ CEP-121G) predicted frequencies at 1624 cm-1 (Table
7), this is in agreement with the very strong experimental
frequencies at 1635 cm-1 in FTIR spectrum. The out of plane
C=O bending vibration mode of m-bromoacetophenone with the
experimental frequency of 140 cm-1 found to be in excellent
agreement. The above conclusions are in agreement with the
literature value [42].
3.8 Isodesmic reaction
The stabilizing effect of a substituent is often assessed by using
isodesmic reactions (conserved bond type). A positive energy
difference (∆) (scheme 1) indicates stabilization of the reactant
by substituent [43], so the negative ∆ refers to more reactivity
for reactants (m-bromoacetophenone) than those for products
(acetophenone).
4. Conclusion
The results of the study lead to the following conclusions. (i)
The proper frequency assignments for the compounds is
performed for the first time from the FTIR. The experimental
FTIR spectra for m-bromoacetophenone was compared with the
theoretical DFT calculations of the vibrational spectra of the
molecule. (ii) The equilibrium geometries of compounds were
determined and analyzed both at DFT level utilizing CEP-121G
basis set, Geometry optimization for m-bromoacetophenone has
been found in a good agreement with experimental data. (iii)
The HOMO-LUMO energy gap and other related molecular
properties were discussed and reported. The presence of the Br
substituent decreases the energy gap of the molecule, this is
one of the important properties obtained in this work, and a
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9983
small energy gap means small excitation energies of manifold of
the exited states. (iv) molecular polarizability was calculated
and the results were discussed , the results showed that the Br
substitution leads to increase the average polarizability and
cause to more reactive than original molecule. (v) The electronic
properties (IP, EA, K, η, S, ω) were calculated by using DFT.
Figure (1) : The molecules under study
acetophenone
m-bromoacetophenone
Table 1: Optimized geometrical parameters of acetophenone and
bromoacetophenone isomers, bond length(Å), Interaxial angles(ᵒ)
Expt.[24,25]
Our data
bond angles
Expt.[24,25]
Our data
bond length
Molecules
-
120.085
H12-C3-C4
-
1.097
C8-H17
Acetophenone
-
120.021
C5-C4-C3
-
1.510
C6-C7
-
121.310
H14-C5-C4
-
1.532
C10-C8
-
120.388
C6-C1-C2
-
1.087
C4- H13
-
119.795
C6-C7-O9
-
1.265
C7-O9
-
118.855
H10-C1-C2
-
1.408
C5-C4
-
121.716
C8-C7-C6
-
1.413
C2-C3
-
120.076
H11-C2-C1
-
1.420
C1-C6
120.000
120.578
H13-C3-C4
1.113
1.097
C10-H15
m-Bromo
Acetophenone
121.000
122.021
C5-C4-C3
1.351
1.514
C6-C8
120.000
121.538
H14-C5-C6
1.512
1.531
C10-C8
120.200
120.492
C6-C1-C2
1.881
1.972
C4-Br7
118.900
119.634
C6-C8-O9
1.208
1.264
C8-O9
120.000
121.365
H11-C1-C2
1.395
1.409
C5-C4
120.000
121.819
C10-C8-C6
1.395
1.417
C2-C3
119.000
120.076
H12-C2-C1
1.395
1.422
C1-C6
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9984
Table 2: Total energy, Electronic states and Energy gap for molecules
calculated by DFT with B3LYP system and CEP-121G basis set .
Molecule
Symmetry
Energy
(a.u)
Electronic States(a.u)
Energy
Gaps (a.u)
HOMO
LUMO
acetophenone
C1
-65.8964
-0.2597
-0.0728
0.1869
m-Bromoacetophenone
C1
-78.6637
-0.2638
-0.0843
0.1757
Table 3: calculated dipole moment μ (debye), components of αi (i =
xx,yy,zz) an average of the dipole polarizability ˂ α ˃ in atomic units
for molecules.
Molecule
μ
αxx
αyy
αzz
˂ α ˃
acetophenone
3.4867
126.317
98.521
45.104
89.98
m-Bromoacetophenone
1.4260
155.397
116.150
47.160
106.23
Table 4 Comparison of related molecular properties of acetophenone
with its bromoacetophenone isomers calculated by DFT with B3LYP
system and CEP-121G basis set .
Molecule
IP
EA
K
S
η
χ
acetophenone
0.2597
0.0728
-0.1663
5.348
0.0934
0.1663
m-Bromoacetophenone
0.2638
0.0843
-0.1741
5.571
0.0897
0.1741
Table 5 : Comparison of Thermodynamic properties of acetophenone
with its bromo -acetophenone isomers calculated by DFT with B3LYP
system and CEP-121G basis set .
∆Gᵒ
(kcal/mole)
∆Aᵒ
(kcal/mole)
∆Sᵒ
(cal/mole K)
∆Hᵒ
(kcal/mole)
∆Uᵒ
(kcal/mole)
Molecule
65.55728
64.96486
85.330
90.99842
90.406
acetophenone
56.94054
56.34812
95.579
85.43742
84.845
m-bromo
acetophenone
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9985
Table 6. Electronic densities for molecules calculated by DFT with
B3LYP system and CEP-121G basis set
m-Bromoacetophenone
Atom
Acetophenone
Atom
4.258151
C1
4.185615
C1
4.112427
C2
4.16965
C2
4.119201
C3
4.14233
C3
4.393534
C4
4.143278
C4
4.131932
C5
4.254717
C5
3.638567
C6
3.651727
C6
6.851167
Br7
4.128597
C7
4.122377
C8
4.592329
C8
6.125523
O9
6.132994
O9
4.591251
C10
0.819933
H10
0.776626
H11
0.843527
H11
0.833219
H12
0.842802
H12
0.807417
H13
0.83968
H13
0.782089
H14
0.783683
H14
0.84146
H15
0.845938
H15
0.807518
H16
0.811585
H16
0.807542
H17
0.811614
H17
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9986
Table 7: Vibrational wavenumbers obtained for 3-bromoacetophenone
at B3LYP/ CEP-121G [harmonic frequency (cm-1)] IR intensities (km
mol-1).
Characterization of
Normal modes
3-Br.acetophenone
acetophenone
exp cm-1
IR int.
cal cm-1
IR int.
cal cm-1
τCH3 torsion
-
0.782
41
0.899
22
lattice vibration
-
0.943
59
4.88
45
γ C=O + γCH
-
7.97
140
0.077
160
CH3 torsion
-
2.54
144
6.10
231
CH3 torsion+ βCH
-
0.020
154
0.791
369
γ C-Br
-
0.597
186
-
-
β C-Br
-
3.19
276
-
-
β C-H
-
6.355
295
2.088
468
γ C-H
430
0.638
371
27.29
570
γ C-H
-
0.473
432
9.66
616
γ C-C-C
538
4.09
472
0.672
628
β C-C-O
590
1.41
478
38.67
710
CH3 twisting+ υ C-Br
636
30.37
576
-
-
υ C-Br
660
0.119
662
-
-
ring breathing
683
14.32
661
0.475
889
β C-C-C
785
16.47
701
3.531
972
γ C-H
838
26.97
768
20.32
979
γ C-H
901
59.53
834
1.763
1002
γ C-H
960
13.70
919
0.978
1020
γ C-H
987
1.18
975
5.536
1033
γ C-H
996
16.66
982
2.96
1048
δ ring + γC-H
1020
6.85
998
0.682
1069
CH3 twisting
1064
4.16
1044
1.639
1086
γ C-H + β C-C
1091
38.80
1067
7.002
1103
β C-H
1101
0.78
1068
0.576
1192
υ C-C+ β C-H
1124
0.40
1096
18.23
1210
δ C-H
1186
6.16
1116
214.85
1280
υ C-C+ βC-H
1268
6.10
1199
6.290
1338
ρ C-H
1315
269.04
1270
4.183
1355
γ C-C
1357
18.10
1319
37.03
1421
CH3 wagging
1405
2.19
1340
16.94
1462
υ C-C
1450
39.15
1427
9.92
1495
δ C-H3
1470
0.53
1483
11.32
1497
υ C-C
1494
10.54
1494
6.805
1518
υ C-C
1516
17.24
1509
106.13
1586
υ C-C
1566
143.7
1573
62.59
1618
υ C-C
1592
29.16
1607
16.28
1629
υ C=O
1635
50.93
1624
6.988
1612
υs CH3
3066
5.28
3016
11.90
3090
υas CH3
3127
10.08
3091
21.39
3133
υas CH3
3153
20.60
3137
0.504
3147
ring (υ C-H)+ υ C-H3
3197
10.99
3164
13.76
3160
ring (υ C-H)+ υ C-H3
3220
14.79
3201
36.89
3174
ring (υ C-H)
3238
2.19
3211
9.68
3194
Khulood O. Kazar, Mohammed Alaa Abdul Zahra, Naseer K. Shreef, Loay G. Abd Ali,
Manal Abed Mohammed, Khlowd M. Jasem- Molecular Structure, Vibrational
Spectroscopic and HOMO- LUMO Studies of m-Bromoacetophenone by
Quantum Chemical Investigations
EUROPEAN ACADEMIC RESEARCH - Vol. III, Issue 9 / December 2015
9987
Scheme 1. Evaluation of substituted effects (energies ∆, in a.u)
( ) = ( ) - ( ) = - 0.0067 a.u
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