Optical, Fluorescence with quantum analysis of hydrazine (1, 3- Dinitro Phenyl) by DFT and Ab initio approach

Article abstract of DOI:10.1016/j.molstruc.2017.12.046

Experimental and computational study of molecular structure, vibrational and UV-spectral analysis of Hydrazine (1, 3- Dinitrophenyl) (HDP) derivatives. The crystal was grown by slow cooling method and the crystalline perfection of single crystals was evaluated by high resolution X-ray diffractometry (HRXRD) using a multicrystal X–ray diffractometer. Fluorescence, FT-IR and FT-Raman spectra of HDP crystal were recorded. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) followed by scaled quantum force field methodology (SQMFF). NMR studies have confirmed respectively the crystal structure and functional groups of the grown crystal. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) result complements the experimental findings. The calculated MESP, UV, HOMO-LUMO energies show that charge transfer done within the molecule. And various thermodynamic parameters are studied. Fukui determines the local reactive site of electrophilic, nucleophilic, descriptor.

Full text of DOI:10.1016/j.molstruc.2017.12.046

Accepted Manuscript
Optical, Fluorescence with Quantum analysis of Hydrazine (1, 3- Dinitro Phenyl) by
DFT and Ab initio approach
D. Cecily. Mary Glory, K. Sambathkumar, R. Madivanane, G. Velmurugan, R.
Gayathri, S. Nithiyanantham, M. Venkatachalapathy, N. Rajkamal
PII:
S0022-2860(17)31666-6
10.1016/j.molstruc.2017.12.046
MOLSTR 24665
DOI:
Reference:
To appear in: Journal of Molecular Structure
Please cite this article as: D. Cecily. Mary Glory, K. Sambathkumar, R. Madivanane, G. Velmurugan, R.
Gayathri, S. Nithiyanantham, M. Venkatachalapathy, N. Rajkamal, Optical, Fluorescence with Quantum
analysis of Hydrazine (1, 3- Dinitro Phenyl) by DFT and Ab initio approach, Journal of Molecular
Structure (2017), doi: 10.1016/j.molstruc.2017.12.046
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Highlights
•
•
•
•
•
Hydrazine (1, 3- Dinitro Phenyl) crystal
Optical, Fluorescence studies, Molecular structure – XRD,
FTIR, FT-Raman, UV – stretching and opticals.
Vibrations – HOMO-LUMO, SQMFF, NMR, MESP calculations.
DFT, Ab intio calculation,

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Fig caption
Figure 1. Cleaved Crystal of Hydrazine (1, 3- Dinitrophenyl).
Figure 2. Powder XRD of Hydrazine (1, 3- Dinitrophenyl).
Figure 3. High-resolution X-ray diffraction curve of Hydrazine (1, 3- Dinitrophenyl).
Figure 4. Emission spectrum of Hydrazine (1, 3- Dinitrophenyl).
Figure 5. Molecular structure of Hydrazine (1, 3- Dinitrophenyl).
Figure 6. Various conformers of Hydrazine (1, 3- Dinitrophenyl).
Figure 7. Comparison of observed and calculated IR spectra of Hydrazine (1, 3-
Dinitrophenyl) (a) observed in solid phase (b) calculated with B3LYP\6-311+G(d,p) and (c)
calculated with B3LYP\6-311++G(d,p) level.
Figure 8. Comparison of observed and calculated Raman spectra of Hydrazine (1, 3-
Dinitrophenyl) (a) observed in solid phase (b) calculated with B3LYP \ 6 -311+G(d,p) and
(c)calculated with B3LYP\6-311++G(d,p) level.
Figure 9. Frontier orbital energy of Hydrazine (1, 3- Dinitrophenyl).
Figure 10. Experimental NMR spectrum of Hydrazine (1, 3- Dinitrophenyl).
Figure 11. UV spectrum of Hydrazine (1, 3- Dinitrophenyl).
Figure 12. The total electron density surface of Hydrazine (1, 3- Dinitrophenyl).
Figure 13. The contour map of electrostatic potential surface of Hydrazine (1, 3-
Dinitrophenyl).
Figure 14. The molecular electrostatic potential surface of Hydrazine (1, 3- Dinitrophenyl).
Figure 15. Correlation graphic of thermodynamic parameters and Temperature for entropy
(S), heat capacity at constant pressure (Cp), Gibb’s free energy(G) energy change of
Hydrazine (1, 3- Dinitrophenyl).
Figure 16. Correlation graphic of condensed fukui function of Hydrazine (1, 3-
Dinitrophenyl).

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Figure..1.
Figure..2.

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Figure.3.
Figure .4.

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Figure .5.

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A
B
C
D
Figure. 6.

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Figure.7

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Figure. 8.

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(First excited state)
ELUMO= -3.37eV
∆
E = 3.49eV
EHOMO
= -6.85eV
(Ground State)
Figure.9.

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Figure. 10.

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Figure .11.

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Figure. 12.
Figure. 13.

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Figure. 14.

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s
Cp
G
350
300
250
200
150
100
50
0
0
50
100
150
200
250
300
Temperature(Kelvin)
Figure .15.
Figure. 16.

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1
Optical, Fluorescence with Quantum analysis of Hydrazine (1, 3- Dinitro
Phenyl) by DFT and Ab initio approach
1
,2
2,3
, 4
5
D. Cecily. Mary Glory, K. Sambathkumar R. Madivanane, G. Velmurugan,
6
7
8
8
R. Gayathri S. Nithiyanantham, , M.Venkatachalapathy, N.Rajkamal
1
Research and Development Centre, Bharathiar University. Coimbatore, India-641046.
2
Idhaya College of Arts and Science for Women, Puducherry, India-605008.
3
PG.& Research Department of Physics, (Crystal growth centre), A.A.Govt.Arts College,
Villupuram, Tamilnadu, India- 605602.
4
Department of Physics, Mahatma Govt. College, Maye, Puducherry, India- 673311.
5
Department of Chemistry, Indian Institute of Technology Bombay, Mumbai, India-400076.
6
Department of Physics, Cauvery College for Women, Tiruchirappalli, India- 620018.
7
Post Gradute and Research Department of Physics, (Solid state devices and Thin film laboratory
Divisions), Thiru. Vi. Kalyanasundaram Govt Arts and Science College, Thiruvaur, Tamilnadu,
India - 610003. (Affiliated to Bharathidasan University, Thiruchirapalli)
8
PG & Research Department of Physics, Thiru.A.Govindasamy Govt Arts College, Tindivanam,
Tamilnadu, India – 604002.
Corresponding author : s_nithu59@rediffmail.com
Contact: +91 9840980869
Abstract
Experimental and computational study of molecular structure, vibrational and UV-spectral
analysis of Hydrazine (1, 3- Dinitrophenyl) (HDP) derivatives. The crystal was grown by slow
cooling method and the crystalline perfection of single crystals was evaluated by high resolution
X-ray diffractometry (HRXRD) using a multicrystal X–ray diffractometer. Fluorescence, FT-IR
and FT-Raman spectra of HDP crystal were recorded. The assignments of the vibrational spectra

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2
have been carried out with the help of normal co-ordinate analysis (NCA) followed by scaled
quantum force field methodology (SQMFF). NMR studies have confirmed respectively the
crystal structure and functional groups of the grown crystal. The energy and oscillator strength
calculated by Time-Dependent Density Functional Theory (TD-DFT) result complements the
experimental findings. The calculated MESP, UV, HOMO-LUMO energies show that charge
transfer done within the molecule. And various thermodynamic parameters are studied. Fukui
determines the local reactive site of electrophilic, nucleophilic, descriptor.
Key words: HDP, HRXRD, DFT, FMO Analysis, NMR.
1
. Introduction
Hydrazones and hydrazides compounds are well known to possess various kinds of biological
activities [1]. Hydrazone derivatives are used as fungicides, and in the treatment of diseases such
as tuberculosis, leprosy and mental disorders etc. The complexes of various hydrazones and
hydrazide are reported to act inhibitors of enzymes [2]. Many substituted hydrazides and
hydrazones are employed in the treatment of psychotic and psychoneurotic conditions.
Carboxylic acid hydrazones are known to exhibit strong antibacterial activities which are
enhanced by complexation with metal ions. The study of biological activity on Hydrazine (1,3-
dinitrophenyl) (HDP) proved that HDP is an important material for biological applications.
Dinitrophenyl hydrazine is the constituents in various biomedical, pharmaceutical and related
products and etc., [3, 4]. To our knowledge, the vibrational spectra and the theoretical
calculations of Hydrazine (1,3-dinitrophenyl) have not been reported so far. In the present work
the FT-IR, FT-Raman and UV-Visible-NIR spectral analysis were used. Quantum chemical
computations have been recently used as an effective tool in the vibrational analysis of drug
molecules, biological compounds and natural products, whereas substituted benzene derivatives

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3
with high optical non-linearity are very promising materials for future optoelectronics and non-
linear optical applications. Synthesis and grown crystal give Non-linear optical effects of
compound depend on the polarizability of organic material are generally contribution from the
lattice components because of the weak intermolecular bonding and hence possesses the high
degree of delocalization. Single crystal X-ray diffraction study shows that HDP crystallizes in a
monoclinic system. By combining all these facts, the present study has been aimed, to investigate
the vibrational spectra of hydrazine (1,3- dinitrophenyl)(HDP) [5 - 9].
Investigations have also been carried out to identify the HOMO-LUMO energy gap, NLO
property of first hyperpolarizability, chemical hardness, chemical potential and delocalization
activity of the electron clouds in the optimized molecular structure. So, in this work, the
vibrational wave numbers, geometrical parameters, modes of vibrations, minimum energy,
proton NMR chemical shifts are calculated. Theoretical studies of bioactive compounds are of
interest in order to gain a deeper insight on their action and thus helping in the design of new
compounds with therapeutic effects. The knowledge of physico-chemical properties and sites of
reaction of title compound will provide a deeper insight of its probable action. Particularly,
molecular electrostatic potential is related to the electronic density and is a very useful descriptor
in understanding sites for electrophilic attack and nucleophilic reactions as well as hydrogen
bonding interactions. The calculated value of molecular and electronic properties is used to
interpret the biological activity of the molecule [10-12].
2
. Experimental procedure
Synthesis and crystal growth
In this experiment, about 85gm (866 mmol) of potassium acetate is added with 35gm
(355.3 mmol) of hydrazine sulfate dissolved in 125ml of hot water in a 400ml beaker with
constant stirring. The mixture is boiled for 5 minutes and then cooled to about 70° C. To this

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7
5ml of alcohol is added and the generated solid is filtered and washed with 75ml of hot alcohol.
The filtered hydrazine solution is used for the next step. To this hydrazine solution1about
0.5gm (512.6 mmol) of 1,3-Dinitrochloro benzene is dissolved in 250 ml of alcohol is added
5
and the mixture is refluxed with stirring for an hour in a flask fitted with stirring and reflux
condenser. In the first ten minutes most of the product separates out. It is then cooled, filtered
and washed with 50ml of hot alcohol to remove unchanged halide and then with 50ml of hot
water. The pure solid weighs 30gm (304.5mmol) and melts at 190–192° C with evolution of gas.
About total yield of 40-42 gm less pure second crop is obtained by distilling half the alcohol
from the filtrate and recrystallized 30ml of from n-butyl alcohol .Alternatively 70% yield of
hydrazine (dinitrophenyl) is obtained by substituting 10gm of NaOH for every 35gm of
potassium acetate by boiling for five minutes without filtering the salt. Crystals were grown by
the slow cooling method by reducing the temperature from 30°C at the rate of 0.1°C per day. The
two important factors influence the habit of growing crystal, (i) the polarity of the solvents and
stirring the solution. (ii) Solvent offering moderate solubility temperature gradient to yield
prismatic growth [5-7].
3
Forming of Single crystal dimension is 8 x 4 x 2 mm was grown (Fig. 1) in a period of 7 days.
All chemical obtain from the Lancaster chemical company, UK, the chemicals were of reagent
grade and used as commercially purchased without additional purification. All solvents were
dried and distilled before use.
3
. Characterization Techniques
Single-crystal X-ray diffraction analysis of HDP was carried out using ENRAF NONIUS
CAD-4 diffractometer with Mo Kα (0.71073 Å) radiation. A PANalytical X’Pert PRO MRD
high-resolution XRD system, with Cu Kα radiation, was employed to assess the crystalline
1

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perfection of grown crystals. The rocking curves of the crystals for the (200) diffraction planes
were recorded in symmetrical Bragg geometry using the (100) natural facets by performing an x
scan with triple-axis geometry. The monochromated X-ray beam incident on the specimen was
obtained using a hybrid two-bounce Ge (220) monochromator with a parabolic multilayer mirror
assembly. The diffracted beam from the specimen was detected using a scintillation detector with
a triple- axis three bounce Ge(220) analyzer. FTIR and FT-Raman spectrum were recorded using
the Perkin Elmer spectrum one FTIR spectrometer by KBr pellet technique and Brucker RFS 27
-1
in the region 4000–400 cm . The NMR spectra recorded using JEOL GSX 400 model at 23 °C.
The experiment was carried out in the frequency range 100 Hz–5 MHz at room temperature. The
grown crystals were tested for their micro hardness property using Shimadzu HMV Vickers’s
micro hardness tester fitted with diamond indenter. UV spectrum was recorded using Shimadzu
model 1601 in the range of 300 – 1000 nm.
3
.1. X-Ray Diffraction analysis
Single crystal X-ray diffraction studies Single crystal X-ray diffraction analysis of the
grown HDP crystal has been carried out to confirm the crystallinity and also to identify the unit
cell parameters. HDP exhibited as a monoclinic structure with space group of P21/c. Also, the
powder XRD pattern recorded are indexed and shown in Fig 2. The lattice parameters were
calculated from single crystal data and the calculated values are given in Table 1 and the final
atomic coordinates are listed in Table 2 with values reported in the literature for the sake of
comparison. The results are in agreement with the earlier reported values [8].
3
.2. High Resolution X-Ray Diffraction
Before recording the diffraction curve to remove the non-crystallized solute atoms
remained on the surface of the HDP crystal and also to ensure the surface planarity, the specimen

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was first lapped and chemically etched in a non-preferential etchent of acetone and water mixture
in 2: 1 volume ratio. Fig 3 shows the high-resolution diffraction curve (DC). The solid line
(convoluted curve) is well fitted with the experimental points represented by the filled rectangles.
On deconvolution of the diffraction curve, it is clear that the curve contains two additional peaks,
which are 125 and 157 arc away from the main peak. These two additional peaks correspond to
two internal structural low angle (tilt angle ≥ 1 arc min but less than a degree) boundaries [9]
whose tilt angles (misorientation angle between the two crystalline regions on both sides of the
structural grain boundary) are 125 and 157 arc sec from their adjoining regions. The FWHM (full
width at half maximum) of the main peak and the low angle boundaries are respectively 102, 96
and 170 arc sec. Though the specimen contains low angle boundaries, the relatively low angular
spread of around 10 arc min of the diffraction curve and the low FWHM values show that the
crystalline perfection is reasonably good. The effect of such low angle boundaries may not be
very significant in many applications, but for the phase matching applications, it is better to
know these minute details regarding crystalline perfection [10].
3
.3. Fluorescence Studies
Fluorescence may be expected generally in molecules that are aromatic or contain
multiple conjugated double bonds with a high degree of resonance stability [11]. Fluorescence
finds wide application in the branches of biochemical, medical, and chemical research fields, for
analyzing organic compounds. It is also used as lighting of fluorescent lamps, LED etc. The
emission spectrum for HDP was recorded using FP-6500 Spectrofluorometer in the range 320 –
5
20 nm (Fig. 4). It is observed that the compound was excited at 320 nm. The emission spectrum
shows a sharp peak at 335 nm due to π - π* transition, and broad peaks at 398 nm is due to n - π*
transition.
3
.4. Computational Methodology

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7
Initial geometry of HDP was optimized using the B3LYP method using of GAUSSIAN
9W package [12]. The vibrational frequency analysis was computed using B3LYP/6-
11++G(d,p) level of theory to determine the nature of a stationary point found by geometry
0
3
optimization. The hyperpolarizability and the chemical shift of the atoms of HDP have been
calculated using B3LYP/6-311++G(d,p) level of theory. The frontier molecular analysis has been
carried out to explain the charge transfer within the compound. The chemical hardness (η) and
chemical potential (µ) have been calculated. The comparison between the calculated and the
observed vibrational spectra helps us to understand the observed spectral features. In order to
improve the agreement of calculated frequencies with experimentally calculated frequencies, it is
necessary to scale down the theoretically calculated harmonic frequencies. Hence, the vibrational
frequencies theoretically calculated at B3LYP/6-311+G(d,p) and 6-311++G(d,p) are scaled down
by using MOLVIB 7.0 version written by Tom Sundius [13,14]. The Raman activities (Si)
calculated by GAUSSIAN 09W package have been suitably adjusted by the scaling procedure
with MOLVIB and subsequently converted to relative Raman intensities (I ) using the following
i
relationship derived from the basic theory of Raman scattering [15-17].
(1)
-1
o i
where ν is the exciting frequency (cm units). ν is the vibrational wave number of the
th
i normal mode, h, c and k are universal constants for cell parameter, and f is the suitably chosen
common scaling factor for all peak intensities.
4
. Results and Discussion
4
.1. Optimized Geometry
The optimized molecular structure and numbering scheme of HDP are represented in Fig
5
. The geometry of the compound under investigation is considered by possessing C point group
1

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8
symmetry. The geometrical parameters of the title compound are given in Table 3. Detailed
description of vibrational modes can be given by means of normal coordinate analysis. The
internal coordinates describe the position of the atoms in terms of distances, and dihedral angles
with respect to an origin atom. The symmetry coordinates are constructed using the set of
internal coordinates. This study explains the full set of 66 standard internal coordinates
(containing 12 redundancies) for HDP (Table 4). From these, a non-redundant set of local
symmetry coordinates were constructed by suitable linear combinations of internal coordinates
following the recommendations of Fogarasi et al [18.19] are summarized in Table 5. In order to
find the most optimized geometry, the energy calculations are carried out for various possible
conformers. The various possible conformers of HDP are shown in Fig 6. In Figure 6 (B) is the
molecule structure of HDP. For the molecules, the global minimum energy calculations are
carried out for four different possible conformers. The (*) represents global minimum energies
obtained for these conformers are listed in Tables. 6. The most stable structure obtained for the
HDP via B3LYP/6-311++G(d,p) level. To check whether the chosen set of symmetric coordinates
contribute maximum to the potential energy associated with the molecule, the TED has been
carried out.
4
.2. Vibrational Frequency Analysis
The title compound consists of 20 atoms and its 54 normal modes distributed amongst
the symmetry spaces as
’
”
3
N-6 = 37 A (in - plane) +17 A (out-of-plane)
(2)
All the vibrational assignments of the 54 fundamentals of HDP along with the experimentally
and theoretically calculated IR, Raman frequencies, IR intensities, Raman activities, and force
constants are presented in Table 7. The FT-IR and FT-Raman spectra of the title compound are

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9
shown in (Figs.7-8), respectively. Since the identification of all normal modes of vibration of
compounds is not trivial, we tried to simplify the problem by considering each compound as
substituted benzene. Such an idea has already been successfully utilized by several workers for
vibrational assignment of compounds containing multiple Homo-Lumo and aromatic rings [4].
4
.2.1. N-H Vibrations
The hetero aromatic molecule containing an N–H group shows its stretching absorption
−
1
in the region 3500–3220 cm . The position of absorption in this region depends upon the degree
of hydrogen bonding, and hence upon the physical state of the sample or the polarity of the
solvent. The vibrational bands due to the N–H stretching are sharper and weaker than those of
NH stretching vibrations by virtue of which they can be easily identified [20]. In our present
2
−
1
study the very weak band observed in FT Raman spectrum at 3176 cm are assigned to N–H
stretching vibration. The theoretically computed wave numbers by B3LYP/6-311++G(d,p)
−
1
method at 3175 cm is attributed to N–H stretching vibration. The in-plane and out-of-plane
bending vibration of N-H group are also supported by the literature [21].
4
.2.2. C−C Vibrations
The benzene possesses six stretching vibrations of which the four with highest wave
-1
numbers occurring near 1650-1400 cm are good group vibrations [21]. With heavy substituents,
the bonds tend to shift to somewhat lower wavenumbers and greater the number of substituents
on the ring, broader the absorption regions. As predicted in the earlier references, in this present
investigation, the C−C stretching (weak- very weak) vibrations observed at 1699, 1687, 1664,
−1
−1
1
651 cm in FT-IR and 1679, 1670 cm very weak band observed in FT-Raman spectrum for
HDP. The theoretically computed wave number by B3LYP/6-311++G(d,p) level at 1795-1687

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1
0
−
1
cm is attributed to C–H stretching vibration. The C−C in-plane and out-of-plane bending
modes of HDP are summarized in Table 7.
4
.2.3. C−N Vibrations
The C–N stretching frequencies in the side chain are a rather difficult task, since there are
problems in identifying these frequencies from other vibrations. The C–N stretching usually lies
−1
in the region 1400–1200 cm , since, mixing of bands is possible in this region [21]. However,
with the help of force field calculations, the C–N vibrations are identified for the title compound.
−1
In this study, the C–N stretching (very strong – strong)vibrations of HDP are found at 1589 cm
−1
in the FT-IR spectra and at 1593, 1574 cm in the FT-Raman spectrum. The theoretically
−
1
computed wave number by B3LYP/6-311++G(d,p) method at 1595-1575 cm is attributed to C–
N stretching vibration. The C−N bending vibrations and deformations are in close agreement
with literature values.
4
.2.4. C−H Vibrations
-1
The aromatic compounds commonly exhibit multiple bands in the region 3100–3000 cm
due to C-H stretching vibrations. In this molecule, the strong to medium strong bands are
-1
observed at 3144, 3098 and 3077 cm assigned to C-H ring stretching vibrations. The
−
1
theoretically computed wave number by B3LYP/6-311++G(d,p) level at 3142-3078 cm is
attributed to C–H stretching vibration. Here, the IR bands are strong, whereas the Raman bands
are weak. The C-H in plane ring bending vibrations normally occurred as a number of strong to
-1
weak intensity sharp bands in the region 1300–1000 cm [21]. The bands for C-H in plane
-1
−1
bending vibrations are identified at 1392 cm for FT-IR spectrum and at 1496, 1373 cm in the
FT-Raman spectrum. The C-H out of plane bending vibrations is normally observed in the region

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1
1
-1
9
50-809 cm . In the present case, the C-H out of plane bending bands is observed at 1003, 975
-1
and 991 cm . Like in plane bending, all the strong to weak bands were observed in FT-IR and
Raman spectrum. The assigned frequencies for C-H vibrations are found to be well within their
characteristic regions and it is infer that, C-H vibrations have not affected by the substitutions.
4
.2.5. NO Vibrations
2
There are six normal modes due to an NO group namely asymmetric NO stretching,
2
2
symmetric NO
2
stretching, NO
2
rocking, NO
2
2 2
wagging and NO torsion. The NO asymmetric
-1
stretching vibration band range is 1625 - 1540 cm and that of symmetric stretching vibration is
-1
1
400 - 1360 cm [22]. Here, the very weak NO
2
asymmetric stretching vibrations for both IR
-1
spectra are observed at 1646 and 1635 cm . The weak to very weak symmetric stretching
-1
vibration is observed at 1619 and 1610 cm in FTIR spectrum for HDP. The theoretically
−
1
computed wave number by B3LYP/6-311++G(d,p) level at 1642-1613 cm is attributed to NO
2
(
asymmetric and symmetric) stretching vibration.. The weak NO scissoring vibration is
2
-1
−1
observed at 931 cm in IR spectrum and at 927 cm in the FT-Raman spectrum. The
deformation vibrations of NO group (rocking, wagging and twisting) contribute to several
2
normal modes in the low frequency region. These bands are also found well within the
characteristic region and are presented in Table 7.
4
.2.6. NH Vibrations
2
The molecule of HDP under consideration possesses NH group in the fifth position of
2
the heterocyclic ring. The NH group gives rise to six internal modes of vibrations viz., the
2
symmetric stretching, the anti symmetric stretching, the symmetric deformation or the scissoring,
the rocking, the wagging and torsional modes [23]. The NH group has two NH stretching
2
vibrations, one begging asymmetric and the other symmetric. The frequency of asymmetric

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1
2
vibration is higher than that of symmetric one. In HDP the very weak to very strong bands
-1
observed at 3312 and 3228 cm in the FT-IR are assigned to asymmetric and symmetric
stretching vibration respectively. Based on the above conclusion, the theoretically scaled down
−
1
wave number at 3313 and 3229 cm B3LYP\6-311++G(d,p) method are assigned to NH2
asymmetric and symmetric stretching vibrations respectively. In addition the NH group has
2
scissoring, rocking, wagging and torsion modes. The deformation vibration observed in the FT-
−
1
IR spectrum as a weak band at 1628 cm is assigned to NH
2
scissoring vibration. The
−
1
theoretically scaled down values at 1629 cm by B3LYP\6-311++G(d,p) level respectively
−
1
assigned to NH
2
scissoring vibration. The scaled down wave number at 1279 cm is assigned to
NH rocking vibration and this vibration is far below the recorded spectral range. The weak
2
−
1
frequency in the FT-IR spectrum at 1212 cm assigned to NH wagging mode correlates with the
2
−
1
frequencies 1213 cm computed by the B3LYP\6-311++G(d,p) levels respectively. The NH2
−
1
twisting vibration computed by B3LYP\6-311+G(d,p) level at 286 cm shows good agreement
−
1
with the recorded weak FT-Raman frequency of 284 cm .
4
.3. Prediction of First Hyperpolrizability (β)
The hyperpolarizability (β ) of this novel molecular system and the related properties
0
(
β ,α ) of HDP are calculated using the B3LYP/6-311+G(d,p) and B3LYP/6-311++G(d,p) level,
0 0
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. The hyperpolarizability is a third-rank tensor that can be
described by a 3 × 3 × 3 matrix. The 27 components of the 3D matrix can be reduced to 10
components due to the Kleinman symmetry [23]. It can be given in the lower tetrahedral. The
components of β 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 homogenous, this
expansion becomes:

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1
3
0 α α α β α γ α β γ
E= E – ꢀ F – 1/2ααβF F – 1/6β β F F F +....... (3)
Where E
are the components of dipole moment, polarizability and the first hyperpolarizabilities,
respectively.
0
α αβ
is the energy of the unperturbed molecules, F the field of the origin and ꢀα, α
α γ
and β β
The total static dipole moment ꢀ, the mean polarizability α
0
and the mean first
hyperpolarizability β0, using the x, y, z components [12]
The β components of GAUSSIAN 09W output are reported in atomic units and therefore
0
-33
the calculated values are converted into e.s.u. units (1 a.u. = 8.3693 × 10 e.s.u.). The calculated
value of hyperpolarizability and polarizability of HDP are in Table 8.
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.4. Electric fields effects on Transport Properties
The spatial redistribution of the frontier orbital is a three dimensional representation of
local density of states which visually shows the electron density of the molecule. The highest
occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) are the
frontier orbital’s, the difference between them are known as HOMO-LUMO gap (HLG). HLG is
one of the key factors determining the transport properties of the molecule. Large decrease in the
HLG predicts the possibility of having reasonable conduction through the molecule, since, the
conductivity increases with decreases in HLG. As the field increases the HLG extensively
decreases from which is calculated from Gaussian 09 programme package. Fig 9 illustrates the
spatial redistribution of the molecular orbital of the molecule. Table 9, even though small HLG
exists in this molecular system, the possibility of conduction through the molecules is found to
be very less, therefore, it almost act as an insulator. The analysis of the wave function is mainly
described by one-electron excitation from the highest occupied molecular orbital (HOMO) to the
lowest unoccupied molecular orbital. The HOMO–LUMO analysis of these compound is done at

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B3LYP/6- 311++G(d,p) level of theory. Fig.5 illustrates the orbital distributions of HOMO and
LUMO levels of the title compound. HOMO is delocalized mainly on ring carbons; the oxygen
takes part in the formation of HOMO of HDP. Fig. 9 shows that there is no electronic projection
in HOMO and LUMO over the ring hydrogen atoms of the compound [24].
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.4.1. Inhibition efficiency through back donations (ꢀEback-donation
)
The electronic back donations process might be occurring governing the interaction
between the inhibitor molecule and the metal surface. The concept establishes that if both
processes occur, namely charge transfer to the molecule and back-donation from the molecule,
the energy change is directly proportional to the hardness of the molecule as indicated in
following expression:
ꢁEback-donation= -η/4
(4)
The ꢁEback-donations suggest that when η>0 and ꢁEback-donation<0 the charge transfer to a
molecule is actively favored followed by a back – donation from the molecule. In this
environment, it is possible to balance the stabilization among inhibiting molecules. The
maximum charge transfer ꢁNmax is also used to predicate the inhibitor efficiency. The values of
ꢁNmax indicate the trend within a set of molecules and the highest value of ꢁNmax is related to
high inhibitor efficiency. All the calculated ꢁNmax and ꢁEback-donation of Rose and its derivatives
are collected. In this study, the highest value of ꢁEback-donation is -0.2691 eV which is tabulated in
Table 9.
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.5. NMR Spectral Analysis
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C NMR chemical shift is one of the pioneer tools in determining the presence or the absence
of a particular atom in a molecule. In a molecule, shielding of atoms is greatly affected by the
neighbouring bonded atoms. Similar bonded atoms give different shielding values in different
environments. In the present analysis, the chemical shift values for Carbon and Hydrogen atoms

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were studied. The structural parameter for NMR calculation was taken from the optimized
geometries at B3LYP/6-311+G(d,p) level of theory. All the calculations were performed using
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Gauss view molecular visualization program and GAUSSIAN 09W program package. C and
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H NMR spectra of the title molecule are shown in Fig 10. The result shows that the range C
NMR chemical shift of the typical organic molecule usually is >100 ppm, the accuracy ensures
reliable interpretation of spectroscopic parameters. The values obtained for all the carbon atoms
show similar range except few. It is reasonable to discuss those carbon atoms, which possess
distinguished chemical shift values from the others. The few carbon atoms have the shift value
in higher and lower range. This can be attributed to the bond formed with electronegative atom,
which causes the transfer of electron cloud around electronegative atoms from carbon thus
deshielding the carbon. The peculiar thing is to be noted that the functional groups have been
greatly affected in NMR studies, and high shift values are found in the structure requiring low
field for resonance. C1 atom is mostly localized on periphery of the molecules and their
chemical shifts would be more susceptible to intermolecular interactions in the aqueous
solutions as compared to other atoms. Aromatic carbons give signals in overlapped areas of the
spectrum with chemical shift values from 100 to 150 ppm [25-27]. In this study, the theoretical
chemical shift and experimental values of aromatic carbons except C1 of HDP are in the range
of 82.734 -187.473 and 25.635 (H11) 22.678 (H15)ppm. The chemical shift of C1 and H11
(118.009 ppm and 21.66 ppm in gas phase values) values of carbons because of the substitution
of H group in HDP. The theoretical C4 and H15 atoms are due to the presence of
electronegative oxygen in the ‘O’ group. The theoretical chemical shift values of HDP are
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compared with experimental values. O has a very wide chemical shift range which for small
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molecules partially compensates for its broad signals. The theoretical values of O is ranging
from - 40 to 1120 ppm [34]. In the title compound, the peaks at 137.53 and 141.11 ppm are
assigned to O and O which is HDP oxygen of the compound. Noticeably, the oxygen
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