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Introduction
processes. The interaction of radiation with matter can cause redirection of the radiation and
absorption via transitions between the energy levels of the atoms or molecules. Spectroscopy is
widely used to study structural and dynamical aspect of molecular systems; it is a reliable tool
for the characterization of crystalline materials. Modern spectroscopic techniques such as FTIR,
FT-Raman, UV-visible, fluorescence and nuclear magnetic resonance (NMR) have proven to be
an exceptionally powerful technique for solving many drug molecules, pesticide molecules and
the natural products because of the availability of sophisticated instrumentation methods. This
chapter emphasizes the spectroscopic techniques used and the interpretation methods adopted
techniques used for the research work are explained briefly in this chapter. The names of
different regions along with the order of the range of frequencies and wavelength are shown in
12
Fig. 2.1 Electromagnetic spectrum
Infrared spectroscopy is a branch of spectroscopy that deals about the vibration of atoms
in a molecule. Transition of atoms between the vibrational levels result in the vibrational spectra
which gives an insight in to the discrete motion of the atoms in the molecular system. Infrared
spectroscopy has been a workhorse technique for material analysis in the laboratory for over
seventy years. Functional groups have characteristic vibrational frequencies make the spectra as
one of the most reliable methods for understanding the structure of molecules [Sathyanarayana
1995]. IR region of electromagnetic spectrum is generally subdivided into 3 regions such as near
IR (12,500-4000 cm-1), mid IR (4000-400 cm-1) and far IR (400-50 cm-1). The mid IR is the
region most commonly employed in standard laboratory investigations, as it covers most of the
vibrational transitions. The mid IR region provides more information upon the structures of
compounds and consequently it is much used as a procedure for identifying organic compounds
for which it remains a form of functional group finger printing [Fayer & Fayer 2001; Bellamy
13
1980]. Because each different material is a unique combination of atoms, no two compounds
produce the exact same infrared spectrum [Gunzler & Gremlich 2002]. The main goal of IR
spectroscopic analysis is to identify the chemical functional groups in the sample. Thus, IR
spectroscopy is an important and popular tool for structural elucidation and compound
radiation ‘h’ by the molecule should be equal to the energy difference between two states
represented by the wave functions ‘ i ’ and ‘ j ’. The transition between these states under the
influence of electromagnetic radiation depends on the interaction of the electric field of the
from a state ‘i’ to the state ‘j’ is proportional to the square of the transition moment.
ij i * j dτ (2.1)
The dipole moment of a molecule is a function of the normal coordinates ‘Qk’ of the
0 Qk .....
(2.2)
Qk 0
ij 0 i* j dτ i* Qk j d (2.3)
Qk 0
14
The first term vanishes (Orthogonality condition) and the conditions for the second term to be
nonzero are:
(i) must be finite at least for one component of the dipole moment. That is, for a mode
Qk 0
of vibration to be infrared active; the vibrational motion of that mode must give rise to change in
dipole moment.
In infrared spectroscopy, IR radiation is passed through a sample. Some of the infrared radiation
is absorbed by the sample and the remaining part is transmitted. The resulting spectrum
represents the molecular absorption and transmission, creating a molecular fingerprint of the
sample. Fourier transform infrared (FTIR) spectrometry was developed in order to overcome the
limitations encountered with dispersive instruments. The main difficulty in the dispersive
instrument was the slow scanning process. A method for measuring all of the infrared
frequencies simultaneously, rather than individually, was needed. A solution was developed
2.1.2.1 Instrumentation
the idea of the interference of radiation between two beams to yield an interferogram, in which a
signal is produced as a function of the change in path length between the two beams. The two
domains of distance and frequency are interconvertible by the mathematical method of Fourier-
15
transformation. The basic components of FTIR spectrometer are shown in fig. 2.2. The radiation
emerging from the source is passed through an interferometer to the sample before reaching a
detector. Upon amplification of the signal, in which high-frequency contributions have been
eliminated by a filter, the data are converted to digital form by an analog-to-digital converter
2.1.2.2 Source
In the mid IR several type of sources are used. They are either a lamp filament, or a
hollow rod, 1-3 mm in diameter and 2-4 cm long, made of fused mixtures of zirconium oxide or
rare earth oxides (Nernst source) heated by Joule effect by means of an internal resistor
(Globar). These sources are heated to 15000 C, without a protective shield. They dissipate power
of the order of a hundred watts by emitting radiation over a large domain ranging from visible to
thermal IR.
2.1.2.3 Sample
For solid samples pellet technique is used. In Pellet technique first setup is to grind the
sample very finely with potassium bromide. The mixture is then pressed into transparent
pellets with the help of suitable dye. This is then placed in the IR beam in a suitable sample
2.1.2.4 Interferometer
interferometer, which consists of two perpendicularly arranged plane mirrors, one of which can
travel in a direction perpendicular to the plane. A beam splitter (semi-reflecting film) bisects the
planes of these two mirrors. The beam splitter material has to be chosen according to the region
to be examined. Materials such as germanium or iron oxide are coated onto an ‘infrared-
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transparent’ substrate such as potassium bromide or caesium iodide to produce beam splitters for
is passed into an ideal beam splitter, 50% of the incident radiation will be reflected to one of the
mirrors, while 50% will be transmitted to the other mirror. The two beams are reflected from
these mirrors, returning to the beam splitter, where they recombine and interfere. Fifty percent
of the beam reflected from the fixed mirror is transmitted through the beam splitter, while 50%
is reflected back in the direction of the source. The beam which emerges from the interferometer
at 90◦ to the input beam is called the transmitted beam, and this is the beam detected in FTIR
spectrometry. The moving mirror produces an optical path difference between the two arms of
the interferometer. For path differences of (n + 1/β) , the two beams interfere destructively in
the case of the transmitted beam and constructively in the case of the reflected beam. The
moving mirror is a crucial component of the interferometer. The beam enters the interferometer
where the “spectral encoding” takes place. The resulting interferogram signal then exits the
interferometer.
2.1.2.5 Detector
There are two commonly used detectors employed for the mid-infrared region. The normal
detector for routine use is a pyroelectric device incorporating deuterium tryglycine sulfate
(DTGS) in a temperature-resistant alkali halide window. For more sensitive work, mercury
cadmium telluride (MCT) can be used, but this has to be cooled to liquid nitrogen temperature.
A detector must have adequate sensitivity to the radiation arriving from the sample and
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Fig. 2.2 Diagram of FTIR spectrometer
Introduction
the particles (e.g., molecules, atoms, or ions) constituting it. If the dimensions of the particles
are equal to or smaller than that of its wavelength then it undergoes scattering. Raman
spectroscopy is based on inelastic scattering of light by matter. It has been observed that most of
the scattered radiation has exactly the same wavelength as that of the incident radiation. Such a
scattering is referred to as Rayleigh scattering. However, a very small fraction (to the tune of
about 1 in 107) of the scattered radiation is found to have a wavelength different from that of the
incident radiation. This is called Raman scattering and the existence of Raman scattering is
called Raman effect. The intense peak in the centre of the spectrum having the same wavelength
(or wavenumber) as that of the incident radiation is called the Rayleigh peak and the other
signals on either side of the Rayleigh peak are the Raman lines. The lines to the left of Rayleigh
peak and having lower wavenumber (energy) are called Stokes lines, while the other on the right
having higher wavenumber (energy) are called anti-Stokes lines [Jacek 2005].
18
2.2.1 Classical theory of Raman Effect
under go polarization. The polarization ‘P’ so induced is proportional to the applied electric field
‘E’asμ
P = E (2.4)
molecules, each molecule experiences a varying electric field. This field depends on the incident
E = E0 cos 2 0 t (2.5)
Consider the vibrational motion of the molecule. If ‘q’ is the normal co-ordinate
associated with a particular mode of vibrational frequency ‘m’ of the molecule, the harmonic
For small vibrational amplitudes, the polarizability ‘ ’ can be expanded using Taylor series
as:
0 q ... (2.7)
q 0
where, ‘ 0 ’ is the polarizability at the equilibrium position. The term is the rate of
q 0
change of ‘ ’ with respect to ‘q’, evaluated at the equilibrium position. The induced dipole
moment is therefore:
19
1
P = 0 E0 cos 2 0t q0 E0 cos 2 0 m t cos 2 0 m t (2.8)
2 q 0
The first term represents Rayleigh scattering and the second term represents anti-Stokes
0 m and Stokes 0 m lines of Raman scattering. For Raman active vibrations, the
i.e. 0 . (2.9)
q 0
correctly describes the frequencies of the Raman lines 0 m , it fails to predict correct
intense source (usually a laser) in the UV-visible or IR region and the scattered light is
generally observed in a direction perpendicular to the incident beam. The scattered light consists
of two types. One is elastic Raleigh scattering, which is strong and has the same frequency as
incident beam (ν0). The other one is inelastic Raman scattering and is weak, approximately
105 times weaker than the incident beam, and has frequencies of (ν0νm) where νm is the
from the incident frequency (ν0) [Ferraro & Nakamoto 1994]. Stokes lines are those represented
by 0m shift while the anti-Stokes lines are those represented by 0m shift, the process
terms, for an incident photon of wavenumber (cm-1), the inelastic scattering processes are
20
represented by the following equations,
of the incident radiation, and νm is the wavenumber equivalent to the energy difference between
the lowest and first excited vibrational energy levels (fig. 2.3).
Raman spectrometers basically employ one of the two techniques either dispersion or
Fourier Transform (FT) for the collection of spectral data. Dispersive Raman spectrometers
Furthermore, the cost of this type of equipments and its maintenance are quite high. So FT-
Raman spectrometer replaces the dispersive Raman without producing sample fluorescence.
Sample is irradiated with longer wavelength excitation laser, so the virtual state is lower and it
will overlap with an upper electronic state. This greatly reduces fluorescence interferences and
therefore Raman signals are free from distortions. Conventional Raman spectroscopy measures
21
intensity versus frequency. But, FT-Raman is a time domain spectroscopy which measures the
fig. 2.4. The three basic spectrometer components in an FT system are source, interferometer
2.2.3.1 Source
With the advent of lasers with highly desirable properties of high intensity, single
wavelength and coherence, the modern spectrometers almost exclusively use laser sources. The
intensity of Raman scattering is dependent on the fourth power of the frequency of the exciting
radiation, besides concentration and other factors. The argon and krypton ion laser sources are
more intense than the other lasers being used at the same power and accordingly give better
spectra. On the other hand the low frequency lasers i.e., diode laser and Nd/YAG laser can be
used at higher power and also have an added advantage that these do not generate the interfering
2.2.3.2 Sample
A solid sample is ground to a fine powder and packed into a small cavity to be kept in the
path of incident radiation. When the sample is placed in the radiation path, the incident laser
beam enters the sample through the window and undergoes multiple reflections in the sample.
The scattered light at right angles to the sample is then suitably collected and measured.
2.2.3.3 Detector
In initial versions of the spectrometers, photographic plates were used to detect the
scattered radiation. This was followed by more sensitive photomultiplier tubes (PMTs) that
allowed electronic data collection and manipulation. However they had the disadvantage for
they could count only one wavelength at a time. Today most of the Raman spectrometers are FT
radiation has a major component of the Rayleigh scattering, this is eliminated by using a suitable
22
filtering device like holographic grating or interference filters before the detector. Therefore, the
Detector detects the interferogram signals and fed to the computer. It is the time domain
spectrum and records the detector response changes versus time within the mirror scan. If the
sample happens to absorb the signal at this frequency, the amplitude of the sinusoidal wave is
reduced by an amount proportional to the amount of sample in the beam. The interferogram
contains the information over the entire Raman region to which detector is responsive. The
required Raman shift is obtained after calibrating the original data with respect to the known
wavenumber relationship. The plot represents the wavenumber and the relative scattering
The IR and Raman activities of different modes of vibration of a molecule depend on its
symmetry properties. An analysis of the IR and Raman spectra of a large number of molecules
has lead to an extremely important general rule known as the rule of mutual exclusion. It states
23
that, “for a molecule having a centre of symmetry the Raman active vibrations are IR inactive
and vice versa”. However, if the molecule does not have a centre of symmetry then some
Introduction
electronic states which fall in the visible and ultraviolet regions of the electromagnetic spectrum
[Francis & Annick 2007]. UV-Visible region of the spectrum is conventionally divided into
three sub-domains termed as near UV (185-400 nm), visible (400-700 nm) and very near
infrared (700-1100 nm). Most commercial spectrophotometers cover the spectral range of 185 to
900 nm. The origin of absorption in this domain is the interaction of photons from a source with
ions or molecules of the sample. When a molecule absorbs a photon from the UV-Vis region,
the corresponding energy is captured by one (or several) of its outermost electrons. UV-Vis
spectrometers collate the data over the required range and generate the spectrum of the
compound under analysis as a graph representing the transmittance (or the absorbance) as a
function of wavelength along the abscissa, given in nanometres. In UV-visible spectroscopy, the
the comparison between the intensities of the transmitted light (I) and the incident light (I0)
according to whether the sample is placed, or not, in the optical pathway between the source and
the detector.
2.4.1 Instrumentation
monochomator), and detection system as shown in fig. 2.5. More than one type of source can be
24
used in the same instrument, which automatically swaps lamps when scanning between the UV
and visible region. For the visible region of the spectrum, an incandescent lamp fitted with a
tungsten filament housed in a silica glass and for the UV region a deuterium arc lamp working
under a slight pressure to maintain an emission continuum (< 350nm) and alternatively, for the
entire region 200 to 1100 nm, a xenon arc lamp can be used for routine apparatus.
The light emitted by the source is dispersed through either a planar or concave grating,
which forms part of a monochromator assembly. This device permits the extraction of a narrow
interval of the emission spectrum. The wavelength or more precisely the width of the spectral
band, which is a function of the slit width, can be varied gradually by pivoting the grating.
Optical paths with long focal lengths (0.2 to 0.5 m) yield the best resolution. A sample
compartment is inserted into the optical path either before or after the dispersive system
The detector converts the intensity of the light reaching it to an electrical signal. It is by
nature a single channel device. Two types of detector are used, either a photomultiplier tube or a
semiconductor. For both of which, the sensitivity depends upon the wavelength. For
system, the light intensity at all wavelengths is measured practically at the same instant by
Introduction
whether pure or in solution, emit light when they are excited by photons from the visible or the
near ultra-violet regions. Among the analytical applications of this phenomenon, known as
photoluminescence, is fluorimetry, a selective and highly sensitive method for which a wide
range of measurements are accessible. The intensity of the fluorescence is proportional to the
concentration of the analyte and the measurements are made with the aid of spectrofluorometers.
The extremely rapid extinction of the light intensity when excitation ceases is the object of
time. Many compounds, when excited by a light source in the visible or near ultraviolet region
absorb energy which is nearly instantaneously re-emitted in the form of radiation. According to
Stokes’ law, the maximum of the spectral emission band is located at a longer wavelength than
that of the original excitation light. These are fluorescent compounds [David & Churchill 1999].
In addition to fluorescence (the desired decay route), there are nonradiative decay processes,
leading to release of energy in the form of heat rather than light. Other sample constituents may
interact with an excited analyte molecule in such a way as to prevent it from fluorescing; such
2.5.1 Instrumentation
sample and detector. A shimadzu F-4500 fluorescence spectrometer is shown in fig. 2.6. In
addition to the optical components shown, most fluorometers have dedicated computers, which
control instrumental operating parameters and the acquisition of spectral data, and also may be
26
Fig. 2.6 Schematic diagram of a fluorescence spectrometer
2.5.1.1 Source
molecules formed per unit time. Thus, the source must produce high optical power. Because
molecular absorption spectra usually are broad, a highly monochromatic source is not generally
needed; an intense continuum source that emits throughout the UV, visible and near infrared
regions is adequate. The source used in most commercial fluorometers is the xenon arc lamp
Such instruments are used when it is sufficient to measure fluorescence intensity at a single
excitation and emission wavelength [Alarie et al. 1993; Brennan et al. 1993]. Filters can
transmit a very large number of photons from source to sample and from sample to detector.
viewed at a 90° angle relative to the direction of the exciting light beam. This geometry is
27
suitable for weakly absorbing solution samples. For solutions that absorb strongly at the
excitation wavelength, and for solids, a front surface geometry is preferable. For solution
samples, rectangular 1cm glass or fused silica cuvettes with four optical windows are usually
2.5.1.4 Detector
The fluorescence signal for an analyte present at low concentration is small; thus, a key
requirement for a detector is its ability to detect weak optical signals. A photomultiplier tube
(PMT) is used as the detector in most fluorescence spectrometers. PMTs used in fluorometry are
chosen for low noise and high sensitivity, and are sometimes operated at subambient
2.5.1.5 Working
emission pair to get the best results. Knowing the UV-Vis spectrum of the compound, the
procedure can be decomposed in the following steps such as the excitation monochromator is set
to the value corresponding to the maximum of the UV absorption spectrum, the fluorescence
spectrum is recorded and the emission monochromator is set to the wavelength of maximum
fluorescence and the excitation wavelength is varied. The excitation spectrum is obtained
allowing the best final choice of the excitation radiation [Francis & Annick 2007].
Introduction
theoretically complex analytical tool that allows the study of compounds in either solution or in
the solid state and serves equally in quantitative as in structural analysis, it is very efficient in
field, a sample can absorb electromagnetic radiation in the radio frequency (r.f) region at
28
frequencies governed by the characteristics of the sample [Francis & Annick 2007; David &
Churchill 1999.]
All nuclei carry a charge, in some nuclei this charge "spins" on the nuclear axis, and this
circulation of nuclear charge generates a magnetic dipole along the axis. The angular
momentum of the spinning charge can be described in terms of quantum spin numbers I: these
numbers have values of 0,1/2,1,3/2 and so on (I=0 denotes no spin). The intrinsic magnitude of
the generated dipole is expressed in terms of nuclear magnetic moment, . The fundamental
NMR equation correlating the applied radio frequency radiation ( 1 ) with the magnetic field
strength ( B0 ) is
1 B0 (2.12)
2
where is called magnetogyric ratio.
A-Sample container, B-Transmitter coil, C-Sweep generator coils, D-Receiver coil, E- Magnet
The basic layout of a continuous wave NMR spectrometer is shown in fig. 2.7. NMR
spectrometer consists of Sample container, Transmitter coil, Sweep generator coils, Receiver
coil, Magnet, detector and recorder. These instruments were the original type of instrument and
An electromagnet is one which gives a powerful, stable and homogeneous magnetic field
[Herald 1994]. The field must be constant over the area of the sample and over the period of
time of the experiment. A sweep generator supplies a variable current to a secondary magnet so
that the total applied magnetic field can be varied over a small range. The sample container is
usally a glass tube (5 mm OD) spun by an air-driven turbine to average the magnetic field over
the sample container. The process is often referred to as the spinning of the sample. A radio
frequency oscillator is connected to a coil, called the transmitter coil, which transmits the energy
to the sample. The axis of the coil has to be perpendicular to the magnetic field. A radio
frequency receiver is connected to a coil, called the receiver coil, which encircles the sample. Its
axis has to be perpendicular to both the magnetic field and the axis of the transmitter coil. The
transmitter and receiver coils and the sample holder are constructed in to a single unit called
probe. In addition to the major components there is a read out system consisting of an radio
frequency amplifier, recorder and other accessories to increase the sensitivity, resolution and
accuracy.
The sample is placed in the sample container and is spun in the fixed magnetic field at ca
30 revolutions/s by means of an air turbine thus ensuring uniformity of the magnetic field across
the sample in a horizontal direction. The sample is analysed in a deuterated solvent to ensure
there is no interference from protons in the relatively much larger amount of solvent with the
signal from the sample protons. The reference point of 0 parts per million (ppm) is determined
by the frequency at which the protons in tetramethyl silane (TMS) absorb. Sometimes residual
30
protons in the solvent are used to lock the protons in a spectrum, e.g. the residual proton in
deuterated chloroform is at 7.25 ppm relative to TMS. The receiver coil measures the absorption
of radiation as the frequency is swept over the range being examined. As well as determining the
frequency at which protons in the molecule absorb, the instrument determines the area of each
signal, which is proportional to the number of protons absorbing radiation. Modern instruments,
rather than being based on a continuous wave, are based on a pulsed wave. The data in the form
of pulses are collected in the computer and the mathematical manipulations (Fourier
transformation) are carried out. Then it is combined to produce a spectrum in which the signal to
Proton (1H) NMR is the most commonly used form of NMR because of its sensitivity
and the large amount of structural information it yields. The exact absorption or resonance
frequency of a proton depends on its environment. For example, a proton attached to carbon
atom is affected predominantly by the groups which are separated from the carbon atom to
which it is attached by one bond or to a lesser extent two bonds. As discussed earlier the
chemical shift of a proton is determined in relation to the protons of tetramethylsilane, which are
arbitrarily assigned a shift of 0 ppm. Shift values for individual protons in a molecule are
expressed in ppm and the value of 1 ppm in Hertz depends on the strength of the applied
magnetic field which determines the energy required to excite a proton. The chemical shift is
determined by the extent to which a proton is deshielded by the group to which it is attached.
The more a proton is shielded by the electron density around it, the lower its chemical shift
value.
2.7 Electron displacement effects which affect the spectral nature of compounds
2.7.1 Hybridization
Hybridization is one of the most important concepts of quantum chemistry, since it provides a
31
basis for correlating many physical properties of molecules with electronic structure. This
concept was originally introduced by Pauling 1931, who suggested that a mixture of s and p
atomic orbitals would provide a better function for bond formation than either an s or p orbital
alone. The bond is described by a pair of electrons in atomic orbitals, one on each of the two
centers involved. Thus, hybridization is a valence bond concept. When a carbon atom bonds to
other atoms, the four orbitals in the second shell are somehow mixed together and rearranged to
give four new orbitals of equal energy. These four new orbitals are called hybrid orbitals. Each
of the four hybrid orbitals is equivalent to the others and each contains one electron. These
hybrid orbitals resulted from the combination of a s orbital and three p orbitals are called sp 3
hybrid orbitals or simply sp3 orbitals [Bernard et al. 1977]. There are three types of
hybridization,
(i) sp3 hybridization (involved in saturated organic compounds containing only single
covalent bonds),
(ii) sp2 hybridization (involved in organic compounds having carbon atoms linked by
triple bonds).
When the orbital of a bond is in the trans position with the lone pair of the adjacent
electronegative atom, the electronic charge is back donated from the lone pair to the * orbital.
This will increase the electronic charge in the orbital, and make the bond weaker, decreases the
stretching force constant of the bond, and increases the bond distance and the stretching
vibrational intensity.
32
2.7.3 Induction
The presence of an electron attracting constituents attached to the carbon atom in the
molecule causes the shifting of bonding electron pair, inducing polarity in the carbon atom as
well as on the substituent [Gussoni & Castiglioni 2000]. The electron attracting substituent
develops negative charge in it and produces negative inductive effect whereas the electron
releasing subsituent causes positive inductive effect. In C-H bond, stronger polarization occurs
due to induction in molecules and the presence of electronegative atom. This effect reduces with
the distance of C-H bond from the electronegative atom. Stronger polarization makes the charge
on hydrogen atom to increase. The C-H stretching force constant increases whereas the C-H
2.7.4 Conjugation
The conjugation effect operates on systems with conjugate -bonds, alternate - and -
bonds, in which the electron displacement is relayed through the -electron system. The
vibrational spectral influence of conjugation differs for various systems. For an aliphatic
conjugation of carbon-carbon double bonds, the splitting of C=C stretching band is resulted
[Bellamy 1980]. The conjugation of the carbonyl group causes appreciable shift in C=O
stretching band position and hence most of the aryl ketones produce C=O absorption band in the
lower wavenumber range, 1680-1690 cm-1. Unsaturated aldehydes containing double bond in
the or -positions show a fall in the carbonyl frequency due to conjugation. Aromatic ring in
conjugation with the aldehyde groups also show marked effect on band position and C=O
2.7.5 Hyperconjugation
It is the interaction of orbital of a single bond with the -orbital of an adjacent double /
triple bond. In C-H bonds, the hyperconjugation causes the releasing of electronic charge from a
33
CH to the C-C bond [Gussoni & Castiglioni 2000]. As a result, C-C bond length decreases and
the bond strength increase. Due to the release of electronic charge from CH, the hydrogen
becomes more acidic due to increase of charge on hydrogen. This will increases the C-H bond
ionicity and decreases the C-H bond strength. But due to the decrease of electronic charge in
CH bonding orbital, there should be decrease in C-H bond strength. Due to suitable balance
between these two opposing effects, the bond length and spectral characteristics of C-H bonds of
the hyperconjugated systems do not show direct correlation with the charge on hydrogen.
The compounds having the electron donor and electron acceptor at the end positions of the
responsible for pesticide activity. The ICT causes the electron releasing effect in the acceptor
moiety, affecting the spectral modes. C=C stretching mode of acceptor subunit occurs at lower
wavenumber compared to the corresponding mode of the donor subunit [Ruiz et al. 2003]. For
the conjugated path, ICT induces large variation in the dipole moment as well as in the
molecular polarizability simultaneously during vibration. This produces the IR and Raman
activity for the same mode and hence comparable intensities of IR and Raman bands arise from
the vibrations of conjugated system. The electron donating effect of donor unit also causes
wavenumber shifting in the vibrations of the donor group. The existence of a large ICT at
relatively low energy values depends on the efficiency of the π-electron delocalization through
the bridge and of the electron donor and the electron-acceptor strength of the end groups.
properties of many chemical and biological systems. The H-bond plays a key role in chemistry,
physics, and biology, and its consequences, such as the properties of solid, liquid and gas. The
34
importance of H-bonds is enormous. They are responsible [Scheiner 1997] for the structure and
properties of water, an essential compound for life, as a solvent and in its various phases.
Further, H-bonds also play a key role in determining the shapes, properties, and functions of
biomolecules. This is the basis for several spectroscopic, structural, and thermodynamic
techniques. The characteristic features of X-H∙ ∙ ∙Y-H bond are as follows: (i) the X-H covalent
bond stretches in correlation with the strength of the H-bond; (ii) a small amount of electron
density (0.01-0.03 e) is transferred from the proton-acceptor (Y) to the proton-donor molecule
(X-H); (iii) the band which corresponds to the X-H stretch shifts to lower frequency (red shift),
increases in intensity, and broadens. The value of the red shift and the strength of the H-bond are
correlated. Frequency shifts correlate with various characteristics of the H-bonded system
[Morokuma et al. 1981; Kollman 1981; Singh & Kollman 1984; Silverstein 2005].
Intramolecular hydrogen bonds are formed when the proton donor and acceptor are
present in a single molecule under spatial conditions that allow the required overlap of orbitals,
for example, the formation of a five-or six-membered ring. Intramolecular bonding involving
the same bonding groups is stronger when a six-membered ring is formed than when a smaller
ring results from bonding. Intramolecular hydrogen bonds are formed in all three phases, but in
crystalline state, their strength competes with that of intermolecular hydrogen bonds. The
carbohydrates are rich in intramolecular hydrogen bonding due to the presence of hydroxyl
groups attached to the adjacent carbon atoms. The intramolecular hydrogen bonding is an
internal effect and persists at very low concentrations. When the A-(H)…B distance is very
short, i.e. O…O 2.5Å and N…N 2.6 Å, the strong hydrogen bonds are formed. When the
distances are between 2.5 and 3.2 Å, normal hydrogen bonds may be formed. [George 1997].
structures and activities of organic, organometallic and biological molecules [Takhashi et al.
2003; Reynisson & Steenken 2003]. Intermolecular hydrogen bonding involves association of