Overtone, IR spectroscopy, Raman spectroscopy

BY- MAHMOOD MOHAMMED ALI

At the beginning. This lecture will focus on three main parts. The first section,
explaining the overtones in infrared spectrum. Then we will illustrate the
applications of infrared spectrum on nanoparticles. Finally, we will study Raman
spectroscopy with a simplified explanation.

Overtones
Overtones occur when a vibrational mode is excited from v=0 to v=2, which is
called the first overtone, or v=0 to v=3, the second overtone. The fundamental
transitions, v=±1, are the most commonly occurring, and the probability of
overtones rapid decreases as the number of quanta (Δv=±n) increases. Based on
the harmonic oscillator approximation, the energy of the overtone transition would
be n times larger than the energy of the fundamental transition frequency, but the
anharmonic oscillator calculations show that the overtones are less than a multiple
of the fundamental frequency.

Excitation from ground

state to higher energy
excited states i.c 2nd or
3rd Observed at twice the
frequency of strong
band. Results from
excitation from ground
state to the 2nd or 3rd
excited states and
correspond to integral
multiples of the
frequency of the
fundamental band as
shown in figure 1
Figure 1: overtone energy
Overtones occur at 2v and 3v etc. For example, an absorption in the IR
at v =1400 cm-¹. may have an accompanying peak of higher intensity at v = 2800 cm-
¹. As shown in figure 2

Figure 2 : formation of overtone

Here are some charts that show the overtone bands range for different compounds,
figure 3
 Figure 3: Charts of Overtone

Characterization of Nanoparticles Using Infrared Spectroscopy

IR spectroscopic techniques
have enabled studies
involving a wide variety of Surface-
enhanced
infrared
additional nanomaterials, spectroscopy

which for brevity have not

been detailed herein. Just to Nanotoxicological Characterization
of nanoparticles of nanoparticles
mention a few, recently 2D-IR IR
spectroscopy has been used to Spectroscopy

investigate the sensitivity of a

vibrational mode to spectral
Adsorption
Infrared imaging
processes on
diffusion at the nanometer nanoparticles
of nanoparticles

length scale using porous

SiO2 nanoparticles.

The infrared applications of nanoparticles can be divided according to the above

scheme.
 Characterization of nanoparticles

IR techniques – mainly Fourier transform infrared spectroscopy (FTIR) – for

evaluating the functional groups present within a colloidal suspension of NPs. IR
spectra reveal vibrational signatures of the constituents present in the surrounding
media of the nanoparticles .

For example, Figure (4) shows the absorption bands of silver nanoparticles prepared
by the chemical reduction method, as several bands appear in the FT-spectrum.

Figure (4) absorption bands of silver nanoparticles (IR, that the broad absorption band in the
region (2800-3600) cm-1 belongs to the elastic vibration of the (H-O) bond and the absorption bands (1600 and
1400) cm-1 are for the asymmetric and symmetric stretch absorption, respectively, of the (-COO) bond resulting
from the surrounding jackets With nanoparticles that act as a stabilizer for those particles, either the absorption
bands at (1274 and 1076) cm-1 belong to the flexural and stretching vibration, respectively, of the (O-C) bond,
and the absorption band in the range (1380-1390) cm-1 belongs to the material Nitro NO2 whose source is silver
nitrate AgNO3. Vibrations in metal-metal bonds such as Ag-Ag appear in the region less than (400) cm-1, so they
did not appear because they are outside the measured range(
Core-shell nanoparticles such as AuTiO2, AuZrO2, AgTiO2, AgZrO2, and Ru-Pt
nanoparticles have also been studied by IR spectroscopy to characterize the molecular
nature of the material by analyzing features attributed to Ti-O-Ti and Zr-O-Zr
stretching modes among others. In addition to the chemical structure, IR spectra may
also provide information on the size of NPs. For example, diffuse reflectance near
infrared (DR-FTNIR) spectroscopy.

IR spectroscopy is also useful for characterizing carbon nanomaterials, i.e., carbon

nanotubes, nanodiamonds, graphene quantum dots (GQDs), and carbon dots (CDs)
along with their functionalization via ligands. GQDs provide oxygen-containing
functional groups, namely, carboxyl and hydroxyl groups at the edges of the
nanostructure, which can be readily detected by FTIR spectroscopy.

Surface-enhanced infrared spectroscopy

Raman and infrared (IR) spectroscopy are powerful analytical techniques but have
intrinsically low detection sensitivity. There have been three major steps (i) to advance
the optical system of the light excitation, collection, and detection since 1920s, (ii) to
utilize nanostructure-based surface-enhanced Raman scattering (SERS) and surface
enhanced infrared absorption (SEIRA) since 1990s, and (iii) to rationally couple (i)
and (ii) for maximizing the total detection sensitivity. After surveying the history of
SERS and SEIRA, we outline the principle of plasmonics and the different mechanisms
of SERS and SEIRA. We describe various interactions of light with
nano/microstructures, localized surface plasmon, surface plasmon polariton, and
lightning-rod effect. Their coupling effects can significantly increase the surface
sensitivity by designing nanoparticle nanoparticle and nanoparticle–substrate
configuration. As the nano/microstructures have specific optical near-field and far-
field behaviors, we focus on how to systematically design the macro-optical systems to
maximize the excitation efficiency and detection sensitivity. We enumerate the key
optical designs in particular ATR-based operation modes of directional excitation and
emission from visible to IR spectral region. We also present some latest advancements
on scanning-probe microscopy-based nanoscale spectroscopy. Finally, prospects and
further developments of this field are given with emphasis on emerging techniques and
methodologies.
SEIRA spectroscopy taking advantage of the properties of metallic nanomaterials has
been used for the determination of a variety of organic and inorganic analytes. On the
other hand, the enhancement produced by the metallic nanoparticles can be used for
the characterization of the nanomaterial itself. for in-situ monitoring the synthesis and
deposition of bare gold nanoparticles, as has been demonstrated for the stainless-steel-
assisted synthesis of AuNPs giving rise to enhanced water absorption features within
the evanescent field of an ATR waveguide. Figure 5

Figure 5 : Optical design from nano/micro substrates to macro-optics for SERS

Infrared imaging of nanoparticles

Plasmon resonant metal nanoparticles may strongly enhance optical fields, as
exploited in surface-enhanced infrared absorption spectroscopy. Optical near-field
coupling of such nanostructures separated by a nanoscopic gap may in addition
increase the local field enhancement.

This fact has been exploited to demonstrate nano-resolved infrared imaging of

individual nanoparticles employing near-field coupling in the nanoscopic gap between
the metal tip of a scattering-type near-field optical microscope, and the substrate
supporting the particles. Thus, infrared microscopy of single gold nanoparticles with
diameters around 8 nm is enabled at wavelengths of about ≈ 10 nm. Operating at
infrared frequencies at such dimensions is clearly motivated by the prospects of
performing vibrational spectroscopy for chemical identification at individual
nanoscale objects.
Nanotoxicological of nanoparticles using IR spectroscopy
The increasing use of nanomaterials in consumer and industrial products has initiated
global concern on their interactions with biological systems, and potential
toxicological effects. Although the potential hazards of nanotechnological products has
been described, their general toxicity remains largely uncategorized due to the lack of
scientific consensus in many instances .
A variety of nanomaterials are capable of entering into living cells. Structural changes
of the lipid bilayer as a consequence of the penetration of quantum dots through cell
membranes has been investigated by IR spectroscopy, thereby revealing a markedly
enhanced flexibility of the lipid bilayer in the presence of nanoparticles. IR-ATR
spectroscopy may be also used to identify agent-induced alterations occurring within
cells. Commonly, the use of multivariate techniques such as principal component
analysis (PCA) and linear discriminant analysis (LDA) are needed to clearly reveal
differences between the obtained IR spectra. For example, IR- ATR combined with
multivariate algorithms has been used to examine the effects of different carbon
nanoparticles (i.e., long vs. short multiwalled carbon nanotubes (MWNTs), C60
fullerenes, and fullerene soot) in Gram-negative bacteria and in mammalian cells.
Spectra acquired from nanoparticles alone did not show any peaks in the fingerprint
range (1800-900 cm-1). Thus, only the effects of carbon nanoparticles rather than the
nanoparticles themselves were identified within the acquired spectra. Changes in the
IR bands related to C=O stretching vibrations of lipids, amide I, and amide II bands,
as well as asymmetric and symmetric phosphate stretching vibrations, carbohydrates,
and protein phosphorylation were observed .
Adsorption processes on nanoparticles
The adsorption of organic molecules at metal surfaces and nanosized particles along
with the derivatization of nanoparticles with organic molecules is of substantial
interest. IR-ATR spectroscopy is capable of in-situ characterizing surface adsorption
at nanoparticles in environmentally and biologically relevant media. Furthermore,
since the interfacial region in these media is dynamic, such dynamics may be monitored
by IR-ATR spectroscopy by interrogating a layer of immobilized NPs coated onto an
ATR waveguide surface, while changing the overlying aqueous phase.
 Raman spectrum
In general, when a monochromatic light is scattered by a molecule, in addition to the
Rayleigh scattering that produces exactly the same wavelength (frequency) as the
incident photons, several sharp peaks next to the Rayleigh line are also observed due
to the inelastic scattering of photons. Because these distinctive peaks arise from the
change in vibrational, rotational, or electronic energy of the excited molecule, they
provide a feasible means for “fingerprint-like” molecular identification. As a result,
since the discovery of the Raman effect by C.V. Raman in 1922, Raman scattering
spectroscopy has become a popular analytical tool in materials characterization,
biological and chemical sensing, etc. However, Raman scattering suffers from one
major drawback, that is, it has a very small scattering cross section sRS, which is ~ 12–
14 orders of magnitude lower than that of fluorescence. In other words, for every 1012
photons incident on a molecule, only one or less undergoes Raman scattering.
Therefore, Raman scattering does not produce strong signal easily, particularly in
situations where the concentration of target analyte is very low. Figure7shown the
origin of Raman spectrum in scattered light

Figure7: Origin of Raman spectrum in scattered light

Raman spectroscopy mainly utilized mercury arcs as the source of the exciting
radiation until the development of the laser, and the era of routine laser-Raman work
has only now arrived. Not only is laser light more intense and more coherent, but also
it enables longer wavelengths to be used for excitation, eliminating many problems of
sample decomposition.
State-of-the-art FT laser-Raman spectrometers use a Nd-YAG laser operating at 1064
nm, which minimizes the troublesome fluorescence which arises from many samples if
excitation of shorter wavelength is used.

Differences between infrared and Raman spectra

An infrared absorption arises when infrared light (electromagnetic) interacts with a

fluctuating dipole within the molecule. The Raman effect is not an absorption effect like
infrared, but depends on the polarizability of a vibrating group, and on its ability to
interact and couple with an exciting radiation whose frequency does not match that of
the vibration itself. A given vibrational mode within a molecule may lead to fluctuating
changes in the dipole (an infrared-active vibration), but may not necessarily lead to
changes in the polarizability (a Raman-active vibration), the converse also being true.
Many absorptions that are weak in infrared (for example, the stretching vibrations of
symmetrically substituted C=C and C ≡ C) give strong absorptions in Raman spectra.
Figure 8 show the Differences between infrared and Raman spectra
 Figure 8 : Differences between infrared and Raman spectra

Raman Spectroscopy for Nanomaterials

Surface-enhanced Raman scattering (SERS) offers high specificity in molecular
identification and is a promising technique for making biological and chemical sensors.
However, a major weakness of this technique is the lack of reliable SERS substrates.
Currently available substrates usually contain irregular active sites that suffer from
strong spatial and temporal fluctuation in Raman intensity and thus do not produce
stable Raman output.

Raman technique has been proven to be an effective tool in understanding the

underlying mechanism of SERS, especially the electromagnetic origin of SERS Which
can be used to study the properties of nanomaterials. In this article, we will show simple
examples of applications of this technology in nanoparticles.

Biomedical SERS Studies Using Nanoshells

There is a need in biomedical sciences for improved techniques for monitoring

biomolecular interactions and physiological processes, especially those which can
report in real time. New techniques may find use in (for example) live-cell imaging or
in vitro diagnostics – one such technique is surface enhanced Raman spectroscopy
(SERS). While SERS has been demonstrated using a variety of metal surfaces

Nonlinear Raman Scattering Spectroscopy for Carbon Nanomaterials

Nonlinear vibrational spectroscopy provides accessibility to a range of vibrational
information that is hardly obtainable from conventional linear spectroscopy. Recent
progress in the pulsed laser technology has made the nonlinear Raman effect a widely
applicable analytical method. there are two types of nonlinear Raman techniques,
hyper-Raman scattering (HRS) spectroscopy and timefrequency two-dimensional
broadband coherent anti-Stokes Raman scattering (2D-CARS) spectroscopy, are
applied for characterizing carbon nanomaterials. The former is used as an alternative
for IR spectroscopy. The latter is useful for studying dynamics of nanomaterials.

Ag/Carbon Nanotubes for Surface-Enhanced Raman Scattering

The surface-enhanced Raman scattering (SERS)-active substrates were prepared by
electrodeposition of Ag nanoparticles in multiwalled carbon nanotubes (MWCNTs)-
based nanocomposites for SERS sensor application.