PHYSICAL CHEMISTRY II (CH 1641)
Module 4
Spectroscopy I
➢ Regions of electromagnetic spectrum.
➢ Different units of energy (erg, Joule, calorie, an cm-1, Hz, Ao and eV) and their inter
conversions. Interaction with mater - Quantization of energy - photon, various types of
molecular excitation and types of molecular spectra.
➢ Born-Oppenheimer approximation.
Electromagnetic Radiation
❖ Electromagnetic (EM) radiation is a form of energy that is all around us and takes many forms, such as
radio waves, microwaves, X-rays and gamma rays.
❖ Sunlight is also a form of EM energy, but visible light is only a small portion of the EM spectrum, which
contains a broad range of electromagnetic wavelengths.
❖ Electromagnetic radiation —light— is a form of energy whose behavior is described by the properties of
both waves and particles.
EM spectrum
• The arrangement of different types of electromagnetic radiation according to their wavelengths
(or frequencies) is known as electromagnetic spectrum.
• The EM spectrum is generally divided into seven regions, in order of decreasing wavelength and
increasing energy and frequency.
• The common designations are: radio waves, microwaves, infrared (IR), visible light, ultraviolet (UV),
X-rays and gamma rays.
• Typically, lower-energy radiation, such as radio waves, is expressed as frequency; microwaves, infrared,
visible and UV light are usually expressed as wavelength; and higher-energy radiation, such as X-rays
and gamma rays, is expressed in terms of energy per photon.
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Radio waves
• Radio waves are at the lowest range of the EM spectrum, with frequencies of up to about 30 billion
hertz, or 30 gigahertz (GHz), and wavelengths greater than about 10 millimeters (0.4 inches).
• Radio is used primarily for communications including voice, data and entertainment media.
Microwaves
• Microwaves fall in the range of the EM spectrum between radio and IR.
• They have frequencies from about 3 GHz up to about 30 trillion hertz, or 30 terahertz (THz), and
wavelengths of about 10 mm to 100 micrometers (μm).
• Microwaves are used for high-bandwidth communications, radar and as a heat source for microwave
ovens and industrial applications.
Infrared
• Infrared is in the range of the EM spectrum between microwaves and visible light.
• IR has frequencies from about 30 THz up to about 400 THz and wavelengths of about 100 μm to 740
nanometers (nm).
• IR light is invisible to human eyes, but we can feel it as heat if the intensity is sufficient.
Visible light
• Visible light is found in the middle of the EM spectrum, between IR and UV.
• It has frequencies of about 400 THz to 800 THz and wavelengths of about 740 nm to 380 nm.
• Visible light is defined as the wavelengths that are visible to most human eyes.
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Ultraviolet
• Ultraviolet light is in the range of the EM spectrum between visible light and X-rays.
• It has frequencies of about 8 × 1014 to 3 × 1016 Hz and wavelengths of about 380 nm to about 10 nm.
• UV light is a component of sunlight; however, it is invisible to the human eye.
• It has numerous medical and industrial applications, but it can damage living tissue.
X-rays
• X-rays are roughly classified into two types: soft X-rays and hard X-rays.
• Soft X-rays comprise the range of the EM spectrum between UV and gamma rays.
• Soft X-rays have frequencies of about 3 × 1016 to about 1018 Hz and wavelengths of about 10 nm to
about 100 picometers (pm).
• Hard X-rays occupy the same region of the EM spectrum as gamma rays.
• The only difference between them is their source: X-rays are produced by accelerating electrons, while
gamma rays are produced by atomic nuclei.
Gamma-rays
• Gamma-rays are in the range of the spectrum above soft X-rays.
• Gamma-rays have frequencies greater than about 1018 Hz and wavelengths of less than 100 pm.
• Gamma radiation causes damage to living tissue, which makes it useful for killing cancer cells when
applied in carefully measured doses to small regions.
• Uncontrolled exposure, though, is extremely dangerous to humans.
Eαϑ
E = hϑ
E = h C/λ,
since ϑ- = C/λ
E = hCϑ-, since 1/λ = ϑ-
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Various Types of Molecular Spectra
1. Rotational or Microwave spectra – Microwave region
2. Vibrational or Infrared spectra – Infrared region
3. Raman spectra – scattering of light
4. Electronic spectra – UV-Vis region
5. Nuclear magnetic resonance spectra – Radiofrequency region
6. Electron spin resonance spectra – Microwave region
Rotational or Microwave spectra
❖ Molecular spectra resulting from transitions between the rotational energy levels of a gaseous molecule
on the absorption of microwave radiation.
❖ It occurs in the spectral range 1 - 100 cm-1
❖ Molecule must have a permanent dipole moment
❖ HCl, CO, H2O, NO, etc. show microwave spectra
❖ H2, Cl2, CO2, etc. do not show microwave spectra
Vibrational or Infrared spectra
❖ Molecular spectra resulting from transitions between the vibrational energy levels of a molecule on the
absorption of infrared radiation.
❖ It occurs in the spectral range 500 - 4000 cm-1
❖ Vibrational motion is accompanied by a change in dipole moment of molecule
Raman spectra
❖ Deals with scattering of light
❖ It occurs in the spectral range 12500- 25000 cm-1.
Nuclear magnetic resonance spectra
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❖ Molecular spectra resulting from transitions induced between nuclear spin energy levels of a molecule in
an applied magnetic field.
❖ It occurs in the radiofrequency region, 5 - 100 MHz
Electronic spectra
❖ Molecular spectra resulting from electronic transitions in a molecule by the absorption of UV-Vis
radiation.
❖ It occurs in the spectral range 12500 - 25000 cm-1 in visible region and 25000 - 70000 cm-1 in UV
region.
Electron spin resonance spectra
❖ Molecular spectra resulting from transitions induced between electron spin energy levels of a molecule
in an applied magnetic field.
❖ It occurs in the microwave region, 2 - 9.6 GHz
❖ Systems containing odd electron, free radicals, transition metal ions.
1. Which of the following will give pure rotational spectrum, H2, N2, CO2 or HCl.
HCl
2. Which branch of spectroscopy is used for the identification of free radicals?
Electron spin resonance spectroscopy (ESR spectroscopy)
3. What is Born-Oppenheimer Approximation?
• The approach is named after Max Born and J. Robert Oppenheimer who proposed it in 1927.
• In molecular spectroscopy, using the BO approximation means considering molecular energy as a
sum of independent terms.
e.g.: Total energy of a molecule is the sum of rotational energy (E rot), vibrational energy (E vib),
electronic energy (E ele) and translational energy (Etra)
E total = E electronic + E rotational + E vibrational + E translational
According to Born-Oppenheimer Approximation,
E total = E electronic + E rotational + E vibrational
• Molecular spectra arise from 3 types of transition
1. Rotational
1. 2. Vibrational
2. 3. Electronic transitions