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2-10 Intro To Spectroscopic Methods

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28 views21 pages

2-10 Intro To Spectroscopic Methods

Uploaded by

Amal Patel
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Introduction to Spectroscopic

Methods
 Light may be thought of as either a
electromagnetic wave or as particles called
quanta
 The two models for light are complementary.
The wave model works best when light interacts
with itself and the particle model works best
when light interacts with matter
 The two models are known as a wave-particle
duality
Wave model of light
 According to the wave model of light, light is an
electromagnetic wave which oscillates in both
space and time
 A good analogy is an ocean wave
 If we take a picture of waves coming into shore we
may measure the distance between crests. This
distance is called the wavelength. A plot of the wave
as a function of distance from shore describes how the
wave oscillates with distances in a sinusoidal manner
Wave model of light
 Now imagine yourself on a raft some fixed
distance from shore. You are constantly
bobbing up and down. The time between
crests is called the period. The reciprocal of
the period is the frequency (usually measured
in sec-1)
Wave model of light
 Electromagnetic waves propagate with an
electric field perpendicular to the magnetic
field where both oscillate perpendicular to
the direction of propagation
Wave model of light
 The electric field is responsible for most of
the spectroscopic phenomena, including
transmission, reflection, refraction and
absorption. The magnetic field induces
nuclear transitions
1/p=n
ln=vi
Wave model of light
 The frequency of the light is invariant and
depends on the source
 The speed of light depends on the medium
through which it travels
 In a vacuum light travels at 2.99792 x 10 8
m/s and about 0.03% slower through air.
Hence, to two decimals we can write
ln = c = 3.00 x 108 m/s
Wave model of light
 When the electric field oscillates in one
plane the light is said to be polarized.
Most light emitted from natural sources is
not polarized. When viewed end on the
electric fields are randomly oriented

Polarized light Natural light viewed end on


Polarized irradiation
 Polarized EM radiation is produced by
certain radiant sources. For example, radio
waves emanating from an antenna and
microwaves produced by a klystron tube.
 Polarized UV and visible light is produced
by the passage of radiation through media
that selectively absorb or reflect one plane
of irradiation
Regions of electromagnetic
radiation
Interaction of irradiation with
matter
 When describing the interaction of light with
matter it is best to assume that light behaves like
tiny particles called photons
 The photons each carry one packet or quanta of
energy where
E = hn
h = Planck’s constant = 6.6254 x 10-34 joule-sec
Quantum Theory of matter
 Molecules may exist in discrete energy states
called steady states
 In atoms this applies to discrete orbits of the
electrons about the nucleus. In molecules
vibrations and rotations are also quantized.
 The lowest energy state is called the ground state
and other levels are called excited states
Absorption of radiation
 Absorption is the process by which atoms
and molecules absorb EM radiation and are
excited from a ground state to an excited
state.
 Since energy states are quantized, the
frequency of absorbed light must match the
difference in energy spacing
n1 = (E1-Eo)/h
Absorption
 For atoms, electrons are excited from inner shells
to outer orbitals
 Molecules have energy distributed between
rotational, vibrational and electronic energy states
E = Eelectronic + Erotational + Evibrational
 Irradiation may excite molecules between the
ground and excited states of any of these energy
forms
Diatomic Potential functions
 Diatomics rotate and
vibrate. The
vibrational energy
levels are equally
spaced within the
electronic potential.
 Rotational energy
levels are more
closely spaced within
the vibrational energy
levels
Types of spectroscopy as a
function of wavelength
Summary of Instrument
Components
Instrumentation
 Source
 Deuterium lamp
Wavelength varies from 160 nm to 350 nm
 Tungsten filament
 350 nm to 2500 nm - lower wavelength is limited by glass
components
 Requires close voltage regulation to avoid flicker
Instrumentation
 Wavelength selectors
 Filter (Hg lamp – 254 nm)
 Grating
 Sample containers
 UV work requires quartz or fused silica
 VIS work, glass or plastic cuvettes
Instrumentation
 Photodetector
 Photocell or PMT
 Signal processor and readout
Diode Array Instruments
 Resolution is limited by the dispersion of
the grating and the number of diode
elements
 Generally these instruments can acquire 2 nm
resolution from 200 to 820 nm in less than
0.1 s
 Advantage for doing kinetic work or
improving signal to noise by repeated
scanning
Diode Array Instruments

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