Light and Matter

Light and Matter Interaction

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Electromagnetic Radiation
Properties Particle-like Photon Quantum Wave-like Wavelength, Frequency,

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PHOTON

Electromagnetic nature of photons are the same Differ in energy and frequency
c= E = h = hc /

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Properties of wave

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Properties of a Photon
E

= h h=
6.6 x 10-27 erg sec 6.6 x 10-34 Js

= c/

c=

3 x 1010 cm/sec

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Electromagnetic Spectrum

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Exercises
1. The wavelength of the green light from a traffic signal is centered at 522 nm. What is the frequency of this radiation? 2. Calculate the energy (joules) of a photon with a wavelength of 5.00 x 104 nm (IR region).

3. What is the wavelength of a photon (nm) emitted during a transition from ni = 5 state to the nf = 2 state in the hydrogen atom?

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Spectroscopy
Deals with interaction of electromagnetic radiation (EMR) with a molecule
Transitions between energy levels that involve the absorption or emission of light Uses Quantum mechanics to mathematically describe matter on the atomic scale.

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Interaction of matter and radiation

Absorption
lower to a higher level field transition transfer of energy from the radiation field to an absorber.

Emission
higher to a lower level transition transfer of energy from the emitter to the radiation field. nonradiative decay if no radiation is emitted

Scattering
redirection of light scattering may or may not occur with a transfer of energy, i.e., the scattered radiation may or may not have a different wavelength to the incident light.

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Electromagnetic Spectrum
Type of Radiation gamma-rays X-rays ultraviolet visible near-infrared infrared microwaves radio waves Frequency Range (Hz) 1020-1024 1017-1020 1015-1017 4-7.5x1014 1x1014-4x1014 1013-1014 3x1011-1013 <3x1011 Wavelength Range <1 pm 1 nm-1 pm 400 nm-1 nm 750 nm-400 nm 2.5 m-750 nm 25 m-2.5 m 1 mm-25 m >1 mm Type of Transition nuclear inner electron outer electron outer electron outer electron molecular vibrations molecular vibrations molecular rotations, electron spin flips* nuclear spin flips*

*for energy levels split by a magnetic field

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ABSORPTION MECHANISM

Electrons are promoted to higher orbitals by ultraviolet or visible light

Vibrations are excited by infrared light

Rotations are excited by microwaves

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Jablonski Diagram
Relaxation mechanism for excited state molecules
Vibrational relaxation, 10-12 s

10-5 10-8 s

10-4 s

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Carbenes /Methylenes
6 electrons in outermost shell, : CH2 Singlet and triplet

H H

c
Singlet

H H

triplet
sp 180o paramagnetic

sp2 < 120o diamagnetic

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Emission Spectroscopy
Atomic or Optical Excitation by high-temperature energy source Fluoresence or Phosphoresence Excitation by light Molecular Florescence Laser-induced Fluoresence

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Characteristic of Emission Spectra

continuous
all wavelengths of visible light are present example; sunlight, red-hot/white-hot iron bar glow

line
light emission only at specific wavelength example; atoms in gas phase

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Line Spectrum of gaseous atom

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Series in Atomic Hydrogen emission spectrum

Series

nf

ni

Spectrum Region

Lyman Balmer Paschen

1 2 3

2, 3, 4 3, 4, 5 4, 5, 6

Ultraviolet
Visible and Ultraviolet

Infrared

Brackett

5, 6, 7

Infrared

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Energy levels of Hydrogen atom and different emission series

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Spectrometric Techniques
Technique Basis
Atomic emission after excitation in high Temp gas plasma
Atomic emission after flame excitation

Application
Metals and some nonmetals at trace levels
Alkali and alkaline earth metals

Plasma emission

Flame emission

Atomic Absorption

Atomic absorption after atomization by flame or electrothermal means

Atomic fluorescence emission after flame excitation Atomic or atomic fluorescence emission after excitation by electrons or radiation

Trace metals and some non-metals

Mercury and hydrides of non-metals at trace levels Elemental components of metallurgical and geological samples
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Atomic Fluorescence X-ray emission

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Light and Matter

Spectrometric Techniques
Technique Basis
-ray emission after nuclear excitation
Electronic molecular absorption in solution

Application
Radioactive elements in environmetal samples
Quantitative determination of unsaturated organic compounds Identification of organic compounds Identification and structural analysis of organic compounds Identification and structural analysis of organic compounds
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-spectrometry
Ultraviolet/Visible

Infrared Nuclear Magnetic Resonance

Electronic molecular absorption Nuclear absorption due to change in spin states

Mass spectrometry Ionization and

fragmentation of molecules

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Light and Matter

Separation Techniques
Technique Basis
Differential rates of migration of analytes through a stationary phase by movement of a liquid or gaseous mobile phase

Application
Qualitative analysis of mixtures
Quantitative and qualitative analysis of volatile compounds Quantitative and qualitative analysis of nonvolatile compounds

Thin Layer Chromatography

Gas Chromatography

High Performance Liquid Chromatography

Electrophoresis

Differential rates of migration of analytes through a buffered medium

Quantitative and qualitative analysis of ionic compounds

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Beers Law

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Absorption Law
Known as Beer-Lamberts Law Commonly known as Beers Law Relates factors that affect the attenuation of monochromatic radiation
Absorbing solution of concentration, c

Po

b
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Transmittance
Refers to the amount of radiation that passes through the medium Often expressed as % T

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Absorbance
Refers to radiation taken in by the sample Transfers energy to absorbing molecules Leads to decrease in intensity of radiation

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Beers Law

a = absorptivity or extinction coefficient, k A = absorbance, unitless quantity b = pathlength c = concentration

= molar absorptivity or molar extinction coefficient c = mole/L

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For Mixtures

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Assumptions
Incident radiation is monochromatic Absorbers (molecules, atoms etc.) are independent of each other Incident radiation are of parallel rays, perpendicular to surface of absorbing medium Absorbing medium is homogeneous and does not scatter radiation Path length is uniform over the cross-section of beam. Incident flux will not lead to saturation effects

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Limitations
Beers Law is a limiting Law Only true for dilute solution ( 0.01 M) Affected by extent of interaction between molecules Affected by charge distribution Affected by electrostatic interaction Affected by high concentration of electrolytes/analyte change in refractive index
shift in chemical equilibrium

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Limitations of Beers Law

Scattering of light due to particulates in the sample Stray light Few exceptions to linear relationship of A and b at fixed c More exception between A and c at fixed b real deviation instrumental deviations chemical deviations

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Chemical Deviations

absorption, dissociation or reaction with solvent

monomer-dimer formation metal complex formation acid-base interaction

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Instrumental Deviations
A. Strictly applies only to monochromatic radiation Polychromatic radiation differs when of each varies Select where sample absorbs the most

B. Stray Light Results from scattering and reflection off gratings, mirrors, lenses, filters and windows More significant at high absorbance values
C. Mismatched Cells

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