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Electronic transitions
UV and visible wavelengths
Molecular vibrations
Thermal infrared wavelengths
Increasing energy
Molecular rotations
Microwave and far-IR wavelengths ~10-23 J
ij = Eij/h
(a) allowed transitions (b) positions of the absorption lines in the spectrum of the molecule Line positions are determined by the energy changes of allowed transitions Line strengths are determined by the fraction of molecules that are in a particular initial state required for a transition Multiple degenerate transitions with the same energy may combine
Fluorescence
Fluorescent lighting exploits this phenomenon: certain phosphors emit visible light when bombarded with UV light. Much more efficient than incandescent lighting. Also whitening agents in detergents...
Wavelength
If there are no available quantized energy levels matching the quantum energy of the incident radiation, then the material will be transparent to that radiation
X-ray interactions
Quantum energies of x-ray photons are too high to be absorbed by electronic transitions in most atoms - only possible result is complete removal of an electron from an atom Hence all x-rays are ionizing radiation If all the x-ray energy is given to an electron, it is called photoionization If part of the energy is given to an electron and the remainder to a lower energy photon, it is called Compton scattering
Ultraviolet interactions
Near UV radiation (just shorter than visible wavelengths) is absorbed very strongly in the surface layer of the skin by electron transitions At higher energies, ionization energies for many molecules are reached and the more dangerous photoionization processes occur Sunburn is primarily an effect of UV radiation, and ionization produces the risk of skin cancer
Visible light is also absorbed by electron transitions Higher energies at blue wavelengths relative to red wavelengths: hence red light is less strongly absorbed than blue light Absorption of visible light causes heating, but not ionization Car windshields transmit visible light but absorb higher UV frequencies
Quantum energy of IR photons (0.001-1.7 eV) matches the ranges of energies separating quantum states of molecular vibrations Vibrations arise as molecular bonds are not rigid but behave like springs
Microwave interactions
Quantum energy of microwave photons (0.00001-0.001 eV) matches the ranges of energies separating quantum states of molecular rotations and torsion Note that rotational motion of molecules is quantized, like electronic and vibrational transitions associated absorption/emission lines Absorption of microwave radiation causes heating due to increased molecular rotational activity Most matter transparent to -waves, microwave ovens use high intensity -waves to heat material
Molecules with mirror symmetry like oxygen, nitrogen and carbon dioxide have no permanent dipole moments.
Linear and spherical top molecules have the fewest distinct modes of rotation, and hence the simplest absorption spectra Asymmetric top molecules have the richest set of possible transitions, and the most complex spectra
Note lack of permanent electric dipole moment in CO2 and CH4
No
1 2 3
A normal mode is IR-active if the dipole moment changes during mode motion. Overtones, combinations and differences of fundamental vibrations are also possible (e.g., 2v1, v1+v3 etc.) A non-linear molecule of N atoms has 3N-6 normal modes of vibration; a linear molecule has 3N-5.
1 2c
m1, m2 = atomic mass of vibrating atoms c = speed of light [3108 m s-1] V = wavenumber [cm-1] Av = Avogadros number [6.0231023 atoms mole-1] k = force constant (bond strength) [dynes cm-1]
For a single bond, k = 5105 dynes cm-1 For a double bond, k = 10105 dynes cm-1 For a triple bond, k = 15105 dynes cm-1
Vibrations can be subdivided into two classes, depending on whether the bond length or angle is changing:
Stretching (symmetric and asymmetric) Bending (scissoring, rocking, wagging and twisting) Stretching frequencies are higher than corresponding bending frequencies (it is easier to bend a bond than to stretch or compress it) Bonds to hydrogen have higher stretching frequencies than those to heavier atoms. Triple bonds have higher stretching frequencies than corresponding double bonds, which in turn have higher frequencies than single bonds
Mid IR
Near IR
2.5 - 50
1 - 2.5
25 - 496
496 - 1240
200 - 4000
4000 - 10000
Molecular vibrations
Overtones
Electronic, vibrational and rotational energy levels are superimposed The absorption spectrum of a molecule is determined by all allowed transitions between pairs of energy levels, and whether the molecule exhibits a sufficiently strong electric or magnetic dipole moment (permanent or otherwise) to interact with the radiation field
Vibrational-rotational transitions
P branch (J = -1)
Q branch (J = 0) (pure vibration) R branch (J = +1)
P branch
R branch
Pressure broadening
Absorption coefficient of O2 in the microwave band near 60 GHz at two different pressures. Pressure broadening at 1000 mb obliterates the absorption line structure.
o
asymmetric stretch v3 = 2.66 m
Higher order vibrational transitions (v >1) give weak absorption bands at shorter wavelengths in the shortwave bands 2H isotope (0.03% in atmosphere) and 18O (0.2%) adds new (weak) lines to vibrational spectrum 3 rotational modes (J1, J2, J3) Overtones and combinations of rotational and vibrational transitions lead to several more weak absorption bands in the NIR
bend v2 = 15 m
bend v2 The v3 vibration is a parallel band (dipole moment oscillates parallel to symmetric axis), transition J = 0 is forbidden, no Q branch, greater total intensity than v2 fundamental The v2 vibration is perpendicular band, has P, Q, and R branch The v3 fundamental is the strongest vibrational band, but the v2 fundamental is most effective due to matching of vibrational frequencies with terrestrial Planck emission function 13C isotope (1% of C in atmosphere) and 17/18O isotope (0.2%) cause a weak splitting of rotational and vibrational lines in the CO2 spectrum
v3
v2
Ozone (O3)
Ozone is primarily present in the stratosphere except anthropogenic ozone pollution which exists in the troposphere Asymmetric top similar absorption spectrum to H2O due to similar configuration (nonlinear, triatomic) Strong rotational spectrum of random spaced lines Fundamental vibrational modes
o o o
bend v2 = 14.3 m
o
asymmetric stretch v3 = 9.6 m
14.3 m band masked by CO2 15 m band Strong v3 band and moderately strong v1 band are close in frequency, often seen as one band at 9.6 m 9.6 m band sits in middle of 8-12 m H2O window and near peak of terrestrial Planck function Strong 4.7 m band but near edge of Planck functions
IR Absorption Spectrum of O3
v1/v3
v2
Methane (CH4)
Spherical top 5 atoms, 3(5) 6 = 9 fundamental modes of vibration Due to symmetry of molecule, 5 modes are degenerate, only v3 and v4 fundamentals are IR active No permanent dipole moment => No pure rotational spectrum Fundamental modes
H C H H H v1 v2 v3 = 3.3 m v4 = 7.7 m
v3
v4
7.6 m band in otherwise largely transparent part of atmosphere Methane concentrations also directly/indirectly affected by human activities
v3=4.5 m
v1=7.8 m
v2=17 m
Geological mapping/prospecting
Escondida Mine, Atacama Desert, Chile
ASTER visible
Why are most plants green and then red or yellow in the fall?
Chlorophyll absorbs in the red and blue, and hence reflects in the green.
Its absorption spectrum is due to electronic transitions
In the fall, trees produce carotenoids, which reflect yellow, and anthocyanins, which reflect orange and red.