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METO 621 Lesson 6

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Absorption by gaseous species Particles in the atmosphere are absorbers of radiation. Absorption is inherently a quantum process. A transition takes place from an initial quantum state to a higher quantum state. When the photon energy is close to the energy difference between the lower and the higher states, the process is called resonance. And the absorption is high. When the opposite is true the absorption is small.

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Absorption by gaseous species This energy selectivity is an outstanding characteristic of absorption. Scattering is generally much less selective and occurs over a much larger region of the spectrum. As we shall see later, molecules have a myriad of discrete energy levels and hence have complex absorption spectra. One reason for our interest in the spectra of molecules lies in the fact that many molecules have absorption features in the thermal infra-red and these are responsible for the thermal equilibrium of the atmosphere. Another is that many molecules absorb strongly on the ultraviolet, where the photons have enough energy to break apart the molecules. The resulting radicals start the chemical processes in both the troposphere and stratosphere.

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Blackbody radiation Consider a tiny opening in a hollow sphere The chance of incoming radiation being reflected back out of the hole is extremely small Hence the opening is perfectly absorbing - it is ‘black. Within the sphere the radiation will have reached thermal equilibrium. The radiation emanating from the internal surface is called ‘blackbody radiation’

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Planck’s spectral distribution law Planck introduced in 1901 his hypothesis of quantized oscillators in a radiating body. He derived an expression for the hemispherical blackbody spectral radiative flux Where h is Planck’s constant, m r is the real index of refraction, k B is Boltzmann’s constant

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Planck’s spectral distribution law Approximations for the spectral distribution law are

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Planck’s function As the blackbody radiation is isotropic, the intensity is related to the hemispherical flux through B is known as the Planck function, and has the same units as intensity When dealing with gases m r is set equal to one

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Planck’s function (1) By differentiating the Planck function and equating the result to zero we find the wavelength corresponding to the maximum: m T = 2,897.8 Wien’s displacement law (2) By integrating the blackbody flux over all frequencies we get : F BB = B T 4 Stefan-Boltzmann Law

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Comparison of solar and earth’s blackbody intensity

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Absorption in molecular lines and bands Molecules have three types of energy levels - electronic, vibrational, and rotational Transitions between electronic levels occur mainly in the ultraviolet Transitions between vibrational levels - visible/near IR Transitions between rotational levels - far IR/ mm wave region O 2 and N 2 have essentially no absorption in the IR 4 most important IR absorbers H 2 O, CO 2, O 3, CH 4

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Vibrational levels Consider a diatomic molecule. The two atoms are bound together by a force, and can oscillate along the axis of the molecule. The force between the two atoms is given by The solution of which is

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Vibrational levels 0 is known as the vibrational frequency theoretically 0 can assume all values However in quantum mechanics these values must be discrete v is the vibrational quantum number

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Vibrational levels In general k depends on the separation of the atoms and we have an ‘anharmonic oscillator’

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Selection Rules Not all vibrational excitation in molecules produces radiation. To produce radiation one needs to have an oscillating dipole. When the molecule is set into a vibration mode, the combined electric field at the center of mass must also oscillate O 2 and N 2, homonuclear molecules, do not possess an oscillating dipole at their center of mass when in the ground state and so do not show vibrational spectra in the IR. On the other hand O 16 O 18 does.

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Schematic of vibrational levels

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Various forms of molecular vibration

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Rotational levels Consider a diatomic molecule with different atoms of mass m 1 and m 2, whose distance from the center of mass are r 1 and r 2 respectively The moment of inertia of the system about the center of mass is:

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Rotational levels The classical expression for energy of rotation is where J is the rotational quantum number

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Vibrating Rotator If there were no interaction between the rotation and vibration, then the total energy of a quantum state would be the sum of the two energies. But there is, and we get The wavenumber of a spectral line is given by the difference of the term values of the two states

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Spectroscopic Analysis Part 4 – Molecular Energy Levels and IR Spectroscopy Chulalongkorn University, Bangkok, Thailand January 2012 Dr Ron Beckett Water.

Spectroscopic Analysis Part 4 – Molecular Energy Levels and IR Spectroscopy Chulalongkorn University, Bangkok, Thailand January 2012 Dr Ron Beckett Water.

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