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Atmospheric Turbulencea molecular dynamics perspective$
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Adrian F. Tuck

Print publication date: 2008

Print ISBN-13: 9780199236534

Published to Oxford Scholarship Online: November 2020

DOI: 10.1093/oso/9780199236534.001.0001

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Radiative and Chemical Kinetic Implications

Radiative and Chemical Kinetic Implications

Chapter:
6 Radiative and Chemical Kinetic Implications
Source:
Atmospheric Turbulence
Author(s):

Adrian F. Tuck

Publisher:
Oxford University Press
DOI:10.1093/oso/9780199236534.003.0009

The laws governing the dynamical behaviour of atoms and molecules are quantum mechanical, and specify that their internal energy states are discrete, with only definite photon energies inducing transitions between them, subject to selection rules. These energy levels appear as spectra in different regions of the electromagnetic spectrum: pure rotational lines in the microwave or far infrared, ‘rovibrational’ (rotation + vibration) lines in the middle and near infrared, while electronic transitions, sometimes with associated rotational and vibrational structure (‘rovibronic’) occur from the near infrared through the visible to the ultraviolet. An important feature of these spectra in the atmosphere is that they do not appear as single sharp lines, but are collisionally broadened about the central energy into ‘line shapes’ which frequently overlap with other transitions, both from the same molecule and from others. One of the primary dynamical quantities involved in the processes broadening these line shapes is the relative velocity of the molecules with which the photon absorbing and emitting molecules are colliding. These are primarily N2 and O2 in the atmosphere; if they have an overpopulation of fast moving molecules relative to a Maxwell–Boltzmann distribution, as we have suggested, the line shapes will be affected. Molecules such as carbon dioxide, water vapour, and ozone are all active in the infrared via rovibrational transitions, with water vapour being light enough and so having sufficiently rapid rotation that it has rotational bands appearing in the far infrared rather than the microwave. Nitrous oxide, N2O, and methane, CH4, are also active, but make smaller contributions because of their lower abundances. Molecular nitrogen and molecular oxygen, because they are homonuclear diatomic molecules, do not absorb or emit via electric dipole allowed transitions in the atmospherically important regions of the electromagnetic spectrum. Molecular oxygen, having a triplet ground state, does have weak forbidden and magnetic dipole transitions which, however, play only a very small role in the radiative balance. It should be noted that the translational energy of molecules in a large system like the atmosphere is effectively continuous rather than quantized.

Keywords:   Clausius-Clapeyron equation, Fokker-Planck equation, Kolmogorov scaling, Lorentzian profiles, Voigt profiles, activation energy, chemical reactions, cloud physical implications, deuterium

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