Article
Greenhouse gases
Main article: Greenhouse gas
Quantum mechanics provides the basis for computing the interactions
between molecules and radiation. Most of this interaction occurs when the
frequency of the radiation closely matches that of the spectral lines of the
molecule, determined by the quantization of the modes of vibration and
rotation of the molecule. (The electronic excitations are generally not relevant
for infrared radiation, as they require energy larger than that in an infrared
photon.)
The width of a spectral line is an important element in understanding its
importance for the absorption of radiation. In the Earth’s atmosphere these
spectral widths are primarily determined by “pressure broadening”, which is
the distortion of the spectrum due to the collision with another molecule. Most
of the infrared absorption in the atmosphere can be thought of as occurring
while two molecules are colliding. The absorption due to a photon interacting
with a lone molecule is relatively small. This three-body aspect of the
problem, one photon and two molecules, makes direct quantum mechanical
computation for molecules of interest more challenging. Careful laboratory
spectroscopic measurements, rather than ab initio quantum mechanical
computations, provide the basis for most of the radiative transfer calculations
used in studies of the atmosphere.
The molecules/atoms that constitute the bulk of the atmosphere: oxygen (O2),
nitrogen (N2) and argon (Ar); do not interact with infrared radiation
significantly. While the oxygen and nitrogen molecules can vibrate, because
of their symmetry these vibrations do not create any transient charge
separation. Without such a transient dipole moment, they can neither absorb
nor emit infrared radiation. In the Earth’s atmosphere, the dominant infrared
absorbing gases are water vapor, carbon dioxide, and ozone (O3). The same
molecules are also the dominant infrared emitting molecules. CO2 and O3
have "floppy" vibration motions whose quantum states can be excited by
collisions at energies encountered in the atmosphere. For example, carbon
dioxide is a linear molecule, but it has an important vibrational mode in which
the molecule bends with the carbon in the middle moving one way and the
oxygens on the ends moving the other way, creating some charge
separation, a dipole moment, thus carbon dioxide molecules can absorb IR
radiation. Collisions will immediately transfer this energy to heating the
surrounding gas. On the other hand, other CO2 molecules will be vibrationally
excited by collisions. Roughly 5% of CO2 molecules are vibrationally excited
at room temperature and it is this 5% that radiates. A substantial part of the
greenhouse effect due to carbon dioxide exists because this vibration is
easily excited by infrared radiation. CO2 has two other vibrational modes. The
symmetric stretch does not radiate, and the asymmetric stretch is at too high
a frequency to be effectively excited by atmospheric temperature collisions,
although it does contribute to absorption of IR radiation. The vibrational
modes of water are at too high energies to effectively radiate, but do absorb
higher frequency IR radiation. Water vapor has a bent shape. It has a
permanent dipole moment (the O atom end is electron rich, and the H atoms
electron poor) which means that IR light can be emitted and absorbed during
rotational transitions, and these transitions can also be produced by
collisional energy transfer. Clouds are also very important infrared absorbers.
Therefore, water has multiple effects on infrared radiation, through its vapor
phase and through its condensed phases. Other absorbers of significance
include methane, nitrous oxide and the chlorofluorocarbons.
Discussion of the relative importance of different infrared absorbers is
confused by the overlap between the spectral lines due to different gases,
widened by pressure broadening. As a result, the absorption due to one gas
cannot be thought of as independent of the presence of other gases. One
convenient approach is to remove the chosen constituent, leaving all other
absorbers, and the temperatures, untouched, and monitoring the infrared
radiation escaping to space. The reduction in infrared absorption is then a
measure of the importance of that constituent. More precisely, define the
greenhouse effect (GE) to be the difference between the infrared radiation
that the surface would radiate to space if there were no atmosphere and the
actual infrared radiation escaping to space. Then compute the percentage
reduction in GE when a constituent is removed. The table below is computed
by this method, using a particular 1-dimensional model of the atmosphere.
More recent 3D computations lead to similar results.
Gas removed percent reduction in GE
H2O 36%
CO2 9%
O3 3%
(Source: GISS-GCM ModelE simulation) [4]
By this particular measure, water vapor can be thought of as providing 36%
of the greenhouse effect, and carbon dioxide 9%, but the effect of removal of
both of these constituents will be greater than the total that each reduces the
effect, in this case more than 45%. An additional proviso is that these
numbers are computed holding the cloud distribution fixed. But removing
water vapor from the atmosphere while holding clouds fixed is not likely to be
physically relevant. In addition, the effects of a given gas are typically
nonlinear in the amount of that gas, since the absorption by the gas at one
level in the atmosphere can remove photons that would otherwise interact
with the gas at another altitude. The kinds of estimates presented in the table,
while often encountered in the controversies surrounding global warming,
must be treated with caution. Different estimates found in different sources
typically result from different definitions and do not reflect uncertainties in the
underlying radiative transfer.