Collisions between carbon dioxide molecules
DOI: 10.1063/1.4796876
Can affect greenhouse warming. Visible light coming from the Sun pours down daily and is reflected back from Earth’s surface as IR radiation. Extra warming occurs when some of that IR is absorbed and retained in the atmosphere. Only a trace gas in the atmosphere, CO2 is far outnumbered by O2 and N2 molecules, but its growing presence (mostly due to human activity) and its ability to absorb and trap IR radiation are thought to be instrumental in producing greenhouse effects. The interactions between atoms in a single molecule generate the molecule’s dipole moment and polarizability, two properties that greatly affect how the molecule absorbs or scatters radiation. Going to the next level of complexity, a new study shows in detail how a large class of molecules, including CO2, absorbs and sometimes scatters light energy during intermolecular collisions. Michael Chrysos and his colleagues at the University of Angers (France) and Saint Petersburg State University (Russia) have derived exact mathematical formulas that can be used to calculate how collisions between so-called linear-rotor molecules modify the molecules’ absorption spectra. During a molecular interaction, a transient supermolecular complex arises with its own degrees of freedom—distinct from those of the constituent molecules—and its own dipole moment or polarizability. The net result is that a broad band of frequencies, including many that are unavailable to single molecules, can be absorbed or scattered. The new study is important for several reasons: It allows exact calculations of how the intercepted IR photon energy is converted to kinetic energy and shared among neighboring gas molecules; it allows for the inclusion of higher-order effects, such as the simultaneous collision of three molecules; and it provides evidence that long-range intermolecular interactions are far more important than short-range ones for absorption, a conclusion in conflict with mainstream assumptions. (M. Chrysos et al., Phys. Rev. Lett. 100 , 133007, 2008 .http://dx.doi.org/10.1103/PhysRevLett.100.133007