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Faraday Discuss. 2009;142:9-23; discussion 93-111.

Molecular collisions, from warm to ultracold.

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Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St., Cambridge, Massachusetts 02138, USA.


This introductory article contrasts molecular collisions, particularly reactive collisions, in the familiar "warm" domain with the ultracold regime where the relative deBroglie wavelengths become long compared with the range of interaction of the collision partners. Ultracold collisions have much greater sensitivity to entrance channel interactions, so offer the prospect of tuning by external fields to control onset of reaction. However, for ultracold collisions, kinematic constraints impose severe limitations on the observable dynamical properties. In the exit channel for appreciably exoergic reactions, the deBroglie wavelengths become short, so the exit dynamics are much like those for warm collisions. Reactions of alkali dimers, halides, and monoxide molecules are discussed that seem especially congenial for cold collision studies.


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