Isotopic Fractionation by Ion-Molecule Reactions

Isotopic fractionation in interstellar clouds can occur by ion-molecule reactions at low temperatures. The major effect is not kinetic but thermodynamic in origin in that it arises from the difference in rate coefficients between forward and backward directions in reactions which exchange isotopic atoms. In this article, we concentrate on deuterium fractionation in interstellar clouds; this effect enhances the relative abundances of deuterated isotopomers to their normal counterparts by up to four orders of magnitude as compared with the basic D/H elemental abundance ratio. We also discuss the fractionation of ¹⁵N and ¹³C. This revised version was published online in August 2006 with corrections to the Cover Date.