期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2013
卷号：110
期号：44
页码：17703-17707
DOI：10.1073/pnas.1213080110
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Key experimental and theoretical features of mass-independent fractionation (MIF) of isotopes, also known as the {eta}-effect, are summarized, including its difference from the exit channel zero-point energy difference effect. The latter exactly cancels in the MIF. One key experimental result is that the MIF for O3 formation is a low-pressure phenomenon and, moreover, that it decreases with increasing pressure of third bodies at pressures far below the "Lindemann fall-off" pressures for three-body recombination of O and O2. A possible origin of the MIF is discussed in terms of a role for isotopologue symmetry in intramolecular energy sharing. An explanation is suggested for the large difference in the fall-off pressure for recombination and the pressure for a large decrease in MIF, in terms of a difference between deactivating collisions and what we term here "symmetry-changing collisions". It is noted that the theory of the MIF involves four recombination rate constants and an equilibrium constant, for each trace isotope, seven rate constants in all and two equilibrium constants. A conceptual shortcut is noted. Experimental and computational information that may provide added insight into the MIF mechanism and tests is described.
