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By Paul M. Mayer, Christiane Aubry, John Holmes

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Extra info for Assigning Structures to Ions in Mass Spectrometry

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Such BE or EB double-focusing instruments can have mass-resolving power in excess of 150,000. However, the most important results, as far as research in ion structures is concerned, have come from the use of mass spectrometers of BE geometry wherein an ion of interest can be separated from all others by the magnet (B) and then subjected to a wide range of physical experiments in the field-free region lying between it and the electrostatic sector. Scanning the electrostatic sector permits the analysis of all ionic products from the experiment and in some cases the neutral fragments as well.

The method suffers from the same disadvantages, described in the ensuing sections, as do the other threshold studies mentioned above. Key articles are to be found in Ref. [80]. In principle it would appear that the direct measurement of an AE value should be no more difficult than obtaining an IE. However, this is not so and the following problems must be addressed whenever DfH for a fragment ion is determined from an AE experiment. AE Measurements and Fragment Ion Structures The first issue that must be addressed is the structure of the fragment ion.

C6H5Cl>C6H5Br>C6H5I, consistent with the decreases in the activation energy for the C–X bond cleavage, which are approximately 320, 270 and 230 kJ=mol for the chloride, bromide and iodide, respectively. 4. The metastable ion AE values lie close to the PEPICO data at the lowest rate constants, while the ESE data reflect the longer source residence time for such apparatus of approximately 35 ms. 7a now requires another term: AE(Aþ ) ¼ Df H(Aþ ) þ Df H(B ) À Df H(AB) þ Erev þ KS (1:7b) AE Measurements and the Energy Content of the Products The final problem with these measurements concerns the internal and translational energy contents of the product ion and neutral, Eprods.

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