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Pushing and pulling electrons: the effect on the heat of formation of trifluoromethyl compounds Pushing and pulling electrons: the effect on the heat of formation of trifluoromethyl compounds Bartmess, John; Liebman, Joel 2013-06-23 00:00:00 The effect on heats of formation, of conjoined or proximate functional groups which can interact via polar or resonance effects, is examined using the –CF3 group as a standard. Two metrics are applied: the difference in heat of formation of G–CF3 and G–CH3, where –G is a wide range of functional groups, and also the deviation of the heat of formation of G–CF3 from the average of the heats of formation of G–G and CF3–CF3. This latter metric reveals both stabilizing and destabilizing effects on the heat of formation, of up to 60 kcal/mol, depending on the polar and resonance nature of the –G structure. The possibility of using such metrics as a correction the group additivity values is examined. Structural Chemistry Springer Journals http://www.deepdyve.com/lp/springer-journals/pushing-and-pulling-electrons-the-effect-on-the-heat-of-formation-of-NqPpgHZbdv.
Abstract The effect on heats of formation, of conjoined or proximate functional groups which can interact via polar or resonance effects, is examined using the –CF3 group as a standard. Two metrics are applied: the difference in heat of formation of G–CF3 and G–CH3, where –G is a wide range of functional groups, and also the deviation of the heat of formation of G–CF3 from the average of the heats of formation of G–G and CF3–CF3.
This latter metric reveals both stabilizing and destabilizing effects on the heat of formation, of up to 60 kcal/mol, depending on the polar and resonance nature of the –G structure. The possibility of using such metrics as a correction the group additivity values is examined. Journal Structural Chemistry – Springer Journals Published: Jun 23, 2013.
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[1] We examine signatures of two types of waves that may be involved in the acceleration of energetic electrons in Earth's outer radiation belts. We have compiled a database of ULF wave power from SAMNET and IMAGE ground magnetometer stations for 1987–2001.
Long‐duration, comprehensive, in situ VLF/ELF chorus wave observations are not available, so we infer chorus wave activity from low‐altitude SAMPEX observations of MeV electron microbursts for 1996–2001 since microbursts are thought to be caused by interactions between chorus and trapped electrons. We compare the ULF and microburst observations to in situ trapped electrons observed by high‐altitude satellites from 1989–2001. We find that electron acceleration at low L shells is closely associated with both ULF activity and MeV microbursts and thereby probably also with chorus activity.