The reaction of NO(2) with Fe(2)O(3) has relevance for both atmospheric chemistry and catalysis. Most studies have focused on hematite, α-Fe(2)O(3), as it is the thermodynamic stable state of iron oxide; however, other forms of Fe(2)O(3) naturally occur and may have different chemistries. In this study, we have investigated the reaction products and kinetics for NO(2) reacting with γ-Fe(2)O(3) powder using diffuse reflectance infrared Fourier transform spectroscopy and compared the results to those of previous studies of NO(2) reacting with α-Fe(2)O(3). Both α- and γ-Fe(2)O(3) produce surface-bound nitrate at the pressures examined in this study (24-212 mTorr); surface-bound nitrite products are observed at all pressures for γ-Fe(2)O(3) whereas nitrite was only observed on α-Fe(2)O(3) at lower pressures. Surface-bound NO(+) and Fe-NO products are observed on γ-Fe(2)O(3), which have not been observed with α-Fe(2)O(3). The reaction kinetics show a first-order dependence on NO(2) pressure and this is used to support the hypothesis of unimolecular reaction of adsorbed NO(2) with the γ-Fe(2)O(3) surface as the slow step in the reaction mechanism. The difference in product formation between NO(2) reacting with γ-Fe(2)O(3) and previous studies of α-Fe(2)O(3) illustrate the fact that care must be taken in generalizing reactivity of different polymorphs.

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Polyimides such as 6F‐6F and 6F‐ODA and model N‐arylphthalimides are stabilized against photooxidative degradation by their electron donor (D) – acceptor (A) character. We have investigated the precise origin(s) of this effect using D and A substituents on the N‐aryl groups of these compounds. The lowest excited singlet state (S1) of N‐arylphthalimides is an intramolecular charge transfer (ICT) state. A nominally twisted compound, N‐(2‐t‐butylphenyl)phthalimide, shows greatly diminished CT absorption and blue‐shifted fluorescence with reduced quantum yield when compared to the 4‐t‐butyl isomer with an identical N‐aryl donor group. It therefore seems unnecessary to claim that the ICT state of phthalimides is a so‐called TICT state. Quantum yield and fluorescence lifetime measurements lead to the conclusion that enhanced internal conversion from the ICT state (S1) to the ground state makes a significant contribution to photostabilization of these compounds by suppressing formation of the reactive triplet state. Further stabilization of polymer films may be afforded by triplet state self‐quenching which is enhanced for 6F‐ODA in increasingly poor solvents. N‐alkylarylphthalimides in which the aryl and phthalimide groups are not formally conjugated but, rather, joined by flexible methylene ‘spacers’, exhibit a different kind of fluorescent intramolecular CT singlet state whose formation can also stabilize these compounds by suppressing triplet state formation.

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