W spektroskopii, stany wzbudzone cząsteczek zwykle bada się metodami optycznymi, które pozwalają rejestrować stany dozwolone optycznymi regułami wyboru (stany singletowe). Wykorzystanie własności zderzeń elektronów z cząsteczkami, badanych za pomocą wiązkowych spektrometrów elektronowych, umożliwia obserwację stanów wzbudzonych, do których przejścia optyczne są wzbronione (stany trypletowe). W artykule przedstawiono elektronową spektroskopię zderzeniową oraz przykładowe badania cząsteczek azotu i pirydazyny.
EN
An excited states of molecules are usually studied using optical methods, which enable observation of the excited states allowed by the optical selection rules (singlet states). An electron collisions with molecules, investigated using crossed-beam electron spectrometers, permit to investigate excited states that are optically-forbidden (triplet states). In this article, an electron collision spectroscopy is presented and illustrated by results obtained for nitrogen and pyridazine molecules.
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The paper presents results of spectral and photophysical studies obtained for molecules representing three different classes of compounds: • Schiff bases with strong intramolecular hydrogen bond, occurring in a few phototautomers, • Aminophtalimides with LE and ICT type electronic excited states forming exciplexes through hydrogen bonds with the solvent molecules, • Thioketones with a thiocarbonyl group becoming exceptionally reactive in the S2 state, quenched by molecules of solvent of different properties. It should be emphasized that for all compounds, irrespective of the complex mechanisms of their deactivation characterised by different dynamics, the dominant final process is the reproduction of the chemically unchanged substrate in the ground state. The necessary condition of the correct interpretation of the complex properties of the compounds studied in electronic excited states is the proper choice of solvents of specific properties. Through this proper choice of solvents it becomes possible to study the role of nonspecific and specific (hydrogen bonds) interactions with the solvent and to observe the intramolecular and intermolecular processes of deactivation. The results presented could be obtained thanks to the use of the steady-state and time-resolved laser methods of absorption and emission spectroscopy with a pico- and femtosecond resolution. The results obtained can be helpful in the study of compounds of similar properties and more complex systems including biological systems.
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