Reactividad Química a Dos Estados: Algunos Ejemplos en Química Orgánica, Inorgánica y Organometálica

Abstract

A variety of chemical phenomena are governed by transitions at crossing points of potential energy surfaces of electronic states with different spin multiplicities, if not directly, but indirectly in the midst of the processes. In other words, this intercrossing transition makes one of the most significant key mechanisms in chemical reactivity. Since the basic theory is now available to treat the transitions with appropriate theoretical methods and techniques, it is possible to comprehend the chemical reactivity of chemical systems, ranging from organic, inorganic, as well as realistic model systems of chemical processes in heterogeneous catalysis with the effects of transitions taken into account properly. Furthermore, it becomes feasible to control chemical reactivity by controlling the transitions at crossing points, and also to develop new molecular functions by using peculiar properties of non-adiabatic transitions. These may be realized, if we apply appropriately designed laser fields. This Ph.D. Thesis is focused on the above mentioned ideas based on the authors’ recent publications. In particular, we have considered three areas where TSR mechanisms appear. We present examples of TSR in organic, organometallic and inorganic chemistry. In organic chemistry, the study of the thermal ring opening rearrangement of 1H-bicyclo[3.1.0]hexa-3,5-dien2-one has been carried out. In organometallic chemistry have been focused on the framework of the heterogeneous catalysis, in particular, on the selective oxidation of methanol to formaldehyde on supported and hydrated vanadium oxides, and also the dehydrogenation of methanol on supported reduced vanadium oxides. Finally, the examples in inorganic chemistry involve the oxidation of H2 by means of MO2 oxides (M=Ti, Zr, Hf). Thus, the non-adiabatic chemical reactivity is expected to open a new dimension of Chemistry.