Molecular Conformation and Organic Photochemistry: Time-Resolved Photoionization Studies

ISBN-13: 9783642426742 / Angielski / Miękka / 2014 / 124 str.

Rasmus Y. Brogaard

Opis

Rasmus Brogaard's thesis digs into the fundamental issue of how the shape of a molecule relates to its photochemical reactivity. This relation is drastically different from that of ground-state chemistry, since lifetimes of excited states are often comparable to or even shorter than the time scales of conformational changes. Combining theoretical and experimental efforts in femto-second time-resolved photoionization Rasmus Brogaard finds that a requirement for an efficient photochemical reaction is the prearrangement of the constituents in a reactive conformation.
Furthermore, he is able to show that by exploiting a strong ionic interaction between two chromophores, a coherent molecular motion can be induced and probed in real-time. This way of using bichromophoric interactions provides a promising strategy for future research on conformational dynamics.

Spis treści

Aspects and investigation of photochemical dynamics.- A time-resolved probing method: photoionization.- Simulation of time-resolved photoionization signals.- Simulation: the Norrish type-I reaction in acetone.- Experimental setups.- Paracyclophanes I: [2+2]cycloaddition of ethylenes.- Paracyclophanes II: The Paternò-Büchi reaction.- Probing structural dynamics by interaction between chromophores.

Blurb

Rasmus Brogaard's thesis digs into the fundamental issue of how the shape of a molecules relates to its photochemical reactivity. This relation is drastically different from that of ground-state chemistry, since lifetimes of excited states are often comparable to or even shorter than the time scales of conformational changes. Combining theoretical and experimental efforts in femto-second time-resolved photoionization Rasmus Brogaard finds that a requirement for an efficient photochemical reaction is the prearrangement of the constituents in a reactive conformation.
Furthermore, he is able to show that by exploiting a strong ionic interaction between two chromophores, a coherent molecular motion can be induced and probed in real-time. This way of using bichromophoric interactions provides a promising strategy for future research on conformational dynamics.