The search for functional molecular architectures on surfaces calls for new strategies in controlling surface reactions. Here, we show for ether cleavage on Si(001) as a test system that controlled electronic and vibrational excitation can open reaction channels beyond thermally activated reaction schemes: tip-induced excitation of the system in an STM leads to new final products and the type of final products is controlled by selectively addressing different excitation channels: Above a threshold voltage of 2.5 V, direct electron transfer into the antibonding C-O orbital of the tetrahydrofuran (THF) molecules induces ether cleavage of the datively-bonded intermediate of THF on Si(001). Below the threshold, ether cleavage is induced by multiple excitation of vibrational modes. The distributions of final products are different when compared to thermal excitation and significantly differ for the two non-thermal excitation modes. The results thus demonstrate how the final reaction products can be controlled by means of the different excitation mechanisms which in turn can be selectively addressed by the tunneling voltage [1]. When we compare the results of THF with diethylether on Si(001), we find surprising differences. The comparison gives detailed insight into the driving forces of such chemical reactions of organic molecules on semiconductor surfaces.<br/>

Semiconductor surface chemistry beyond thermal activation: Surface reactions on Si(001) controlled by electronic and vibrational excitation

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.