Print Email Facebook Twitter Charge transfer versus molecular conductance: Molecular orbital symmetry turns quantum interference rules upside down Title Charge transfer versus molecular conductance: Molecular orbital symmetry turns quantum interference rules upside down Author Gorczak, N. Renaud, N. Tarkuç, S. Houtepen, A.J. Eelkema, R. Siebbeles, L.D.A. Grozema, F.A. Faculty Applied Sciences Department Chemical Engineering Date 2015-05-11 Abstract Destructive quantum interference has been shown to strongly reduce charge tunneling rates across molecular bridges. The current consensus is that destructive quantum interference occurs in cross-conjugated molecules, while linearly conjugated molecules exhibit constructive interference. Our experimental results on photoinduced charge transfer in donor-bridge-acceptor systems, however, show that hole transfer is ten times faster through a cross-conjugated biphenyl bridge than through a linearly conjugated biphenyl bridge. Electronic structure calculations reveal that the surprisingly low hole transfer rate across the linearly conjugated biphenyl bridge is caused by the presence of destructive instead of constructive interference. We find that the specific molecular orbital symmetry of the involved donor and acceptor states leads to interference conditions that are different from those valid in single molecule conduction experiments. Furthermore, the results indicate that by utilizing molecular orbital symmetry in a smart way new opportunities of engineering charge transfer emerge. Subject Open Access To reference this document use: http://resolver.tudelft.nl/uuid:4fba60ed-0c2d-49de-99fd-fbf6198ea71a DOI https://doi.org/10.1039/c5sc01104c Publisher RSC publishing ISSN 2041-6539 Source Chem. Sci., 2015,6, 4196-4206 Part of collection Institutional Repository Document type journal article Rights (c) RSC Files PDF c5sc01104c.pdf 1.87 MB Close viewer /islandora/object/uuid:4fba60ed-0c2d-49de-99fd-fbf6198ea71a/datastream/OBJ/view