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Linking Molecular Switches to Platinum Electrodes Studied with DFT

Jacob, Timo and Blanco, Mario and Goddard, William A., III (2007) Linking Molecular Switches to Platinum Electrodes Studied with DFT. Journal of Physical Chemistry C, 111 (6). pp. 2749-2758. ISSN 1932-7447. doi:10.1021/jp0632844.

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Density functional theory (DFT) with the B3LYP exchange−correlation functional was used to study new linkages between electrodes and molecular switches (alligator-clip compounds) for molecular electronics using Pt electrodes. Starting with the commonly used molecule 3-methyl-1,2-dithiolane (MDTL), which forms a five-membered ring structure in the gas phase, we found the most stable structure of the adsorbed MDTL to be the ring-opened molecule (32.44 kcal/mol) with each S atom bound to a surface bridge position. Afterward we calculated binding energies and geometries for a variety of different compounds:  S/O-based (oxathiolanes), O-based (methanol), N-based (imidazole, 1,2,3-triazole, purine, 2,4-diazapentane), and P-based molecules (methylphosphino, PCH_3, 3-methyl-1,2-diphospholane before (MDPL) and after H dissociation (H_(diss)-MDPL)). Among these alternative linkage molecules we find that only the P-based compounds lead to much higher binding energies than MDTL. The best compromise between strong surface attachment and mechanical stability provide the MDPL molecules. For the cis-ring-closed structure of MDPL a binding energy of 47.72 kcal/mol was calculated and even 54.88 kcal/mol for the ring-opened molecule. In the case of H-dissociative adsorption, which leads to H_(diss)-MDPL, both binding energies increase to 53.74 (ring-closed) and 74.99 kcal/mol (ring-opened). Thus, MDPL provides a much more stable link to the metal surface and might increase the conductance between molecular switch and electrode. In addition, the minor differences in charge and spin-density distribution between MDTL and MDPL might indicate similar properties for the attachment of the molecular switch to either of both alligator-clip compounds.

Item Type:Article
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URLURL TypeDescription Information
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2007 American Chemical Society. Received 28 May 2006. Published online 25 January 2007. Published in print 1 February 2007. T.J. gratefully acknowledges support by the “Fonds der Chemischen Industrie” (VCI) and the German academic exchange service (DAAD).
Funding AgencyGrant Number
Fonds der Chemischen IndustrieUNSPECIFIED
Deutscher Akademischer Austauschdienst (DAAD)UNSPECIFIED
Issue or Number:6
Record Number:CaltechAUTHORS:20170711-125443699
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Official Citation:Linking Molecular Switches to Platinum Electrodes Studied with DFT Timo Jacob, Mario Blanco, and William A. Goddard III The Journal of Physical Chemistry C 2007 111 (6), 2749-2758 DOI: 10.1021/jp0632844
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78949
Deposited By: Ruth Sustaita
Deposited On:11 Jul 2017 20:52
Last Modified:15 Nov 2021 17:44

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