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Experimentally-based recommendations of density functionals for predicting properties in mechanically interlocked molecules

Benitez, Diego and Tkatchouk, Ekaterina and Yoon, II and Stoddart, J. Fraser and Goddard, William A., III (2008) Experimentally-based recommendations of density functionals for predicting properties in mechanically interlocked molecules. Journal of the American Chemical Society, 130 (45). pp. 14928-14929. ISSN 0002-7863.

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Mechanically interlocked molecules (rotaxanes and catenanes) have already revolutionized molecular electronics and have the promise of a similar impact in other areas of nanotechnology, ranging from nanoactuators to in vivo drug nanocarriers. However, it would be most useful to have quantitative criteria for predicting structures, binding, and excitation energies for use in designing molecules with mechanical bonds. We assess here the use of density functional theory (DFT) to a noncovalently bound complex and find that no density functional is fully satisfactory. However, we find that the new M06-suite of density functionals, which include attractive medium-range interactions, leads to dramatic improvements in the structures (error of 0.04 Å in the interplanar distances for M06-L compared to 0.42 Å for B3LYP) and excitation energies (within 0.08 eV for TD-M06-HF without empirical correction compared to 2.2 eV error for TD-B3LYP). However, M06 predicts the complex to be too strongly bound by 22.6 kcal mol−1 (B3LYP leads to too weak a bond by 29 kcal mol−1), while current empirical FF DREIDING is too weakly bound by only 15 kcal mol−1.

Item Type:Article
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URLURL TypeDescription
Stoddart, J. Fraser0000-0003-3161-3697
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2008 American Chemical Society. Publication Date (Web): October 20, 2008. This research was partially supported by NSF-NIRT(CTS-0608889) and MARCO-FENA. Facilities were funded by grants from ARO-DURIP and ONR-DURIP. Supporting Information Available: Supplied are NMR spectra, thermodynamic properties, and XYZ coordinates. This material is available free of charge via the Internet at
Funding AgencyGrant Number
Microelectronics Advanced Research Corporation (MARCO)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Center on Functional Engineered NanoArchitectonics (FENA)UNSPECIFIED
Issue or Number:45
Record Number:CaltechAUTHORS:BENjacs08
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:13842
Deposited By: Ruth Sustaita
Deposited On:16 Jul 2009 17:15
Last Modified:03 Oct 2019 00:44

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