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Towards Mesoscale Properties of Self-Assembled Monolayers of SMM on Au(111): An Integrated Ad Hoc FF and DFT Study Guglielmo Fernandez Garcia, Alessandro Lunghi, Federico Totti, and Roberta Sessoli J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.6b05017 • Publication Date (Web): 20 Jun 2016 Downloaded from http://pubs.acs.org on June 23, 2016
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The Journal of Physical Chemistry
Towards Mesoscale Properties of Self-Assembled Monolayers of SMM on Au(111): An Integrated Ad Hoc FF and DFT Study Guglielmo Fernandez Garcia,†,‡ Alessandro Lunghi,†,¶ Federico Totti,∗,† and Roberta Sessoli† Università degli Studi di Firenze. Dipartimento di Chimica “Ugo Schiff ”, Via della Lastruccia 3-13, 50019, Sesto Fiorentino (FI), Italy E-mail:
[email protected] Abstract
scopic properties of SMM monolayers by in silico approach.
In nanotechnology, a preservation of the electronic and magnetic properties of an adsorbated molecular system and the control of its organization on a surface is mandatory for any technological application. Recently, in silico approaches demonstrated to be of fundamental support to experimental investigations in this hot and promising field. In this framework, an integrated MM (Molecular Mechanics) and DFT (Density Functional Theory) approach for the modelization of single molecule magnets (SMMs) on surface has been developed and applied to study the adsorption of [Fe4 (L)2 (dpm)6 ] (Hdpm=dipivaloylmethane and H3 L=2-hydroxymethyl-2-phenylpropane1,3-diol), Fe4 Ph, on an unreconstructed surface of Au(111). The adsorption process and its effects on the geometrical parameters and the magnetic properties are presented. The proposed method shows to be reliable enough to pave the route toward the access to the meso-
Introduction The race to the miniaturization of electronical devices pushed the scientific communities to explore the amazing world at the nanoscale level. However, it is not easy to have a clear picture of properties and behaviors taking place at this lenght scale at the experimental level. Such an issue represents a significant limitation especially considering the upcoming necessity to finely tune nanodevice performances in view of practical technological applications. In this respect, monolayers of magnetic molecules adsorbed on different types of surfaces showing ad hoc or novel properties have becoming more and more important in crucial fields as, for instance, spin valves, 1–3 qubits for quantum computing 4 or memory storage devices. 5 The problem of the rationalization of the structural and magnetic behaviors of SMMs adsorbed on metallic substrates has been shown to be possibly addressed through synergic contributions from several experimental techniques supported by static DFT calculations. 6,7 Another very fruitful strategy, fully computational in nature, requires the exploration of the SMM
∗
To whom correspondence should be addressed Università degli Studi di Firenze ‡ Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, 263 Avenue du Général Leclerc, 35042 Cedex Rennes, France ¶ School of Physics, CRANN and AMBER, Trinity College Dublin 2, Ireland †
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the Fe4 Ph can be found elsewhere. 10
Hisotropic =
3 X
Jci~sc · ~si + J2 (
i
3 X
rhombic, E, parameters: 1 D = Dzz − (Dxx + Dyy ) 2 1 E = |Dxx − Dxx | 2
~si · ~sj ) (1)
i
