[en] We report on a combined experimental and theoretical study of the adsorption of the paramagnetic organic radical 2,2,5,5-tetramethyl-3-carboxypyrrolidine nitroxide (3-carboxyproxyl, 3CP) on a Cu(110) surface. Information from scanning tunneling microscopy (STM), reflection absorption infrared spectroscopy, and periodic density functional theory (DFT) calculations reveals important insights into the nature of the molecule-metal interface. We find that the molecule is robustly anchored to the surface via the formation of two Cu-O bonds between the carboxylate functionality and specific short-bridge adsorption sites on the Cu(110) surface. The adsorbed organic radicals appear in STM as discrete entities on the surface and can be imaged with submolecular resolution. We observe a tendency for local 2D ordering. Importantly, 3CP molecules adopt a preferred site, dictated by the strong interaction of the carboxylate groups and the steric repulsion of the methyl groups with the surface which orient the molecular ring almost perpendicular with respect to the surface. This conformation forces the NO radical away from the surface, and DFT calculations provide strong indications for the survival of the unpaired spin localized on the NO radical.
Disciplines :
Chemistry Physics
Author, co-author :
Robin, A.
Marnell, L.
Bjork, J.
Dyer, M.S
Bermudez, S.
Haq, S.
Barrett, S.D.
Persson, M.
Minoia, A.
Lazzaroni, Roberto ; Université de Mons > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Raval, R.
Language :
English
Title :
Adsorption and Organization of the Organic Radical 3-Carboxyproxyl on a Cu(110) Surface: A Combined STM, RAIRS, and DFT Study
Publication date :
30 July 2009
Journal title :
Journal of Physical Chemistry. C, Nanomaterials and interfaces
ISSN :
1932-7447
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Volume :
113
Issue :
30
Pages :
13223-13230
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S817 - Chimie des matériaux nouveaux
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
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