Understanding the Interaction of the Porphyrin Macrocycle to Reactive Metal Substrates: Structure, Bonding, and Adatom Capture
Artikel i vetenskaplig tidskrift, 2011
We investigate the absorption and conformation of free-base porphines on Cu(110) using STM, reflection absorption infrared spectroscopy, and periodic DFT calculations in order to understand how the central polypyrrole macrocycle, common to all porphyrins, interacts with a reactive metal surface. We find that,the-macrocycle forms a chemisorption bond with the surface,, arising from electron donation into down-shifted, and nearly degenerate unoccupied porphine orbitals accompanied with electron back-donation from molecular pi-orbitals. Our calculations show that van der Waals interactions give rise to an overall Increase in the adsorption energy but only minor changes in the adsorption geometry and electronic structure. In addition, we observe copper adatoms being weakly attracted to adsorbed porphines at specific molecular sites. These results provide important insights into porphyrin-surface interactions that ultimately, will govern the design of robust surface mounted molecular devices based on this important class of molecules.
reflection absorption infrared spectra
Cu(110) surface
tetrapyridyl
van der Waals interactions
scanning
ptcda
free-base porphine
molecular adsorption
ag(110)
tunneling microscopy
au(111)
chemistry
adsorption
functional calculations
cu(110)
density
stm
surface
molecules
Författare
M. S. Dyer
University of Liverpool
A. Robin
University of Liverpool
S. Haq
University of Liverpool
R. Raval
University of Liverpool
Mats Persson
Chalmers, Teknisk fysik, Material- och ytteori
J. Klimes
UCL
ACS Nano
1936-0851 (ISSN) 1936-086X (eISSN)
Vol. 5 3 1831-1838Ämneskategorier (SSIF 2011)
Kemi
DOI
10.1021/nn102610k