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.

tetrapyridyl

cu(110)

Cu(110) surface

ptcda

scanning

chemistry

stm

functional calculations

molecular adsorption

molecules

van der Waals interactions

reflection absorption infrared spectra

adsorption

density

free-base porphine

surface

ag(110)

tunneling microscopy

au(111)

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

University College London (UCL)

ACS Nano

1936-0851 (ISSN) 1936-086X (eISSN)

Vol. 5 3 1831-1838

Ämneskategorier

Kemi

DOI

10.1021/nn102610k