Theoretical investigation on the interaction between RhIII octaethylporphyrin and a graphite basal surface: a comparison study of DFT, DFT-D, and AFM

Physical Chemistry Chemical Physics : PCCP
Kohei TadaShin-Ichi Yamazaki

Abstract

Using density functional theory based calculations and atomic-force-microscopy observations, we investigated the interaction between [RhIII(OEP)(Cl)] (OEP = octaethylporphyrin) and a graphite basal surface, and the electronic structure of [RhIII(OEP)(Cl)]/graphite. The [RhIII(OEP)(Cl)] complex has an electronic structure effective for CO activation, possessing a closed singlet structure as its ground state; hence, both σ-donation from the CO molecule (anode-reaction reactant) to RhIII, and π-back-donation from RhIII to CO, occur, because the [RhIII(OEP)(Cl)] complex does not have a singlet occupied molecular orbital on the porphyrin ring, the π-π stacking interaction between porphyrin and graphite is not present and their interaction is dominated by dispersion forces. The [RhIII(OEP)(Cl)] complex easily diffused on the graphite basal surface, and an aggregated structure of [RhIII(OEP)(Cl)] was observed by atomic force microscopy. The difference of the electronic structures of [RhIII(OEP)(Cl)] before and after its adsorption is very small, the dispersion force being the dominant force for the adsorption. However, the lowest unoccupied molecular orbital of [RhIII(OEP)(Cl)]/graphite is a σ bonding orbital between RhIII and graphit...Continue Reading

References

Oct 29, 1975·Journal of the American Chemical Society·H OgoshiZ Yoshida
Dec 15, 1994·Physical Review. B, Condensed Matter·P E Blöchl
Oct 15, 1996·Physical Review. B, Condensed Matter·G Kresse, J Furthmüller
Jan 1, 1993·Physical Review. B, Condensed Matter·G Kresse, J Hafner
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Jul 1, 2005·Langmuir : the ACS Journal of Surfaces and Colloids·Taichi IkedaToshimi Shimizu
Mar 30, 2006·Angewandte Chemie·Shin-ichi YamazakiTetsuhiko Kobayashi
Jun 14, 2006·Langmuir : the ACS Journal of Surfaces and Colloids·Ayowale OgunrindeL Scudiero
Sep 7, 2006·Journal of Computational Chemistry·Stefan Grimme
Jan 24, 2007·Journal of Computational Chemistry·Edward SanvilleGraeme Henkelman
Apr 10, 2010·Chemical Communications : Chem Comm·Shin-Ichi YamazakiKazuaki Yasuda
Jun 10, 2010·Physical Chemistry Chemical Physics : PCCP·Shin-ichi YamazakiKazuaki Yasuda
Feb 17, 2011·The Journal of Chemical Physics·Min Yu, Dallas R Trinkle
Mar 28, 2012·Chemical Communications : Chem Comm·Shin-ichi YamazakiTsutomu Ioroi
Jun 19, 2012·Journal of Computational Chemistry·Otello M RoscioniJohn M Dyke
May 13, 2014·Physical Chemistry Chemical Physics : PCCP·Khaoula BoukariPhilippe Sonnet
Jul 23, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Shin-Ichi YamazakiTsutomu Ioroi
Aug 13, 2015·Physical Chemistry Chemical Physics : PCCP·Yeliz GurdalMarcella Iannuzzi
Oct 13, 2015·Physical Chemistry Chemical Physics : PCCP·Sarah GautierPhilippe Sautet

❮ Previous
Next ❯

Citations


❮ Previous
Next ❯

Methods Mentioned

BETA
scanning probe microscopy
scanning tunneling microscopy
AFM
X-ray
nuclear magnetic resonance
NMR
atomic force microscopy
of

Software Mentioned

vdw
Gaussian
advance
Advanced
Python
VESTA
PHASE
VASP

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.