Graphene induced molecular flattening of meso-5,10,15,20-tetraphenyl porphyrin

DFT calculations and molecular dynamics simulations

V. A. Karachevtsev, S. G. Stepanian, M. V. Karachevtsev, Ludwik Adamowicz

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Noncovalent functionalization of graphene with porhyrins that possess a large conjugated π-system of bonds can extend the range of practical applications of this nanomaterial. In this work the structures of hybrids formed by porphin and meso-5,10,15,20-tetraphenyl porphyrin (TPP) with graphene and the corresponding intermolecular interaction energies are studied with the DFT and molecular dynamics (MD) calculations. The influence of the peripheral rings arranged around the porphyrin core in the TPP structure on its interaction energy with graphene upon the TPP adsorption on graphene is analyzed. The flattening of the TPP structure occurring due to the adsorption is observed. The interaction of TPP with graphene also leads to distortion of the flat structure of the porphyrin core and to some twisting of its side rings, so the dihedral angle between the planes of the porphyrin core and the side residues decreases from 64° to 50°. In spite of the flattening and the larger size of the TPP structure compared to the porphin structure their interaction energies with graphene are similar (about 20 kcal/mol). It is also shown that TPP alters the uniform distribution of the electrostatic potential on graphene by reducing the zone of small negative potential of graphene located under the porphyrin molecule. The MD simulation performed in this work describes the process of the adsorption of porphin and TPP on graphene in water environment and reveals significant mobility of this molecule on the graphene surface.

Original languageEnglish (US)
Pages (from-to)1-6
Number of pages6
JournalComputational and Theoretical Chemistry
Volume1133
DOIs
StatePublished - Jun 1 2018

Fingerprint

Graphite
Porphyrins
flattening
Molecular Dynamics Simulation
Discrete Fourier transforms
porphyrins
Molecular dynamics
graphene
molecular dynamics
Computer simulation
simulation
Adsorption
adsorption
interactions
Molecules
Nanostructures
rings
twisting
Dihedral angle
Static Electricity

Keywords

  • DFT calculation
  • Graphene
  • Molecular dynamics
  • Porphyrin
  • van der Waals interaction

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Graphene induced molecular flattening of meso-5,10,15,20-tetraphenyl porphyrin : DFT calculations and molecular dynamics simulations. / Karachevtsev, V. A.; Stepanian, S. G.; Karachevtsev, M. V.; Adamowicz, Ludwik.

In: Computational and Theoretical Chemistry, Vol. 1133, 01.06.2018, p. 1-6.

Research output: Contribution to journalArticle

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