Studying physisorption processes and molecular friction of cycloparaphenylene molecules on graphene nano-sized flakes: role of π⋯π and CH⋯π interactions

Abstract

We theoretically study, by means of dispersion-corrected and cost-effective methods, the strength of non-covalent interactions between cyclic organic nanorings and nano-sized graphene flakes acting as substrates.

Structure and Charge Transport Properties of Cycloparaphenylene Monolayers on Graphite

“…For the study of [8]CPP and its self-aggregation process on graphitic surfaces employing atomistic simulations, we first developed a force field able to reproduce the involved nonbonded intermolecular interactions, motivated by previous studies [20] of the energy profile of [8]CPP interacting with finite-size graphene surfaces (circumcoronenes and circumcircumcoronenes). Linear para-phenylenes were formerly studied by Olivier et al [53] employing the AMBER-OPLS force field, [54] with scaled parameters for the nonbonded interactions and refitted torsional energy profiles to reproduce p-quinquephenyl phase behavior.…”

“…The first solid-state characterization of [6]CPP revealed a tubular-like structure, [14] but a recent study revealed that the crystallographic structure might depend on the crystallization conditions, also finding a herringbone configuration a few kcal mol −1 more stable than the tubular one. [20] In the present study, we wish to go a step further and employ a tailored force field and molecular dynamics (MD) simulations to predict the supramolecular structure of thin films of CPPs on graphite surfaces. In these conditions, no solvent molecules are occluded inside the [6]CPP cavity, and thus, a concave-convex structure appears (i.e., molecules tightly packed in a T-like shape minimizing the internal space inside the cavities).…”

“…[19] These findings clearly reveal the subtle yet dominant effect of the weak intermolecular interactions driving the supra molecular self-assembly of these systems. [20] In the present study, we wish to go a step further and employ a tailored force field and molecular dynamics (MD) simulations to predict the supramolecular structure of thin films of CPPs on graphite surfaces. [20] In the present study, we wish to go a step further and employ a tailored force field and molecular dynamics (MD) simulations to predict the supramolecular structure of thin films of CPPs on graphite surfaces.…”

“…Potential energy curves of[8]CPP interacting with finite-size graphene nanoflakes (17.44 Å × 15.73 Å) in different configurations. HF-3c potential energy curves were obtained from ref [20],. HF-3c potential energy curves were obtained from ref [20],.…”

“…Motivated by this, some of us investigated in a previous theoretical work the adsorption energies of [8]CPP on small carbon nanoflakes (circumcirmcumcoronene) and how these through-space weak forces can serve to immobilize the systems in energetically favored configuration. [20] In the present study, we wish to go a step further and employ a tailored force field and molecular dynamics (MD) simulations to predict the supramolecular structure of thin films of CPPs on graphite surfaces. The systematic exploration of the adsorption The nanoscale organization of cycloparaphenylene molecules when physisorbed on a graphite surface is theoretically investigated by means of atomistic molecular dynamics simulations employing a tailored and benchmarked force field.…”