High Stability and Properties of Adsorbed Polycyclic Aromatic Hydrocarbons (PAHs) onto Phosphorene: An atomistic DFT study

01 September 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


In this work, we report the structure, intermolecular forces, electronic/optical properties, and stability in solution of complexes formed between polycyclic aromatic hydrocarbons (PAH) and phosphorene nanoflakes by density functional theory modeling. PAH molecules reach a strong affinity with phosphorene by forming well-ordered domains, whose interaction strength decreases 13-21% compared to the interaction onto carbonaceous surfaces, e.g., graphene. The adsorption energies are in linear relation with the NH:NC ratio of PAHs, where NH and NC are the numbers of H and C atoms; consequently, the cohesive energy of phosphorene-graphene heterostructures is estimated in 44 meV/atom. Energy decomposition (ALMO-EDA) and electron-density-based analyses support the major role of electrostatics driving forces in the interaction mechanism, which is balanced with dispersion effects for larger PAHs. In addition, phosphorene-PAH complexes display outstanding stability in solution under polar/non-polar solvents, which is due to the high polarity of the complexes and strong overcompensation of destabilizing solvation energies with stabilizing electrostatic effects. Moreover, PAHs behave as n-dopants for phosphorene, inducing small bandgap opening and weak effects on the photophysical fingerprint of phosphorene. Nevertheless, strong electron acceptor/donor and larger PAHs (NH:NC<0.5) lead to major effects on the bandgap control, acting as active sites for orbital-controlled interactions. These findings serve as a framework for further investigation of phosphorene-based materials for remediation of PAH pollutants in water treatment technologies and uses of PAHs for phosphorene surface passivation or bandgap engineering for sensing.


dft calculations
water treatment
solvent effects
smd model
interaction mechanisms
intermolecular interactions
polycyclic aromatic hydrocarbons
electronic properties
adsorption energy
cohesive energy
graphene-phosphorene heterostructures
vdw heterostructures
binding energy
igmh analysis
AIM analysis
bond critical points
charge transfer
computational chemistry
surface science
absorption spectra
simplified time-dependent DFT
Independent Gradient Model
nanostructured materials
quantum chemistry


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