Range-Separated Hybrid Functionals for Mixed-Dimensional Heterojunctions: Application to Phthalocyanines/MoS2

Abstract

We analyze the electronic structure and level alignment of transition-metal phthalocyanine (MPc) molecules adsorbed on two-dimensional MoS${}_2$ employing density functional theory (DFT) calculations. We develop a procedure for multi-objective optimal tuning of parameters of range-separated hybrid functionals in these mixed-dimensional systems. Using this procedure, which leads to the asymptotically-correct exchange-correlation potential between molecule and two-dimensional material, we obtain electronic structures consistent with experimental photoemission results for both energy level alignment and electronic bandgaps, representing a significant advance compared to standard DFT methods. We elucidate the MoS${}_2$ valence resonance with the transition-metal phthalocyanine non-frontier 3$d$ orbitals and its dependence on the transition metal atomic number. Based on our calculations, we derive parameter-free, model self-energy corrections that quantitatively accounts for the effects of the heterogeneous dielectric environment on the electronic structure of these mixed-dimensional heterojunctions.

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Cited by in corpus (4)

• Transferable screened range-separated hybrid functionals for electronic and optical properties of van der Waals materials
• Quasiparticle electronic structure of phthalocyanine:TMD interfaces from first-principles $GW$
• Density functional descriptions of interfacial electronic structure
• Collective Electrostatics and Band Alignment in Janus MoSTe nanotubes