Translation of metal-phthalocyanines adsorbed on Au(111): from van der Waals interaction to strong electronic correlation

L Buimaga-Iarinca,C Morari

doi:10.1038/s41598-018-31147-5

Abstract

Using first-principles calculations, we investigate the binding energy for six transition metal - phthalocyanine molecules adsorbed on Au(111). We focus on the effect of translation on molecule - surface physical properties; van der Waals interactions as well as the strong correlation in d orbitals of transition metals are taken into account in all calculations. We found that dispersion interaction and charge transfer have the dominant role in the molecule-surface interaction, while the interaction between the transition metal and gold has a rather indirect influence over the physics of the molecule-surface system. A detailed analysis of the physical properties of the adsorbates at different geometric configurations allows us to propose qualitative models to account for all values of interface dipole charge transfer and magnetic moment of metal-phthalocyanines adsorbed on Au(111).

Highlights

Metal phthalocyanines are highly symmetric organic molecules that incorporate a metal atom as the center of the organic ligand
We investigate the atomic contributions to HOMO-LUMO orbitals by integrating the projected density of states over each atomic state at energies corresponding to HOMO-LUMO eigenvalues of the Hamiltonian
Our analysis was performed using van der Waals adapted exchange-correlation functionals, while the strong correlations in d orbitals of the transition metals were taken into account by the DFT + U method

Summary

Introduction

Metal phthalocyanines are highly symmetric organic molecules that incorporate a metal atom as the center of the organic ligand. Depending on the system, such mismatch can lead to substrate-induced template effects, which affect the supramolecular arrangement as proven by STM investigations[18,19,20,21,22,23,24] Such symmetry mismatch is expected to play a role in the on-surface template synthesis of phthalocyanines, holding one of the top positions for future applications[25,26,27,28,29,30]. The aim of the present investigation is to provide a model for the binding energy landscape formed by adsorbing TMPC on different positions on gold surface www.nature.com/scientificreports/

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Results

Conclusion