Excited-state potential-energy surfaces of metal-adsorbed organic molecules from Linear Expansion \Delta-Self-Consistent Field Density-Functional Theory (\Delta SCF-DFT)

TL;DR

This paper evaluates and advances the linear expansion elta-SCF-DFT method for simulating excited states of metal-adsorbed organic molecules, focusing on molecular switching on metal surfaces and the effects of substrate interactions.

Contribution

The work extends the elta-SCF-DFT method for better excited-state PES accuracy and applies it to azobenzene on metal surfaces, revealing substrate effects on molecular switching.

Findings

Substrate electronic states alter excited-state PES topologies.

Gas-phase and surface-adsorbed molecules show different resonance behaviors.

Surface interactions may reduce molecular switching efficiency.

Abstract

Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion \Delta Self-Consistent Field (le\Delta SCF) method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)] presents an efficient alternative to time consuming quasi-particle calculations. In this method the standard Kohn-Sham equations of Density-Functional Theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.