Tailoring a Molecule's Optical Absorbance Using Surface Plasmonics

TL;DR

This paper introduces a computational method to accurately predict and tailor the optical absorption spectra of molecules on metal surfaces by incorporating substrate effects, enabling targeted design of surface-enhanced optical properties.

Contribution

The authors develop a hybrid $G_0[W_0+ riangle W]$-BSE approach that efficiently models molecule-surface interactions, allowing precise control over molecular absorbance through surface plasmon tuning.

Findings

Benzene's exciton energy remains unchanged with substrate variation.

Terry's exciton hybridizes with surface plasmon, enabling energy tuning.

Fullerene's excitons hybridize with surface plasmon, activating new modes.

Abstract

The design of novel functional materials in silico is severely hampered by the lack of robust and computationally efficient methods for describing both molecular absorbance and screening on substrates. Here we employ our hybrid $G_0[W_0+\Delta W]$-BSE implementation, which incorporates the substrate via its screening $\Delta W$ at both the quasiparticle $G_0W_0$ level and when solving the Bethe-Salpeter equation (BSE). We show this method can be used to both efficiently and accurately describe the absorption spectra of physisorbed molecules on metal substrates and thereby tailor the molecule's absorbance by altering the surface plasmon's energy. Specifically, we investigate how the optical absorption spectra of three prototypical $\pi$-conjugated molecules: benzene (C$_6$H$_6$), terrylene (C$_{30}$H$_{16}$) and fullerene (C$_{60}$), depends on the Wigner-Seitz radius $r_s$ of the metallic substrate. To gain further understanding of the light--molecule/substrate interaction, we also study the bright exciton's electron and hole densities and their interactions with infrared active vibrational modes. Our results show that (1) benzene's bright $E_{1u}^1$ exciton at 7.0 eV, whose energy is insensitive to changes in $r_s$, could be relevant for photocatalytic dehydrogenation and polymerization reactions, (2) terrylene's bright $B_{3u}$ exciton at 2.3 eV hybridizes with the surface plasmon, allowing the tailoring of the excitonic energy and optical activation of a surface plasmon-like exciton, and (3) fullerene's $\pi-\pi^*$ bright and dark excitons at 6.4 and 6.8 eV hybridize with the surface plasmon, resulting in the tailoring of their excitonic energy and the activation of both a surface plasmon-like exciton and a dark quadrupolar mode via symmetry breaking by the substrate.