Cavity-modulated ionization potentials and electron affinities from quantum electrodynamics coupled-cluster theory.

Area of Science:

• Quantum chemistry
• Theoretical chemistry
• Materials science

Background:

• Understanding how external fields influence molecular properties is crucial.
• Optical cavities can modify quantum electrodynamic (QED) effects.
• Sodium halides (NaX) are model systems for studying chemical bonding and electronic properties.

Purpose of the Study:

• To investigate the impact of strong coupling to an optical cavity on the ground-state properties of sodium halide compounds.
• To quantify changes in ionization potentials (IPs) and electron affinities (EAs) using Quantum Electrodynamics Coupled-Cluster (QED-CC) theory.
• To determine the sensitivity of IPs and EAs to cavity interactions.

Main Methods:

• Employing Quantum Electrodynamics Coupled-Cluster (QED-CC) theory.
• Modeling a series of sodium halide compounds (NaX, X = F, Cl, Br, I).
• Simulating strong coupling between the molecules and an optical cavity.

Main Results:

• Electron affinities (EAs) of NaX compounds are highly sensitive to cavity interactions.
• Ionization potentials (IPs) show significantly less sensitivity to the optical cavity.
• QED-CC predictions indicate EAs can be reduced by up to 0.22 eV (≈50%) under experimentally accessible coupling conditions.

Conclusions:

• Cavity quantum electrodynamics offers a powerful route to tune molecular electronic properties, particularly electron affinities.
• The strong modulation of EAs suggests potential applications in controlling molecular reactivity and electronic behavior.
• QED-CC theory provides accurate predictions for these vacuum-field-induced changes.