Local Chiral Optical Responses in Phthalocyanine Molecular Assemblies Revealed by Photoinduced Force Microscopy

Abstract

Photoinduced force microscopy (PiFM) provides a force-based probe of nanoscale polarization-dependent molecular excitations. Here, we theoretically investigate PiFM images of zinc phthalocyanine assemblies using the discrete dipole approximation with nonlocal molecular susceptibilities. Under linearly polarized illumination, intermolecular dipole coupling splits the molecular resonance into bonding and antibonding modes. These modes produce distinct force distributions: bonding modes enhance signals at molecular termini, whereas antibonding modes localize responses in intermolecular regions, reflecting collective intermolecular polarization modes. Under circularly polarized illumination, intermolecular coupling and anisotropic molecular packing generate spatially varying local circular dichroism signals with enhanced asymmetric force factors. These results establish PiFM as a real-space probe of collective polarization modes and coupling-induced local chiral optical responses.

arXiv comment7 pages, 5 figures, supporting information included; updated version corresponding to the initial journal-submitted manuscript, with revised computational conditions, numerical results, and refined conclusions