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We present a theoretical study of the measurements of photoinduced forcemicroscopy (PiFM) for composite molecular systems. Using the discrete dipoleapproximation, we calculate the self-consistent response electric field of theentire sample including the PiFM tip, substrate, and composite molecules. Wedemonstrate a higher sensitivity for the PiFM measurement on resonant moleculesthan by the previously obtained tip-sample distance dependency $z^{-4}$ owingof the multifold enhancement of the field between the localized electric fieldinduced at the tip-substrate nanogap and the molecular polarization. Theenhanced localized electric field induced at the tip-substrate nanogap in PiFMallows high-resolution observation of the forbidden optical electronictransition in dimer molecules. We investigated the wavelength dependence ofPiFM for dimer molecules and obtained images at incident light wavelengthscorresponding to allowed and forbidden transitions. We reveal that these PiFMimages drastically change with the frequency-dependent spatial structures ofthe localized electric field vectors and resolve different types ofnanoparticles beyond the resolution for the optically allowed transitions. Thisstudy demonstrates that PiFM provides multifaceted information based onmicroscopic interactions between nanomaterials and light.

Theoretical Analysis of Optically Selective Imaging in Photoinduced Force Microscopy