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Substituent-induced intermolecular interaction in organic crystals revealed by precise band-dispersion measurements

, : Substituent-induced intermolecular interaction in organic crystals revealed by precise band-dispersion measurements. Physical Review Letters 111(8): 086602-086602

We reveal quite small but different intermolecular valence band dispersions of sub-100-meV scale in crystalline films of Zn and Mn phthalocyanine (ZnPc and MnPc) and fluorinated ZnPc (F16ZnPc). The intermolecular transfer integrals are found to be reasonably dependent on the intermolecular distance with the 75±5 meV/Å relation. Furthermore, the angle-resolved photoemission spectra show anomalous dispersive behaviors such as phase flips and local-dimerization-derived periodicities, which originate from the site-specific intermolecular interaction induced by substituents.


PMID: 24010459

DOI: 10.1103/PhysRevLett.111.086602

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