Mapping the excited states of single hexa-peri-benzocoronene oligomers.

Soe, We-Hyo; Wong, Hon Seng; Manzano, Carlos; Grisolia, Maricarmen; Hliwa, Mohamed; Feng, Xinliang; Müllen, Klaus; Joachim, Christian · ACS Nano · 2012

basic_science · Level V

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Abstract

Electronic states of a molecule are usually analyzed via their decomposition in linear superposition of multielectronic Slater determinants built up from monoelectronics molecular orbitals. It is generally believed that a scanning tunneling microscope (STM) is able to map those molecular orbitals. Using a low-temperature ultrahigh vacuum (LT-UHV) STM, the dI/dV conductance maps of large single hexabenzocoronene (HBC) monomer, dimer, trimer, and tetramer molecules were recorded. We demonstrate that the attribution of a tunnel electronic resonance to a peculiar π molecular orbital of the molecule (or σ intermonomer chemical bond) in the STM junction is inappropriate. With an STM weak-measurement-like procedure, a dI/dV resonance results from the conductance contribution of many molecular states whose superposition makes it difficult to reconstruct an apparent molecular orbital electron probability density map.