A bottom-up valence bond derivation of excitation energies in 1D-like delocalized systems

Képénékian, Mikaël; Robert, Vincent; Boilleau, Corentin; Malrieu, Jean‐Paul

doi:10.1039/c1cp23390d

Cited by 1 publication

(1 citation statement)

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“…However, it is delicate to take into account this effect in our perturbation model. 29 To compensate, we have selected a U value slightly larger than usual. 30,31 Interestingly, with this simple model, the weight of the closed-shell determinant for N = 10 is only 62% of the total ground state, reproducing the contamination of the ground state by at least doubly excited electronic configurations, and confirming that the observed dI/dV electronic resonances cannot be attributed simply to monoelectronic MO resonances.…”

Section: Resultsmentioning

confidence: 99%

Electronic Resonances and Gap Stabilization of Higher Acenes on a Gold Surface

et al. 2018

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On-surface synthesis provides a powerful method for the generation of long acene molecules, making possible the detailed investigation of the electronic properties of single higher acenes on a surface. By means of scanning tunneling microscopy and spectroscopy combined with theoretical considerations, we discuss the polyradical character of the ground state of higher acenes as a function of the number of linearly fused benzene rings. We present energy and spatial mapping of the tunneling resonances of hexacene, heptacene, and decacene, and discuss the role of molecular orbitals in the observed tunneling conductance maps. We show that the energy gap between the first electronic tunneling resonances below and above the Fermi energy stabilizes to a finite value, determined by a first diradical electronic perturbative contribution to the polyacene electronic ground state. Up to decacene, the main contributor to the ground state of acenes remains the lowest-energy closed-shell electronic configuration.

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Section: Resultsmentioning

confidence: 99%