Reorganization energy and polaronic effects of pentacene on NaCl films

Abstract

Due to recent advances in scanning-probe technology, the electronic structure of individual molecules can now also be investigated if they are immobilized by adsorption on non-conductive substrates. As a consequence, different molecular charge-states are now experimentally accessible. Thus motivated, we investigate as an experimentally relevant example the electronic and structural properties of a NaCl(001) surface with and without pentacene adsorbed (neutral and charged) by employing density functional theory. We estimate the polaronic reorganization energy to be $E_{\text{reorg}}\simeq 0.8-1.0$ eV, consistent with experimental results obtained for molecules of similar size. To account for environmental effects on this estimate, different models for charge screening are compared. Finally, we calculate the density profile of one of the frontier orbitals for different occupation and confirm the experimentally observed localization of the charge density upon relaxation of the substrate from ab-initio calculations.

arXiv comment11 pages + 13 figures; Supporting Information (2 pages + 4 figures), typos corrected, corresponds to the published version

References in corpus (9)

• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• How to mesh up Ewald sums (I): A theoretical and numerical comparison of various particle mesh routines
• Adsorption structures and energetics of molecules on metal surfaces: Bridging experiment and theory
• Molecular structure elucidation with charge-state control
• Investigating Atomic Contrast in Atomic Force Microscopy and Kelvin Probe Force Microscopy on Ionic Systems using Functionalized Tips
• A multi-scale approach to the electronic structure of doped semiconductor surfaces
• Frontier molecular orbitals of single molecules adsorbed on thin insulating films supported by a metal substrate: A simplified density functional theory approach
• The electrostatic interaction of an external charged system with a metal surface: a simplified density functional theory approach
• A simplified density functional theory method for charged adsorbates on an ultrathin, insulating film supported by a metal substrate

Cited by in corpus (3)

• Many-body description of STM-induced fluorescence of charged molecules
• Spin-orbit interaction induces charge beatings in a lightwave-STM single molecule junction
• Substrate stabilization of Jahn-Teller distortion in a single molecule