A Green's Function Approach for Determining Surface Induced Broadening and Shifting of Molecular Energy Levels.
Nano Lett
; 22(24): 9854-9860, 2022 Dec 28.
Article
em En
| MEDLINE
| ID: mdl-36525585
ABSTRACT
Upon adsorption of a molecule onto a surface, the molecular energy levels (MELs) broaden and change their alignment. This phenomenon directly affects electron transfer across the interface and is, therefore, a fundamental observable that influences electrochemical device performance. Here, we propose a rigorous parameter-free framework, built upon the theoretical construct of Green's functions, for studying the interface between a molecule and a bulk surface and its effect on MELs. The method extends beyond the usual wide-band limit approximation, and its generality allows its use with any level of electronic structure theory. We demonstrate its ability to predict the broadening and shifting of MELs as a function of intramolecular coupling, molecule/surface coupling, and the surface density of states for a molecule with two MELs adsorbed on a one-dimensional model metal surface. The new approach could help provide guidelines for the design and experimental characterization of electrochemical devices with optimal electron transport.
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MEDLINE
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En
Ano de publicação:
2022
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Article