Understanding Current Density in Molecules Using Molecular Orbitals

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningfagfællebedømt

While the use of molecular orbitals (MOs) and their isosurfaces to explain physical phenomena in chemical systems is a time-honored tool, we show that the nodes are an equally important component for understanding the current density through single-molecule junctions. We investigate three different model systems consisting of an alkane, alkene, and even [n]cumulene and show that we can explain the form of the current density using the MOs of the molecule. Essentially, the MOs define the region in which current can flow and their gradients define the direction in which current flows within that region. We also show that it is possible to simplify the current density for improved understanding by either partitioning the current density into more chemically intuitive parts, such as σ- and π-systems, or by filtering out MOs with negligible contributions to the overall current density. Our work highlights that it is possible to infer a non-equilibrium property (current density) given only equilibrium properties (MOs and their gradients), and this, in turn, grants deeper insight into coherent electron transport.

OriginalsprogEngelsk
TidsskriftThe journal of physical chemistry. A
Vol/bind127
Udgave nummer43
Sider (fra-til)9003-9012
Antal sider10
ISSN1089-5639
DOI
StatusUdgivet - 2023

ID: 373873247