Understanding Current Density In Molecules Using Molecular Orbitals

Abstract

While the use of molecular orbitals (MOs) and their isosurfaces to explain physical phenomena in chemical systems are 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 dif- ferent 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 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 possi- ble 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.