TY - JOUR
T1 - Understanding Current Density in Molecules Using Molecular Orbitals
AU - Bro-Jørgensen, William
AU - Solomon, Gemma C.
PY - 2023
Y1 - 2023
N2 - 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.
AB - 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.
U2 - 10.1021/acs.jpca.3c04631
DO - 10.1021/acs.jpca.3c04631
M3 - Journal article
C2 - 37856785
AN - SCOPUS:85175878342
VL - 127
SP - 9003
EP - 9012
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
SN - 1089-5639
IS - 43
ER -