TY - JOUR
T1 - When Current Does Not Follow Bonds: Current Density in Saturated Molecules
AU - Jensen, Anders
AU - Garner, Marc H.
AU - Solomon, Gemma C.
PY - 2019/5/16
Y1 - 2019/5/16
N2 - The tools commonly used to understand structure-property relationships in molecular conductance, interatomic currents and conductance eigenchannels, generally give us a sense of familiarity, with the chemical bonding framework and molecular orbitals reflected in the current. Here we show that while this picture is true for conjugated molecules, it breaks down in saturated systems. We investigate the current density in saturated chains of alkanes, silanes, and germanes and show that the current density does not follow the bonds, but rather the nuclei define the diameter of a pipe through which the current flows. We discuss how this picture of current density can be used to understand details about the electron transport properties of these molecules. Understanding the spatial distribution of current through molecules, rather than simply the magnitude, provides a powerful tool for chemical insight into physical properties of molecules that are related to current flow. Our work emphasizes that the spatial understanding of coherent electron transport must be derived from current density, rather than other spatial representations, to ensure that accurate conclusions are drawn.
AB - The tools commonly used to understand structure-property relationships in molecular conductance, interatomic currents and conductance eigenchannels, generally give us a sense of familiarity, with the chemical bonding framework and molecular orbitals reflected in the current. Here we show that while this picture is true for conjugated molecules, it breaks down in saturated systems. We investigate the current density in saturated chains of alkanes, silanes, and germanes and show that the current density does not follow the bonds, but rather the nuclei define the diameter of a pipe through which the current flows. We discuss how this picture of current density can be used to understand details about the electron transport properties of these molecules. Understanding the spatial distribution of current through molecules, rather than simply the magnitude, provides a powerful tool for chemical insight into physical properties of molecules that are related to current flow. Our work emphasizes that the spatial understanding of coherent electron transport must be derived from current density, rather than other spatial representations, to ensure that accurate conclusions are drawn.
U2 - 10.1021/acs.jpcc.8b11092
DO - 10.1021/acs.jpcc.8b11092
M3 - Journal article
SN - 1932-7447
VL - 123
SP - 12042
EP - 12051
JO - The Journal of Physical Chemistry Part C
JF - The Journal of Physical Chemistry Part C
IS - 19
ER -