Assessing the importance of multireference correlation in predicting reversed conductance decay.

Abstract

In a classical electronic resistor, conductance decays as the device length increases according to Ohm's Law. While most molecular series display a comparable exponential decay in conductance with increasing molecular length, a class of single-molecule device series exists where conductance instead increases with molecular/device length, a phenomenon called reversed conductance decay. While reversals of conductance decay have been repeatedly theoretically predicted, they have been far more difficult to demonstrate experimentally. Previous studies have suggested that theoretical multi-reference(static) correlation errors may be a major cause of this discrepancy, yet most single-molecule transport methods are unable to treat multireference correlation. Using our unique multireference transport method based on non-equilibrium Green's function and multiconfigurational pair-density functional theory (NEGF-MCPDFT), we examined a previously predicted case of reversed conductance decay in systems of linear chains of phenyl rings with varying lengths and electrode designs. We compare our NEGF-MCPDFT results to those of non-multireference NEGF methods to quantify the exact role of static correlation in conductance decay reversals and clarify their relative importance to geometric and electrode design/coupling considerations.