Quantum chemistry calculations for molecules coupled to reservoirs: formalism, implementation, and application to benzenedithiol

J Chem Phys. 2007 May 7;126(17):174101. doi: 10.1063/1.2716664.

Abstract

Modern quantum chemistry calculations are usually implemented for isolated systems-big molecules or atom clusters; total energy and particle number are fixed. However, in many situations, like quantum transport calculations or molecules in a electrochemical environment, the molecule can exchange particles (and energy) with a reservoir. Calculations for such cases require to switch from the canonical to a grand canonical description, where one fixes the chemical potential rather than particle number. To achieve this goal, the authors propose an implementation in standard quantum chemistry packages. An application to the nonlinear charge transport through 1,4-benzenedithiol will be presented. They explain the leading finite bias effect on the transmission as a consequence of a nonequilibrium Stark effect and discuss the relation to earlier work.