The kinetic approach adapted to describe charge transmission in molecular junctions, is used for the analysis of the photocurrent under conditions of moderate light intensity of the photochromic molecule. In the framework of the HOMO-LUMO model for the single electron molecular states, the analytic expressions describing the temporary behavior of the transient and steady state sequential (hopping) as well as direct (tunnel) current components have been derived. The conditions at which the current components achieve their maximal values are indicated. It is shown that if the rates of charge transmission in the unbiased molecular diode are much lower than the intramolecular singlet-singlet excitation/de-excitation rate, and the threefold degenerated triplet excited state of the molecule behaves like a trap blocking the charge transmission, a possibility of a large peak-like transient switch-on photocurrent arises.
Light-induced charge transmission through a molecular junction (molecular
diode) is studied in the framework of a HOMO-LUMO model and in using a kinetic
description. Expressions are presented for the sequential (hopping) and direct
(tunneling) transient current components together with kinetic equations
governing the time-dependent populations of the neutral and charged molecular
states which participate in the current formation. Resonant and off-resonant
charge transmission processes are analyzed in detail. It is demonstrated that
the transient currents are associated with a molecular charging process which
is initiated by photo excitation of the molecule. If the coupling of the
molecule to the electrodes is strongly asymmetric the transient currents can
significantly exceed the steady state current.Comment: 17 pages, 12 figures, accepted for publication in Chemical Physic
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