Marcus hush theory
The Marcus-Hush theory, an extension of Marcus theory, focuses on
electron transfer processes. It builds on the classical Marcus theory, which
was originally developed to explain outer-sphere electron transfer (ET)
where the reactants do not share a common bonding framework. Noel Hush
extended the theory to include inner-sphere electron transfer, which involves
a direct bond between reactants.
The theory calculates the energy needed for an electron to move
between two reactants, considering factors like solvent reorganization
and molecular vibrations. In particular, the theory suggests that the rate of
electron transfer depends on how the solvent and molecular structure
reorganize around the reactants before and after the electron transfer, a
process governed by quantum mechanical principles.
The asymmetric Marcus-Hush theory refines this model to address
deviations found in experimental data, particularly in electrochemical
systems like redox reactions at electrodes, where vibrational and
solvation effects play key roles
Detail
Key Concepts of Marcus Theory
The original Marcus theory deals with the energetics of ET in solution,
focusing on how solvent reorganization affects the transfer. The key
components include:
• Reorganization Energy (λ): This represents the energy required for the
solvent and reactants to rearrange before the electron jumps between
them. It is divided into:
o Outer-sphere reorganization energy, due to the solvent
molecules’ rearrangement.
o Inner-sphere reorganization energy, involving changes in bond
lengths or angles of the reactants themselves.
• Activation Free Energy (ΔG#): This refers to the energy barrier that
must be overcome for the electron transfer to occur. This depends on
the difference between the free energy of reaction (ΔG⁰) and the
reorganization energy.
• Rate of Electron Transfer: The Marcus equation calculates the rate of
ET using a parabolic energy surface model where reactants and
products move on potential energy surfaces corresponding to their
nuclear configurations. The electron transfer occurs when these
surfaces cross, leading to an activation energy derived from the
intersection of these parabolas
Marcus-Hush Extension
Noel Hush expanded Marcus's theory to include inner-sphere electron
transfer, which involves a more direct interaction between the donor and
acceptor. In this case, a chemical bond or bridge facilitates the electron's
movement between the two, often mediated by a shared ligand. The Marcus-
Hush theory also accounts for the electronic coupling between donor and
acceptor, which was not part of the original Marcus model. This coupling
determines how effectively the electron can tunnel through the bridge.
Asymmetric Marcus-Hush Theory
In many practical systems, experimental observations deviate from the
predictions of the symmetric Marcus-Hush model. For example, in
voltammetry (a method used in electrochemistry), the rate of electron
transfer between a redox-active species and an electrode often exhibits
asymmetry. This means that the energy surfaces for the donor and acceptor
may not be identical, leading to different reorganization energies. The
asymmetric Marcus-Hush theory addresses these complexities by
accounting for different force constants related to molecular vibrations and
solvation effects
6. Applications
The Marcus-Hush theory has been instrumental in various fields:
• Biological Electron Transfer: It helps explain ET in proteins and
enzymes, such as in cellular respiration and photosynthesis, where ET
happens across multiple centers.
• Electrochemistry: The theory is critical for understanding how
electrons transfer between molecules and electrodes in systems like
batteries and fuel cells.
• Molecular Electronics: It helps model the ET in organic molecules
used in molecular circuits, guiding the design of nanoscale electronic
devices
In summary, the Marcus-Hush theory provides a powerful framework for
predicting and analyzing electron transfer processes, making it essential for
fields ranging from electrochemistry to biological systems.
This graph represents the key aspects of Marcus theory, showing the
potential energy surfaces for the reactants (blue curve) and products (red
curve) as functions of the reaction coordinate. These parabolic surfaces
describe how the system's energy changes as the nuclear configuration of the
molecules adjusts before and after electron transfer.
The transition state is where the two parabolas intersect (indicated by the
green dashed line). At this point, the electron transfer occurs, and the
activation energy barrier is defined by the vertical distance between the
minimum of the reactants' curve and the intersection point.
• Reactants Energy Surface: Shows how the energy changes as the
system reorganizes in preparation for electron transfer.
• Products Energy Surface: Represents the energy state after the
electron has transferred, with the system reorganized accordingly.
• The reorganization energy (λ) represents the curvature and separation
between the reactants and products.
This visualization helps illustrate how Marcus theory predicts electron
transfer based on nuclear and solvent reorganization.
