Photoinduced electron transfer

Photoinduced electron transfer is an electron transfer which occurs when certain photoactive materials interact with light. [Highlights of the spectroscopy, photochemistry and electrochemistry of [M(CO)4(α-diimine)] complexes, M=Cr, Mo, W Antonín Vlcek "Coord. Chem. Rev." 230 (2002) 225-242.] [Organic and Inorganic Photochemistry V. Ramamurthy and Kirk S. Schanze 1998 Marcel Dekker ISBN 0824701747]

Breadth

Such materials including semiconductors that can be photoactivated like many solar cells, biological systems such as those used in photosynthesis, and small molecules with suitable absorptions and redox states.

Process

It is common to describe where electrons reside as a electron bands in bulk materials and electron orbitals in molecules. For the sake of expedience the following description will be described in molecular terms. When a photon excites a molecule an electron in a ground state orbital can be excited to a higher energy orbital. This excited state leaves a vacancy in a ground state orbitals that can be filled by a electron donor. It produces an electron in a high energy orbital which it can donate to an electron acceptor. In these respects a photoexcited molecule can act as a good oxidizing agent or a good reducing agent.

:Photoinduced Oxidation

: [ML_n] ²⁺ + hν → [ML_n] ²⁺*

: [ML_n] ²⁺* + donor → [ML_n] ⁺ + donor⁺

:Photoinduced Reduction

: [ML_n] ²⁺ + hν → [ML_n] ²⁺*

: [ML_n] ²⁺* + acceptor → [ML_n] ³⁺ + acceptor^-

The end result of both reactions is that an electron is delivered to an orbital that is higher in energy than where it previously resided. This is often described as a charge separated electron-hole pair when working with semiconductors.

In the absence of a proper electron donor or acceptor it is possibe for such molecules to undergo ordinary fluorescence emission. The electron transfer is one form of photoquenching.

Subsequent Processes

In many photo-productive systems this charge separation is kinetically isolated by delivery of the electron to a lower energy conductor attached to the p/n junction or into a electron transport chain. In this case some of the energy can be captured to do work. If the electron is not kinetically isolated thermodynamics will take over and the products will react with each other to regenerate the ground state starting material. This process is called recombination and the photon's energy is released as heat.

:Recombination of Photoinduced Oxidation

: [ML_n] ⁺ + donor⁺ → [ML_n] ²⁺ + donor

Potential induced photon production

The reverse process to photoinduced electron transfer is displayed by light emitting diodes (LED) and chemiluminescence. Where potential gradients are used to create excited states that decay by emitting by light.

References