Photochemical Dynamics of Molecular Oxygen Complexes
Summary
The photochemical dynamics of molecular oxygen complexes encompass the processes by which oxygen interacts with light and adjacent chemical species, leading to a cascade of electronic and structural changes. In its ground state, dioxygen is a triplet biradical; photoexcitation can induce singlet or higher excited states that exhibit markedly different reactivities. These excited‐state oxygen species participate in energy and electron transfer reactions, underpinning mechanisms in photodynamic therapy, solar energy conversion and atmospheric chemistry. Central to understanding these processes are the rates and efficiencies of intersystem crossing and internal conversion, which govern the lifetime and fate of singlet oxygen and other reactive intermediates. Studies probe how coordination to metals or incorporation into organic frameworks modulates potential energy surfaces, spin–orbit coupling and orbital mixing. Advances in ultrafast spectroscopy and quantum‐chemical modelling now permit direct observation of transient peroxo and superoxo adducts, revealing the interplay between solvent, ligand environment and electronic structure. By elucidating these pathways, researchers aim to control singlet oxygen yield in medicinal applications, to optimise photocatalytic water splitting and to predict oxidative processes in the atmosphere.
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Photochemical Dynamics of Molecular Oxygen Complexes publication trend
The graph below shows the total number of articles in photochemical dynamics of molecular oxygen complexes across all publications each year (not limited to Nature Index journals).
Technical terms
Triplet ground state: The lowest‐energy electronic configuration of dioxygen, characterised by two unpaired electrons with parallel spins.
Singlet oxygen: An excited electronic state of O₂ in which paired spins result in higher reactivity than the triplet ground state.
Intersystem crossing (ISC): A non‐radiative transition between electronic states of different spin multiplicity, such as singlet to triplet or vice versa.
Internal conversion (IC): A radiationless transition between electronic states of the same spin multiplicity, leading to redistribution of energy into vibrational modes.
Peroxo species: A complex in which oxygen is bound as an O₂²⁻ ligand, often formed transiently during photochemical reactions.
Superoxo species: A complex in which oxygen is bound as an O₂⁻ radical, typically exhibiting strong oxidising behaviour.
Potential energy surface (PES): A multidimensional surface describing how the energy of a molecular system varies with nuclear coordinates.
Spin–orbit coupling: An interaction between an electron’s spin and its orbital motion, facilitating intersystem crossing in heavy‐atom systems.
Time‐resolved spectroscopy: Techniques that track changes in absorption, emission or scattering on ultrafast timescales to monitor transient species.
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