Theory of photochemical reactions

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Science  27 Feb 1976:
Vol. 191, Issue 4229, pp. 822-830
DOI: 10.1126/science.1251196


Although the great number of electronic states available to an excited molecule might seem to preclude a coherent picture of photochemical reaction mechanisms, it is possible to bring out some basic features common to a great many reactions. The electronic states of the primary diradical intermediates, surface crossings, topicity, and avoided surface crossings have been shown to be essential components of the electronic theory of photochemical reactions. Diradicals have four important electronic states. Knowing these states, and making a simple electron count, it is possible to draw state correlation diagrams. Some diagrams show a typical surface crossing of the ground singlet state with the lowest (singlet, triplet) pair of excited states, with clear-cut consequences of quantum yields under various conditions. In other reactions the surfaces stay apart. The critical discriminating feature that determines the type of correlation diagram is the topicity. Photochemical reactions can be classified according to topicity, which is useful in interpreting their mechanisms (53). Avoided surface crossings can also be classified into different types. Figure 7, which illustrates the interplay of a covalent and an ionic surface responsible for photochemical electron transfer, is a typical multidimensional representation of a photochemical reaction. The chemical behavior of the excited zwitterionic states of common intermediates, such as twisted ethylene or diallyl, reflects the quantum mechanical nature of photochemical processes. In these states, for perfectly symmetric systems, charge oscillates back and forth between two symmetry-equivalent sites. Slight geometric perturbations can create a sudden polarization of the excited molecule, with localization of almost a full charge at one end of the molecule. A photon is transformed into an electrical signal thanks to an appropriate molecular distortion. Nature may have used this simple process in the N-retinylidene visual chromophore to trigger an electrical response to vision.

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