'On the fly' direct dynamics studies of photochemical reactivity development of derivative mc-scf

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Project objective

Research objectives and content The research programme involves development of a fully direct derivative MC-SCF programme and applications to organic photochemistry. a) Development: In direct MC-SCF theory AO integrals are computed directly during the solution of the MC-SCF equations. Such techniques are essential if MC-SCF methods are to applied to real problems in organic reactivity because one can avoid the need lo store integrals on slow external disk storage. Further, the size of computation that can be run depends only on the amount of computer time available rather than the disk capacity of the computer. Our major objective is to implement the same type of algorithm for derivative MC-SCF. b) Applications Modern time-resolved spectroscopic measurements are now being used to probe the intimate mechanistic details of some small molecule organic photochemical reactivity problems. The initial focus of our work will be the complementary theoretical work. The experimental experience provide details of very short lived intermediates and even transition states, quantities such as rate may be strongly influenced by dynamics associated the evolution of the excited states itself. The theoretical work may suggest new experiments or the re-interpretation of older ones. Recently the photochemical decabonylation of cyclopentanone to produce tertramethylene diradicals has been studied on the femptosecond timescale. However. the mechanism of the decarbonylation is completely unknown. We are in a unique position to probe the details of the dynamics on the excited state and the subsequent evolution of ground state products.

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Participants

• KING'S COLLEGE LONDON · LONDONCoordinatorUnited Kingdom

Links

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