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Content archived on 2024-05-29

Can QM/MM calculations reproduce experimental kinetic isotope effects

Objective

Transition states (TS) hold a fundamental position in chemical reactivity. A good knowledge of the nature of Structure is the key to answer questions of selectivity and efficiency for chemical processes in, for example, industry, biochemical processes and drug design. One of the most powerful experimental techniques for probing the nature of the TS is the measurement of a kinetic isotope effect (KIE). Yet, the interpretation of KIE as admeasure of TS structure requires an appropriate theoretical framework. It is generally assumed that the quantum mechanical (QM) methods now commonly used for studying chemical reactivity can provide this framework. However, important recent work has found that conventional QM methods are not able to reproduce the range offices measured experimentally for a prototypical reaction of organic chemistry. The aim of this project is to investigate ways to overcome this gap between theory and experiment. In particular hybrid quantum/classical approaches will be used with explicit salvation in combination with molecular dynamics methods to study two examples of nucleophilic substitution reactions. In contrast to all previous calculations of Kites, attention will be directed to treating the TS as a family of individual transition structures corresponding to different configurations of solvent molecules, and will consider how Kites should be computed as average properties. Besides contributing significantly to the applicant's development as an independent researcher, the project will provide answers to fill an important gap in existing scientific knowledge. In doing so it will establish a strong link between Upscale and Bath within the context of building a wider network of effective collaboration, thereby increasing the attractiveness of research in Europe and its worldwide competitiveness.

Fields of science (EuroSciVoc)

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Keywords

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Topic(s)

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Call for proposal

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FP6-2002-MOBILITY-5
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Funding Scheme

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EIF - Marie Curie actions-Intra-European Fellowships

Coordinator

UNIVERSITY OF BATH.
EU contribution
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Address
Claverton Down
BATH
United Kingdom

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Total cost

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