Shaping Conical Intersections for Intramolecular Proton Transfer

Ziel

Excited-state intramolecular proton transfer (ESIPT) - where proton transfer occurs after the absorption of a photon - is an important topic for the understanding of photoreactions in organic systems. The central aim of this proposal is to apply a unique combination of novel computational tools to understand such processes. We will study methyl salicylate (MS), a ‘floppy’ molecule with a slow proton transfer. Computationally, our first objective will be to map out the reaction paths and conical intersection seams accessible to excited states, characterised as critical points linked by minimum energy paths that preserve the degeneracy of the two states. Having determined the molecular geometries at which decay to S0 takes place, we will be able to suggest strategies to control the dynamics on the excited state. Multiple decay pathways make MS and related systems suitable for coherent control investigations; experiments which are planned by the experimental group of Prof. Fielding at University College London. MS is a challenge for quantum methods in which the dynamic electron correlation is cruzial for obtaining accurate excitation energies and realistic barrier heights. Our second objective is to compare the CASPT2 approach - which the applicant knows from his PhD- with the RASSCF one. Calculating CASPT2 energies at CASSCF geometries is a state-dependent approximation: there is the potential with RASSCF to go beyond this. There is scope to develop the projects further including environmental effects (QM/MM), or to study quantum dynamics. This fellowship proposal combines the experience of excited state calculations developed by the applicant with the complementary experience in computational methods of the host group. It will lead to new insights into the mechanism of ESIPT and greater experience in crossing seam mapping. Furthermore, there is scope for developing long-term collaborations between both computational & experimental groups in the UK & Spain.

Wissenschaftliches Gebiet

Koordinator

IMPERIAL COLLEGE OF SCIENCE TECHNOLOGY AND MEDICINE

EU-Beitrag

€ 172 740,80

Adresse

SOUTH KENSINGTON CAMPUS EXHIBITION ROAD
SW7 2AZ LONDON
Vereinigtes Königreich

Region

London Inner London — West Westminster

Aktivitätstyp

Higher or Secondary Education Establishments

Kontakt Verwaltung

Brooke Alasya (Ms.)

Links

Die Organisation kontaktieren Website

Gesamtkosten

Keine Daten

Ziel

Wissenschaftliches Gebiet

Programm/Programme

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Aufforderung zur Vorschlagseinreichung

Finanzierungsplan

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