Toward a molecular scale interpretation of excitation energy transfer in solvated bichromophoric systems

TitleToward a molecular scale interpretation of excitation energy transfer in solvated bichromophoric systems
Publication TypeJournal Article
Year of Publication2005
AuthorsCurutchet, C, Mennucci B
JournalJournal of the American Chemical Society
Volume127
Issue47
Pagination16733 - 16744
Date Published2005
ISBN Number0002-7863
Keywordsab-initio, charge-transfer, density-functional theory, light-harvesting complex, linked free-base, polarizable continuum model, purple bacteria, q-like bands, through-bond, transfer excited-states
AbstractThis paper presents a quantum-mechanical study of the intramolecular excitation energy transfer (EET) coupling in naphthalene-bridge-naphthalene systems in gas phase and in solution. ZINDO and TDDFT response schemes are compared using both an exact and an approximate solution. The approximate solution based on a perturbative approach uses the single chromophore properties to reconstruct the real system coupling thus neglecting possible through-bond effects which conversely are accounted for in the exact solution. The comparison of the results of the two approaches with the experiments allows a detailed analysis of the relative importance of through-bond and through-space effects as well as a more complete understanding of the modifications in the EET coupling with the size of the system, the chromophore-chromophore distance, and solvation.