Title | Toward a molecular scale interpretation of excitation energy transfer in solvated bichromophoric systems |
Publication Type | Journal Article |
Year of Publication | 2005 |
Authors | Curutchet, C, Mennucci B |
Journal | Journal of the American Chemical Society |
Volume | 127 |
Issue | 47 |
Pagination | 16733 - 16744 |
Date Published | 2005 |
ISBN Number | 0002-7863 |
Keywords | ab-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 |
Abstract | This 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. |