Towards proper parametrization in the exciton transfer and relaxation problem: dimer

• Published in: Chemical physics Vol. 270; no. 1; pp. 141 - 156
• Main Authors: Čápek, Vladislav, Barvı́k, Ivan, Heřman, Pavel
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.07.2001
• ISSN: 0301-0104
• DOI: 10.1016/S0301-0104(01)00384-6

We confront several parametrization schemes which have been used for transfer and relaxation of Frenkel exciton interacting with a responsive bath. Standard projection formalism yields dynamic equations for the single-exciton density matrix ρ complementing the usual single-exciton Liouville equation by adding terms describing the bath influence. The latter terms must, on the other hand, be properly parametrized. Using the simplest model systems, namely symmetric dimer in Part I and symmetric trimer in Part II, we found, that a usual parametrization scheme, called the Redfield secular approximation could distort true time dependence of physical quantities calculated by means of ρ.