title: Simulations of the Ultrafast Transient Absorption Dynamics of a Donor-Acceptor Biaryl in Solution.
abstract: A model for simulating the transient electronic absorption spectra of donor-acceptor dyads undergoing ultrafast intramolecular charge transfer in solution has been developed. It is based on the stochastic multichannel point-transition approach and includes the reorganization of high-frequency intramolecular modes (treated quantum mechanically) and of low frequency intramolecular and solvent modes (described classically). The relaxation of the slow modes is assumed to be exponential with time constants taken from experiments. The excited-state dynamics is obtained by simulating the population distribution of each quantum state after optical excitation and upon electronic and vibrational transitions. This model was used to simulate the transient electronic absorption spectra measured previously with a pyrylium phenolate in acetonitrile. A very good agreement between the simulated and measured spectra was obtained assuming a three-level model including the ground state, the optically excited state, and a dark state with large charge-transfer character and a substantially different geometry relative to that of the optically excited state. The merit of this approach to disentangle the contributions of both population changes and relaxation processes to the ultrafast spectral dynamics will be discussed.
authors.affiliation: Volgograd State University , University Avenue 100, Volgograd 400062, Russia.
authors.forename: Roman G
authors.initials: RG
authors.lastname: Fedunov
authors.affiliation: Volgograd State University , University Avenue 100, Volgograd 400062, Russia.
authors.forename: Anastasiia V
authors.initials: AV
authors.lastname: Plotnikova
authors.affiliation: Volgograd State University , University Avenue 100, Volgograd 400062, Russia.
authors.forename: Anatoly I
authors.identifier: http://orcid.org/0000-0002-4420-5863
authors.initials: AI
authors.lastname: Ivanov
authors.affiliation: Department of Physical Chemistry, University of Geneva , 30 quai Ernest-Ansermet, CH-1211 Geneva 4, Switzerland.
authors.forename: Eric
authors.identifier: http://orcid.org/0000-0002-9580-9683
authors.initials: E
authors.lastname: Vauthey