Effect of the transition rate between two excited states on the spectral dynamics of dual fluorescence: Blurring of the isoemissive point

Nazarov, Alexey E.; Ivanov, Anatoly I.

doi:10.1016/j.jphotochem.2020.112881

Cited by 2 publications

(1 citation statement)

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“…For the numerical solution of eq , the Brownian simulation method is used, which operates in terms of stochastic trajectories and was successfully used for simulation of electron transfer kinetics. ,− A set of the stochastic trajectories describe the motion of an ensemble of particles on the free energy surface G ( D m ). The free energy G ( D m ) is numerically found by minimization of the free energy functional G int [Ψ, P⃗ ( r⃗ )] with respect to the dissymmetry parameter D using the golden-section search, so far as the domain of the variable D is restricted and belongs the range −1 ≤ D ≤ 1 as well as the G int [Ψ, P⃗ ( r⃗ )] has only one minimum in this domain for a given value of D m .…”

Section: Theoretical Methodsmentioning

confidence: 99%

Nonstationary Theory of Excited State Charge Transfer Symmetry Breaking Driven by Polar Solvent

Nazarov

Ivanov

2020

J. Phys. Chem. B

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A consistent theory of electron transfer symmetry breaking (SB) dynamics in excited quadrupolar molecules in polar solvents is developed. The interaction of the electronic subsystem of the molecule with intramolecular degrees of freedom and solvent polarization is taken into account and is divided into interaction with inertial and inertialess degrees of freedom. A strong influence of the inertialess polarization of the solvent on the extent of symmetry breaking is revealed. The theory is nonlinear due to the equilibration of inertialess degrees of freedom to the solute electronic state. The interaction of a molecule with the inertial solvent polarization is described in terms of a single variablethe reaction coordinate, for which a rigorous definition is given. The free energy of the system is derived, and the motion of the system along the reaction coordinate is modeled by the Smoluchowski equation. The theory is adapted to describe the dynamics of SB in real solvents characterized by several relaxation time scales. Conditions for the applicability of a much simpler stationary SB model are formulated. The role of thermal fluctuations in the solvent polarization is clarified. Instead of the magnitude of the dissymmetry parameter, a distribution function of molecules over this parameter is introduced. An analysis of the Franck–Condon state created by a short pump pulse shows that it has distinct features of a state with broken symmetry for a wide range of parameters. Thermal fluctuations of the solvent polarization are shown to crucially affect SB.

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