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A model of photoinduced ultrafast charge separation and ensuing charge recombination into the ground state has been developed. The model includes explicit description of the formation and evolution of nonequilibrium state of both the intramolecular vibrations and the surrounding medium. An effect of the high-frequency intramolecular vibrational mode excitation by a pumping pulse on ultrafast charge separation and charge recombination kinetics has been investigated. Simulations, in accord with experiment, have shown that the effect may be both positive (the vibrational mode excitation increases the charge-transfer rate constant) and negative (opposite trend). The effect on charge separation kinetics is predicted to be bigger than that on the charge recombination rate but nevertheless the last is large enough to be observable. The amplitude of both effects falls with decreasing vibrational relaxation time constant, but the effects are expected to be observable up to the time constants as short as 200 fs. Physical interpretation of the effects has been presented. Comparisons with the experimental data have shown that the simulations, in whole, provide results close to that obtained in the experiment. The reasons of the deviations have been discussed.

A significant number of quadrupolar dyes with a D-π-A-π-D or A-π-D-π-A structure, where D and A are electron donor and acceptor groups, were shown to undergo symmetry breaking (SB) upon optical excitation. During this process, the electronic excitation, originally distributed evenly over the molecule, concentrates on one D-π-A branch, and the molecule becomes dipolar. This process can be monitored by time resolved infra-red (TRIR) spectroscopy and causes significant spectral dynamics. A theoretical model of excited-state SB developed earlier (Ivanov, A. I. J. Phys. Chem. C, 2018, 122, 29165-29172) is extended to account for the temporal changes taking place in the IR spectrum upon SB. This model can reproduce the IR spectral dynamics observed in the −C ≡ C− stretching region with a D-π-A-π-D dye in two polar solvents using a single set of molecular parameters. This approach allows estimating the degree of asymmetry of the excited state in different solvents as well as its change during SB. Additionally, the relative contribution of the different mechanisms responsible for the splitting of the symmetric and antisymmetric −C ≡ C− stretching bands, which are both IR active upon SB, can be determined.

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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