Modeling the IR Spectra of Excited Quadrupole Molecules with Broken Symmetry in Polar Solvents

Nazarov, Alexey E.; Ivanov, Anatoly I.

doi:10.1134/s003602442008021x

Cited by 10 publications

(10 citation statements)

References 29 publications

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“…This motion leads to an increase in the dissymmetry parameter with time, which leads to a significant decrease in the transition dipole moment observed in the experiments. , In this article, we do not model the temporal evolution of SB and the transition dipole moment. We only note that the modeling of the SB dynamics and its manifestation in the IR spectral dynamics within the framework of the adopted model is in good agreement with the experimental data. , As far as we know, there are no experimental data on the effect of solvent fluctuations on the transition dipole moment associated with the ground state absorption.…”

Section: Resultssupporting

confidence: 56%

“…We only note that the modeling of the SB dynamics and its manifestation in the IR spectral dynamics within the framework of the adopted model is in good agreement with the experimental data. 61,62 As far as we know, there are no experimental data on the effect of solvent fluctuations on the transition dipole moment associated with the ground state absorption.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The free energy functional of a dye in a polar solvent is where D and D m are independent variables. The first quantity corresponds to an isolated molecule whose Hamiltonian has the form , The value V is defined as half of the energy gap between the energy levels corresponding to the even (ψ even = (φ L + φ R )/√2) and the odd (ψ odd = (φ L – φ R )/√2) excited states of the isolated dye. 2 V can be estimated as the energy difference of the transitions corresponding to the one- and two-photon absorption in weakly polar solvents.…”

Section: Theoretical Methodsmentioning

confidence: 99%

“…This model has a simple analytical solution for stationary states of a dye in a solvent, which makes it easy to apply for the analysis of experimental data. The model is also adapted to quantitatively describe the effect of SB on vibrational spectra of the quadrupolar dyes. − …”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Effect of Symmetry Breaking in Excited Quadrupole Molecules on Transition Dipole Moment

Antipov

Ivanov

2021

J. Phys. Chem. B

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Manifestations of charge transfer symmetry breaking in excited quadrupolar molecules in optical spectra are theoretically studied. The molecules are supposed to have π-conjugated structures of A−π−D−π−A or D−π−A−π−D character, where electron acceptors (A) or electron donors (D) are identical. A theory describing the effect of symmetry breaking and solvent fluctuations on the dipole moments of optical transitions associated with absorption by a quadrupolar dye in the ground and excited states, as well as fluorescence, is developed. Simple equations describing the influence of the symmetry breaking extent on the transition dipole moments are found. The orientational solvent fluctuations are predicted to decrease the transition dipole moment of the ground state absorption. The decrease does not exceed 10%. A considerably larger effect of symmetry breaking and the solvent fluctuations on the emission dipole moment is found. Equations describing dependencies of the transition dipole moment associated with excited state absorption on the solvent polarity and the parameters of the dye are derived. The scale of the changes in the transition dipole moments due to symmetry breaking in the excited state are determined. The influence of the polar solvent fluctuations is also taken into account. The theoretical findings are shown to be consistent with the available experimental data.

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Section: Resultssupporting

confidence: 56%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Theoretical Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Effect of Symmetry Breaking in Excited Quadrupole Molecules on Transition Dipole Moment

Antipov

Ivanov

2021

J. Phys. Chem. B

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“…The applicability range of the two-level model was found in ref . A theory was also formulated describing the effect of SB on vibrational spectra in excited quadrupolar molecules, and its ability to adequately describe experimental data was demonstrated. − …”

Section: Introductionmentioning

confidence: 94%

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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Symmetry breaking charge transfer in excited multibranched molecules and dimers: A unified standpoint

Ivanov

2024

Journal of Photochemistry and Photobiology C: Photochemistry Re

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Modeling the IR Spectra of Excited Quadrupole Molecules with Broken Symmetry in Polar Solvents

Cited by 10 publications

References 29 publications

Effect of Symmetry Breaking in Excited Quadrupole Molecules on Transition Dipole Moment

Effect of Symmetry Breaking in Excited Quadrupole Molecules on Transition Dipole Moment

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

Symmetry breaking charge transfer in excited multibranched molecules and dimers: A unified standpoint

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