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

Ivanov, Anatoly I.

doi:10.1016/j.jphotochemrev.2024.100651

Cited by 3 publications

(1 citation statement)

References 129 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[45][46][47] Recently, a review of the developed models and their applications for interpreting various experimental data from a unified perspective was published. 48 The effect of a dipole moment flip during the transition from the first to the second excited state is predicted. 49 These studies demonstrated the ability of the developed models to quantitatively describe a wide range of experimental data.…”

Section: Introductionmentioning

confidence: 98%

Symmetry breaking charge transfer and control of the transition dipole moment in excited octupolar molecules

Siplivy,

Ivanov

2024

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

The structure of the energy levels of excited symmetric donor–acceptor octupolar molecules suggests a completely symmetric state and a degenerate doublet. For most molecules, the doublet is the first excited state, which is called the normal level order, but there are molecules with the reverse level order. Symmetry breaking charge transfer (SBCT) and its effect on the transient dipole moment in these structures are studied. It has been established that for reverse level order, SBCT is possible only if the reorganization energy exceeds a certain threshold, whereas for the normal level order, there is no such threshold. The lowest completely symmetric excited state is shown to become bright after SBCT. The dependence of the fluorescence transition dipole moment on the SBCT extent is calculated. It was established that the direction and magnitude of the transition dipole moment change similarly to the change in the dipole moment for the reverse level order, whereas for the normal level order, the changes are opposite. The effect of solvent thermal fluctuations on the transition dipole moment is simulated and discussed. A way for controlling the direction of the transition dipole moment by an external electric field is suggested.

show abstract

Section: Introductionmentioning

confidence: 98%

Symmetry breaking charge transfer and control of the transition dipole moment in excited octupolar molecules

Siplivy,

Ivanov

2024

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

show abstract

Excited-state symmetry breaking is an ultrasensitive tool for probing microscopic electric fields

Dereka,

Maroli,

Poronik

et al. 2024

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Effect of locally excited state on fluorescence transition dipole moment in quadrupolar molecules subjected to symmetry breaking charge transfer

Mikhailova,

Ivanov

2024

The Journal of Chemical Physics

View full text Add to dashboard Cite

In excited centrosymmetric donor–acceptor triads of type A–D–A or D–A–D, symmetry breaking charge transfer (SBCT) in polar media has been explored for a few decades. SBCT is accompanied by significant reorganization of the electronic structure of the molecule, which leads to a change in the fluorescence transition dipole moment (TDM). Previously, experiments revealed a 20%–30% reduction in TDM, which occurs on the timescale of SBCT. Simple SBCT models explain this reduction. Here, the effect of the interaction of a locally excited state with zwitterionic states on TDM is investigated. This interaction is shown to have a drastic impact on the TDM and its dependence on the solvent polarity. The magnitude of TDM can decrease monotonically, increase monotonically, and also pass through a maximum with an increase in the SBCT degree due to the locally excited state effect. The scale of changes in TDM in the course of SBCT increases greatly. The conditions for the implementation of a particular scenario have been determined. This work clearly demonstrates the observable influence of upper excited states on the photochemistry and photophysics of molecules. Methods for controlling the fluorescent characteristics of quadrupolar molecules are proposed.

show abstract

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

Cited by 3 publications

References 129 publications

Symmetry breaking charge transfer and control of the transition dipole moment in excited octupolar molecules

Symmetry breaking charge transfer and control of the transition dipole moment in excited octupolar molecules

Excited-state symmetry breaking is an ultrasensitive tool for probing microscopic electric fields

Effect of locally excited state on fluorescence transition dipole moment in quadrupolar molecules subjected to symmetry breaking charge transfer

Contact Info

Product

Resources

About