Effect of intermolecular vibronic coupling on nonradiative transitions and optical absorption of dimers

Пахомов, А. А.; Ekbundit, S.; Lin, Chin‐An; Alden, R. G.; Lin, Su

doi:10.1016/0022-2313(94)00054-g

Cited by 11 publications

(4 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…An approximate, yet quantitative, model for an excitonic dimer of two identical molecules A and B, linearly coupled to a single vibrational mode, was introduced by Fulton and Gouterman , and has since been well established. ,,− It is used in this work to interpret the experimental results and will therefore be outlined here. The vibrational mode, which is assumed to be totally symmetric in the monomer point group, is included in the form of one harmonic oscillator mode per molecule.…”

Section: Theoretical Frameworkmentioning

confidence: 99%

See 1 more Smart Citation

Reduction of the Fluorescence Transition Dipole Moment by Excitation Localization in a Vibronically Coupled Squaraine Dimer

et al. 2019

View full text Add to dashboard Cite

A rigidly bridged squaraine dimer serves as a model compound to study exciton interactions between two chromophores without interfering with conformational or other stereochemical isomers. We describe the synthesis as well as steady state and fs- and ps-time-resolved optical spectroscopic data. The spectra are interpreted using a vibronic coupling model, which considers a single vibrational mode that produces a shallow excited state surface with two minima. These two minima cause symmetry breaking of the excited state, which leads to a partial localization of excitation. The localization of the wave function causes a reduced fluorescence transition moment, although both the absorption and the emission spectra display exchange narrowing typical of excitonically coupled chromophores.

show abstract

Section: Theoretical Frameworkmentioning

confidence: 99%

“…Therefore, the smallest and thus most simple possible aggregate, the dimer, plays a prominent role in basic research on this subject. Among others, effects of relative orientation, distance, heterogeneity of the monomers, and also the influence of vibrational coupling have been studied. − …”

Section: Introductionmentioning

confidence: 99%

Reduction of the Fluorescence Transition Dipole Moment by Excitation Localization in a Vibronically Coupled Squaraine Dimer

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Finally, we discuss the nature of the solute-solvent interaction that facilitates the intermolecular vibronic coupling. The term "intermolecular vibronic coupling" is not entirely new if intermolecular interactions within stable molecular complexes, [33][34][35] aggregates, [36][37][38] or crystals 39,40 are discussed. For such systems, intermolecular interactions are strong in the ground electronic states so that symmetry lowering and changes in the electronic structures accompany.…”

Section: Simulation Of the Excitation Profilesmentioning

confidence: 99%

Solute–solvent intermolecular vibronic coupling as manifested by the molecular near-field effect in resonance hyper-Raman scattering

Shimada

Hamaguchi²

2011

The Journal of Chemical Physics

View full text Add to dashboard Cite

Vibronic coupling within the excited electronic manifold of the solute all-trans-β-carotene through the vibrational motions of the solvent cyclohexane is shown to manifest as the "molecular near-field effect," in which the solvent hyper-Raman bands are subject to marked intensity enhancements under the presence of all-trans-β-carotene. The resonance hyper-Raman excitation profiles of the enhanced solvent bands exhibit similar peaks to those of the solute bands in the wavenumber region of 21,700-25,000 cm(-1) (10,850-12,500 cm(-1) in the hyper-Raman exciting wavenumber), where the solute all-trans-β-carotene shows a strong absorption assigned to the 1A(g) → 1B(u) transition. This fact indicates that the solvent hyper-Raman bands gain their intensities through resonances with the electronic states of the solute. The observed excitation profiles are quantitatively analyzed and are successfully accounted for by an extended vibronic theory of resonance hyper-Raman scattering that incorporates the vibronic coupling within the excited electronic manifold of all-trans-β-carotene through the vibrational motions of cyclohexane. It is shown that the major resonance arises from the B-term (vibronic) coupling between the first excited vibrational level (v = 1) of the 1B(u) state and the ground vibrational level (v = 0) of a nearby A(g) state through ungerade vibrational modes of both the solute and the solvent molecules. The inversion symmetry of the solute all-trans-β-carotene is preserved, suggesting the weak perturbative nature of the solute-solvent interaction in the molecular near-field effect. The present study introduces a new concept, "intermolecular vibronic coupling," which may provide an experimentally accessible∕theoretically tractable model for understanding weak solute-solvent interactions in liquid.

show abstract

“…In some works related to time-resolved signals for complex dye molecules in solution, the system is conceived as few-level density-matrix models with phenomenological dephasing constants, stochastic modulation of the levels, harmonic-oscillator models, or microscopic models of nonBorn-Oppenheimer dynamics on multidimensional excitedstate potential energy surfaces (15). Moreover, the intramolecular coupling is of great importance in various physical and chemical processes, for instance in the study of vibronic coupling in weak transition probabilities forbidden by symmetry in absorption and emission (16), in the study of relaxation rates of internal conversion (17), in femtosecond spectroscopy (employing a simple case of an intersection of harmonic diabatic potential energy surfaces) (18), in the study of the optical absorption band shape of dimers (19), and in the study of resonances in a scattering process (20).…”

Section: Introductionmentioning

confidence: 99%

Study and Characterization of Resonances in the Four-Wave Mixing Signal of a Two-Level System with Intramolecular Coupling

Paz

Cusati

Salazar

et al. 2002

Journal of Molecular Spectroscopy

View full text Add to dashboard Cite

Effect of intermolecular vibronic coupling on nonradiative transitions and optical absorption of dimers

Cited by 11 publications

References 15 publications

Reduction of the Fluorescence Transition Dipole Moment by Excitation Localization in a Vibronically Coupled Squaraine Dimer

Reduction of the Fluorescence Transition Dipole Moment by Excitation Localization in a Vibronically Coupled Squaraine Dimer

Solute–solvent intermolecular vibronic coupling as manifested by the molecular near-field effect in resonance hyper-Raman scattering

Study and Characterization of Resonances in the Four-Wave Mixing Signal of a Two-Level System with Intramolecular Coupling

Contact Info

Product

Resources

About