Vibrational-Mode-Selective Modulation of Electronic Excitation.

Vibrational-mode-selective modulation of electronic excitation is conducted with a synchronized femtosecond (fs) visible (vis) pulse and a picosecond (ps) infrared (IR) pulse. The mechanism of modulation of vibrational and vibronic relaxation behavior of excited state is investigated with ultrafast vis/IR, IR/IR, and vis-IR/IR transient spectroscopy, optical gating experiments and theoretical calculations. An organic molecule, 4'-(N,N-dimethylamino)-3-methoxyflavone (DMA3MHF) is chosen as the model system.

Blue-Shifted and Broadened Fluorescence Enhancement by Visible and Mode-Selective Infrared Double Excitations.

Mode-selective vibrational excitations to modify the electronic states of fluorescein dianion in methanol solutions are carried out with a femtosecond visible pulse synchronized with a tunable high-power, narrow-band picosecond infrared (IR) pulse. In this work, simultaneous intensity enhancement, peak blueshift, and line width broadening of fluorescence are observed in the visible/IR double resonance experiments. Comprehensive investigations on the modulation mechanism with scanning the vibrational excitation frequencies, tuning the time delay between the two excitation pulses, theoretical calculations, and nonlinear and linear spectroscopic measurements suggest that the fluorescence intensity enhancement is caused by the increase of the Franck-Condon factor induced by the vibrational excitations at the electronic ground state.

Regulating the Electrical Double Layer with Supramolecular Cyclodextrin Anions for Dendrite-Free Zinc Electrodeposition.

The interfacial stability of a Zn battery is dependent on the electrical double layer (EDL) that forms at the interface between the electrolyte and the Zn metal anode. A fundamental understanding of the regulation of the EDL structure and stability on the Zn surface is highly desirable for practical applications of aqueous batteries. Herein, the interfacial chemistry of the EDL is regulated by the adsorption of supramolecular cyclodextrin anions in the inner Helmholtz plane (IHP).

Direct observation of conformations of a high-mobility n-type low-bandgap copolymer in solutions and solid films.

The aggregation morphologies of conjugated polymers in solutions and solid films are important for their optoelectronic applications. Due to the amorphous state of the polymers, it remains a great challenge to determine their conformations in either liquids or solids. Herein, a ps/fs synchronized 2D IR technique is applied to investigate the molecular conformations of a high-mobility n-type low-bandgap copolymer, N2200, dissolved in CHCl and CCl, and in solid films cast from both solutions by the vibrational cross-angle method.

What Leads to Aggregation-Induced Emission?

Aggregation-induced emission (AIE), usually referring to the phenomenon in which molecules emit more strongly in the aggregate state than in the solution state, is intriguing and promising in various optoelectronic and biosensing applications. In this Perspective, the basic principles that can lead to AIE and experimental evidence to reveal the AIE mechanism of tetraphenyl ethylene (TPE)-type molecules are discussed. AIE is the consequence of two factors: (1) the fast energy dissipation by crossing a conical intersection (CI) in solutions but not in solids results in low luminescence efficiencies in the solutions, and (2) the weak intermolecular coupling and thus slow intermolecular energy/charge transfers in the AIE solids effectively prevent quenching and result in relatively high luminescence efficiencies.