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The anti-Kasha process provides the possibility of using high-energy excited states to develop novel applications. Our previous research (Nature communications, 2020, 11, 793) has demonstrated a dual-emission anti-Kasha-active fluorophore for bioimaging application, which exhibits near-infrared emissions from the S-1 state and visible anti-Kasha emissions from the S-2 state. Here, we applied tunable blue-side femtosecond stimulated Raman spectroscopy (FSRS) and transient absorption spectroscopy, assisted by quantum calculations, to reveal the anti-Kasha dual emission mechanism, in which the emergence of two fluorescing states is due to the retardation of internal conversion from the S-2 state to the S-1 state. It has been demonstrated that the facts of anti-Kasha high-energy emission are commonly attributed to a large energy gap between the two excited states, leading to a decrease in the internal conversion rate due to a poor Franck-Condon factor. In this study, analysis of the calculation and FSRS experimental results provide us further insight into the dual-emission anti-Kasha mechanism, where the observation of hydrogen out-of-plane Raman modes from FSRS suggested that, in addition to the energy-gap law, the initial photoinduced molecular conformational change plays a key role in influencing the rate of internal conversion.

Understanding how the conformational change of conjugated molecules with acceptor-donor-acceptor (A-D-A) architecture affects their physical and optoelectronic properties is critical for determining their ultimate performance in organic electronic devices. Here, we utilized femtosecond transient absorption, time-resolved upconversion photoluminescence spectroscopy, and tunable femtosecond-stimulated Raman spectroscopy, aided by quantum chemical calculations, to systematically investigate the excited state structural dynamics of the intramolecular charge transfer of the tetramethoxy anthracene-based fluorophore 2,3,6,7-tetramethoxy 9,10-dibenzaldehydeanthracene (AnDA) and its derivative 2,3,6,7-tetramethoxy 9,10-diphenylanthracene (TMDPAn) in chloroform. In the AnDA molecule, the tetramethoxy anthracene and benzaldehyde moieties exhibit a strong ability to donate and withdraw electrons. Upon photoexcitation, AnDA shows intriguing ultrafast fluorescence switch-on and red shift dynamics on charge transfer states, and the temporal evolution of AnDA recorded by ultrafast spectroscopy reveals a dynamic picture of two-step intramolecular charge transfer assisted by ultrafast conformational changes and solvation processes. Removing the aldehyde group from TMDPAn significantly decreases the electron pulling capacity of the phenyl unit and disables charge transfer characteristics.

We experimentally demonstrate enhanced high-order harmonic generation (HHG) from spatially prepared filamentation in Argon. Upon shifting the focus position of an elliptically polarized laser pulse over the filament induced by a linearly polarized laser pulse, an obvious enhancement of harmonic yield by nearly one order of magnitude is observed. The result could be interpreted in terms of the double contributions from both the excited states of target atom and the phase-matching effect of harmonic beam. In contrast to the enhancement phenomena, an obvious suppression of harmonic yield is also presented, which could be attributed to both the ground-state depletion and the plasma effect.

High-order harmonics were generated with neon gas by using 12-fs midinfrared laser pulses with stabilized carrier-envelope phase (CEP). At some specific CEP, a broad “supercontinuum” of the extreme ultraviolet spectrum can be obtained. Two distinct continuous spectral regimes are found by numerical simulation, which come from two adjacent half cycles of the laser pulse. A phase-matching mechanism for high-photon-energy harmonics of a long trajectory driven by a midinfrared laser pulse is found.

We experimentally demonstrate an effective scheme to generate the enhanced high-order harmonics from a coherent superposition state of ground state and excited states in Argon. By controlling the time delay between the pump and probe laser pulses, a surprising enhancement plateau of high-order harmonic generation is observed, with a half lifetime of dozens of picoseconds. In the plateau, the harmonic intensity is enhanced by nearly one order of magnitude compared to the case without pre-excitation. Moreover, the gradual enhancement process is also presented when the pump intensity is increasing for improving the population of excited states, which can be attributed to the Rydberg states created by frustrated tunneling ionization.

The selective generation of an intense single harmonic has been experimentally achieved in argon from a long gas cell with loosely focusing optics using a three-color laser field. When compared with the single harmonic emission from a continuous gas jet, both the intensity and the purity of the selected single harmonic emission from the long gas cell show dramatic improvements; the peak intensity is more intense by as much as 1–2 orders of magnitude, while the contrast ratio (i.e., the spectral purity) is simultaneously increased by several times. The underlying physics of this enhancement can be explained using the strong field approximation model with the propagation effect.