Extraction of Molecular-Frame Electron-Ion Differential Scattering Cross Sections Based on Elliptical Laser-Induced Electron Diffraction.

We extracted the molecular-frame elastic differential cross sections (MFDCSs) for electrons scattering from N_{2}^{+} based on elliptical laser-induced electron diffraction (ELIED), wherein the structural evolution is initialized by the same tunneling ionization and probed by incident angle-resolved laser-induced electron diffraction imaging. To establish ELIED, an intuitive interpretation of the ellipticity-dependent rescattering electron momentum distributions was first provided by analyzing the transverse momentum distribution. It was shown that the incident angle of the laser-induced returning electrons could be tuned within 20° by varying the ellipticity and handedness of the driving laser pulses. Accordingly, the incident angle-resolved DCSs of returning electrons for spherically symmetric targets (Xe^{+} and Ar^{+}) were successfully extracted as a proof-of-principle for ELIED. The MFDCSs for N_{2}^{+} were experimentally obtained at incident angles of 4° and 7°, which were well reproduced by the simulations. The ELIED approach is the only successful method so far for obtaining incident angle-resolved ionic MFDCS, which provides a new sensitive observable for the transient structure retrieval of N_{2}^{+}. Our results suggest that the ELIED has the potential to extract the structural tomographic information of polyatomic molecules with femtosecond and subangstrom spatiotemporal resolutions that can enable the visualization of the nuclear motions in complex chemical reactions as well as chiral recognition.

Coulomb focusing in attosecond angular streaking.

Angular streaking technique employs a close-to-circularly polarized laser pulse to build a mapping between the instant of maximum ionization and the most probable emission angle in the photoelectron momentum distribution, thereby enabling the probe of laser-induced electron dynamics in atoms and molecules with attosecond temporal resolution. Here, through the jointed experimental observations and improved Coulomb-corrected strong-field approximation statistical simulations, we identify that electrons emitted at different initial ionization times converge to the most probable emission angle due to the previously-unexpected Coulomb focusing triggered by the nonadiabatic laser-induced electron tunneling. We reveal that the Coulomb focusing induces the observed nonintuitive energy-dependent trend in the angular streaking measurements on the nonadiabatic tunneling, and that tunneling dynamics under the classically forbidden barrier can leave fingerprints on the resulting signals. Our findings have significant implications for the decoding of the intricate tunneling dynamics with attosecond angular streaking.

Directly imaging excited state-resolved transient structures of water induced by valence and inner-shell ionisation.

Real-time imaging of transient structure of the electronic excited state is fundamentally critical to understand and control ultrafast molecular dynamics. The ejection of electrons from the inner-shell and valence level can lead to the population of different excited states, which trigger manifold ultrafast relaxation processes, however, the accurate imaging of such electronic state-dependent structural evolutions is still lacking. Here, by developing the laser-induced electron recollision-assisted Coulomb explosion imaging approach and molecular dynamics simulations, snapshots of the vibrational wave-packets of the excited (A) and ground states (X) of D2O+ are captured simultaneously with sub-10 picometre and few-femtosecond precision. We visualise that θDOD and ROD are significantly increased by around 50∘ and 10 pm, respectively, within approximately 8 fs after initial ionisation for the A state, and the ROD further extends 9 pm within 2 fs along the ground state of the dication in the present condition. Moreover, the ROD can stretch more than 50 pm within 5 fs along autoionisation state of dication. The accuracies of the results are limited by the simulations. These results provide comprehensive structural information for studying the fascinating molecular dynamics of water, and pave the way towards to make a movie of excited state-resolved ultrafast molecular dynamics and light-induced chemical reaction.

H2 formation via non-Born-Oppenheimer hydrogen migration in photoionized ethane.

Neutral H2 formation via intramolecular hydrogen migration in hydrocarbon molecules plays a vital role in many chemical and biological processes. Here, employing cold target recoil ion momentum spectroscopy (COLTRIMS) and pump-probe technique, we find that the non-adiabatic coupling between the ground and excited ionic states of ethane through conical intersection leads to a significantly high yield of neutral H2 fragment. Based on the analysis of fingerprints that are sensitive to orbital symmetry and electronic state energies in the photoelectron momentum distributions, we tag the initial electronic population of both the ground and excited ionic states and determine the branching ratios of H2 formation channel from those two states. Incorporating theoretical simulation, we established the timescale of the H2 formation to be ~1300 fs. We provide a comprehensive characterization of H2 formation in ionic states of ethane mediated by conical intersection and reveals the significance of non-adiabatic coupling dynamics in the intramolecular hydrogen migration.

Triple ionization and fragmentation of benzene trimers following ultrafast intermolecular Coulombic decay.

Intermolecular interactions involving aromatic rings are ubiquitous in biochemistry and they govern the properties of many organic materials. Nevertheless, our understanding of the structures and dynamics of aromatic clusters remains incomplete, in particular for systems beyond the dimers, despite their high presence in many macromolecular systems such as DNA and proteins. Here, we study the fragmentation dynamics of benzene trimer that represents a prototype of higher-order aromatic clusters. The trimers are initially ionized by electron-collision with the creation of a deep-lying carbon 2s-1 state or one outer-valence and one inner-valence vacancies at two separate molecules. The system can thus relax via ultrafast intermolecular decay mechanisms, leading to the formation of C[Formula: see text]C[Formula: see text]C[Formula: see text] trications and followed by a concerted three-body Coulomb explosion. Triple-coincidence ion momentum spectroscopy, accompanied by ab-initio calculations and further supported by strong-field laser experiments, allows us to elucidate the details on the fragmentation dynamics of benzene trimers.

Femtosecond Time-Resolved Neighbor Roles in the Fragmentation Dynamics of Molecules in a Dimer.

How the neighbor effect plays its role in the fragmentation of molecular clusters attracts great attention for physicists and chemists. Here, we study this effect in the fragmentation of N_{2}O dimer by performing three-body coincidence measurements on the femtosecond timescale. Rotations of bound N_{2}O^{+} triggered by neutral or ionic neighbors are tracked. The forbidden dissociation path between B^{2}Π and ^{4}Π is opened by the spin-exchange effect due to the existence of neighbor ions, leading to a new channel of N_{2}O^{+}→NO+N^{+} originating from B^{2}Π. The formation and dissociation of the metastable product N_{3}O_{2}^{+} from two ion-molecule reaction channels are tracked in real time, and the corresponding trajectories are captured. Our results demonstrate a significant and promising step towards the understanding of neighbor roles in the reactions within clusters.

Channel Coupling Dynamics of Deep-Lying Orbitals in Molecular High-Harmonic Generation.

Investigation on structures in the high-harmonic spectrum has provided profuse information of molecular structure and dynamics in intense laser fields, based on which techniques of molecular ultrafast dynamics imaging have been developed. Combining ab initio calculations and experimental measurements on the high-harmonic spectrum of the CO_{2} molecule, we find a novel dip structure in the low-energy region of the harmonic spectrum which is identified as fingerprints of participation of deeper-lying molecular orbitals in the process and decodes the underlying attosecond multichannel coupling dynamics. Our work sheds new light on the ultrafast dynamics of molecules in intense laser fields.

Ultrahigh Aggregation Induced Emission Efficiency in Multitwist-Based Luminogens under High Pressure.

Increasing aggregation induced emission (AIE) efficiency is of fundamental interest as it directly reflects performance of multitwist-based luminogens in bioimaging and in the photoelectric device field. However, an effective and convenient methodology to increase AIE efficiency significantly remains a challenge. Here, we present a general strategy to increase AIE efficiency of multitwist-based luminogens by pressure, resulting in a 120.1-fold enhancement of the AIE intensity of tris[4-(diethylamino)phenyl]amine (TDAPA) under high pressure compared to that of the traditional method. AIE efficiency of TDAPA increases from 0.5% to 46.1% during compression. Experimental and theoretical investigations reveal that the AIE efficiency enhancement originates from intramolecular vibration and the twisted intramolecular charge transfer are suppressed under high pressure. High AIE efficiency under high pressure provides an important inspiration for improving performance of multitwist-based luminogens in the lighting and biomedical fields.

Förster resonance energy transfer outpaces Auger recombination in CdTe/CdS quantum dots-rhodamine101 molecules system upon compression.

Förster resonance energy transfer (FRET) and Auger recombination in quantum dots (QDs)-molecules system are important mechanisms for affecting performance of their optoelectronic and photosynthesis devices. However, exploring an effective strategy to promote FRET and suppress Auger recombination simultaneously remains a daunting challenge. Here, we report that FRET process is promoted and Auger recombination process is suppressed in CdTe/CdS QDs-Rhodamine101 (Rh101) molecules system upon compression. The greatly improved FRET is attributed to the shortened donor-acceptor distance and increased the number of molecules attached to QDs induced by pressure. The reduced Auger recombination is ascribed to the formation of an alloy layer at the core/shell interface. The FRET can occur 70 times faster than Auger recombination under a high pressure of 0.9 GPa. Our findings demonstrate that high pressure is a robust tool to boost FRET and simultaneously suppress Auger recombination, and provides a new route to QDs-molecules applications.

Revealing Molecular Strong Field Autoionization Dynamics.

The novel strong field autoionization (SFAI) dynamics is identified and investigated by channel-resolved angular streaking measurements of two electrons and two ions for the double-ionized CO. Comparing with the laser-assisted autoionization calculations, we demonstrate the electrons from SFAI are generated from the field-induced decay of the autoionizing state with a following acceleration in the laser fields. The energy-dependent photoelectron angular distributions further reveal that the subcycle ac-Stark effect modulates the lifetime of the autoionizing state and controls the emission of SFAI electrons in molecular frame. Our results pave the way to control the emission of resonant high-harmonic generation and trace the electron-electron correlation and electron-nuclear coupling by strong laser fields. The lifetime modulation of quantum systems in the strong laser field has great potential for quantum manipulation of chemical reactions and beyond.

Quantum dynamics of atomic Rydberg excitation in strong laser fields.

Neutral atoms have been observed to survive intense laser pulses in high Rydberg states with surprisingly large probability. Only with this Rydberg-state excitation (RSE) included is the picture of intense-laser-atom interaction complete. Various mechanisms have been proposed to explain the underlying physics. However, neither one can explain all the features observed in experiments and in time-dependent Schrödinger equation (TDSE) simulations. Here we propose a fully quantum-mechanical model based on the strong-field approximation (SFA). It well reproduces the intensity dependence of RSE obtained by the TDSE, which exhibits a series of modulated peaks. They are due to recapture of the liberated electron and the fact that the pertinent probability strongly depends on the position and the parity of the Rydberg state. We also present measurements of RSE in xenon at 800 nm, which display the peak structure consistent with the calculations.

Ultrafast carrier dynamics in all-inorganic CsPbBr3 perovskite across the pressure-induced phase transition.

The excited-state carrier dynamics of lead halide perovskites play a critical role in their photoelectric properties, and are greatly affected by lattice structural changes. In this work, the carrier dynamics of all-inorganic CsPbBr3 peroveskite, as a function of pressure, are investigated using in situ high-pressure femtosecond transient absorption spectroscopic experiments. Compression is found to drive crystal structural evolution, thereby markedly changing the behavior of charge carriers in CsPbBr3. Before the phase transition, simultaneous prolonging of the carrier relaxation and Auger recombination is achieved alongside a narrowing in the bandgap. The results favor improved efficiency and photovoltaic performance.

Pressure-Induced Tunable Electron Transfer and Auger Recombination Rates in CdSe/ZnS Quantum Dot-Anthraquinone Complexes.

Electron transfer (ET) and Auger recombination (AR) processes in quantum dots (QDs) are key mechanisms for the advance of QD-based devices. However, it still remains a challenge to promote ET and suppress AR simultaneously. Here, we use in situ high-pressure ultrafast transient absorption spectroscopy to explore the impact of pressure on the ET between CdSe/ZnS and anthraquinone (AQ) and AR dissolved in cyclohexane. Remarkably, under compression, ET lifetimes are shorten, while suppression of AR lifetimes is present. The promotion of ET is attributed to the shortened distance between CdSe/ZnS and AQ induced by pressure. We rationalize that for the AR suppression, pressure may enhance the formation of an alloy layer at the core/shell interface. These findings indicate that compression is an effective approach to promote ET and suppress AR simultaneously. This study highlights a brand-new approach for modulating ET and AR and provides new routes toward QD-based applications.

Accurate in situ Measurement of Ellipticity Based on Subcycle Ionization Dynamics.

Elliptically polarized laser pulses (EPLPs) are widely applied in many fields of ultrafast sciences, but the ellipticity (ϵ) has never been in situ measured in the interaction zone of the laser focus. In this Letter, we propose and realize a robust scheme to retrieve the ϵ by temporally overlapping two identical counterrotating EPLPs. The combined linearly electric field is coherently controlled to ionize Xe atoms by varying the phase delay between the two EPLPs. The electron spectra of the above-threshold ionization and the ion yield are sensitively modulated by the phase delay. We demonstrate that these modulations can be used to accurately determine ϵ of the EPLP. We show that the present method is highly reliable and is applicable in a wide range of laser parameters. The accurate retrieval of ϵ offers a better characterization of a laser pulse, promising a more delicate and quantitative control of the subcycle dynamics in many strong field processes.

Lighting Up the Invisible Twisted Intramolecular Charge Transfer State by High Pressure.

The twisted intramolecular charge transfer (TICT) state plays an important role in determining the performance of optoelectronic devices. However, for some nonfluorescent TICT molecules, the "invisible" TICT state could only be visualized by modifying the molecular structure. Here, we introduce a new facile pressure-induced approach to light up the TICT state through the use of a pressure-related liquid-solid phase transition of the surrounding solvent. Combining ultrafast spectroscopy and quantum chemical calculations, it reveals that the "invisible" TICT state can emit fluorescence when the rotation of a donor group is restricted by the frozen acetonitrile solution. Furthermore, the TICT process can even be effectively regulated by the external pressure. Our study offers a unique strategy to achieve dual fluorescence behavior in charge transfer molecules and is of significance for optoelectronic and biomedical applications.

Identifying the Multielectron Effect on Chemical Bond Rearrangement of CH3Cl Molecules in Strong Laser Fields.

Strong field double ionization that triggers the chemical bond rearrangement of CH3Cl is investigated by impulsive control of the alignment of molecules. The alignment and laser intensity dependent H2+ and H3+ yields in linearly polarized femtosecond laser have been measured, and the obtained data show that the maximum signal of H2+ appears at the laser polarization parallel to the C-Cl axis of molecules and H3+ species are more likely to eject at the laser polarization parallel to the C-Cl axis at low laser intensity while the H3+ signal peaks at laser polarization perpendicular to the C-Cl axis at high laser intensity. The measurements indicate that electrons from HOMO - 1 and HOMO - 2 orbitals have been ionized for the generation of bond rearrangement at different laser intensity. Our results demonstrate the importance of multielectron effects and also provide an effective control method in the process of chemical bond rearrangement of the molecules in strong laser fields.

Multielectron Effects in the Strong Field Sequential Ionization of Aligned CH3I Molecules.

Strong field sequential ionization of symmetric-top CH3I molecules is studied experimentally by using a combined method of femtosecond laser-induced impulsive alignment and time-of-flight mass spectrometry. Both alignment- and angular-dependent ion yields have been measured, and the sequential ionization of a multielectron has been discussed. It is found that the maximum ionization occurs when the polarization of probe laser is perpendicular to the internuclear axis of molecules, and the signal of fragment ion peaks at the polarization of the probe laser is parallel to the internuclear axis of molecules. The angular distribution of ions indicated that ionization of π-type orbitals corresponds to generation of charged parent ions and ionization of σ-type orbitals corresponds to generation of fragment ions. The sequential release of multielectrons for Coulomb explosion channels is studied by analysis of the time evolutions of multicharged In+ (n = 1-4) signals.

Ultrafast proton migration and Coulomb explosion of methyl chloride in intense laser fields.

We investigated the ultrafast proton migration and the Coulomb explosion (CE) dynamics of methyl chloride (CH3Cl) in intense femtosecond laser fields at the wavelengths of 800 nm (5.5 × 1014 W/cm2) and 400 nm (4 × 1014 W/cm2), respectively. Various fragment channels from molecular dication and trication were observed by coincidence momentum imaging through the measurement of their kinetic energy releases (KERs). The proton migration from different charged parent ions was analyzed from the obtained KER distributions. For the direct CE channel of CH3+ + Cl+ and CH3+ + Cl2+, the contribution of multiply excited electronic states and multicharged states is identified. In addition, the measurements of relative yields of the fragmentation channel at different laser wavelengths provide a selective control of proton migration for CH3Cl molecules in intense laser fields.

An experimental and theoretical study of solvent hydrogen-bond-donating capacity effects on ultrafast intramolecular charge transfer of LD 490.

The excited-state intramolecular charge transfer (ICT) of LD 490 were investigated in different hydrogen-bond-donating solvents (α scale) on the basis of the Kamlet-Taft solvatochromic parameters (π*, α, ß). The femtosecond transient absorption spectra and the kinetics decay rate reveal that with an increase of solvent's α capacity, the long-lived picosecond process, which is attributed to the ICT, becomes much faster. Combining with time-dependent density functional theory (TDDFT) calculations, we demonstrate that the enhancement of α acidity substantially increases the electronegativity of the carbonyl oxygen in LD 490, which strengthen excited-state intermolecular hydrogen bonding interactions and consequently facilitate the ICT process.

Rotational Dynamics of Quantum State-Selected Symmetric-Top Molecules in Nonresonant Femtosecond Laser Fields.

Rotational dynamics of quantum state selected and unselected CH3I molecules in intense femtosecond laser fields has been studied. The orientation and alignment evolutions are derived from a pump-probe measurement and in good agreement with the numerical results from the time-dependent Schrödinger equation (TDSE) calculation. The different rotational transitions through nonresonant Raman process have been assigned from the Fourier analysis of the orientation and alignment revivals. These revivals are derived from a pump-probe measurement and in good agreement with the numerical results from the TDSE calculation. For the molecules in rotational state |1, ±1, ∓1⟩, the transitions can be assigned to ΔJ = ±1, ±2, while for thermally populated molecules, the transitions are ΔJ = ±2. Our results illustrate that the orientation and alignment revivals of the rotational quantum-state-selected molecules give a deep insight into the rotational excitation pathways for the transition of different rotational states of molecules in ultrafast laser fields.