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Molecules irradiated with intense laser pulses (field intensity ∼1015 W/cm2) exhibit a variety of characteristic processes, such as tunneling ionization, electron rescattering, high-order harmonics...

Ultrafast dynamics of highly excited Rydberg states of ${\mathrm{Xe}}^{+}$ is investigated by time-resolved shot-by-shot photoelectron spectroscopy with EUV--free-electron-laser pump (40.8 eV) and near-infrared probe (1.56 eV) pulses. Sorting the single-shot spectra in the order of relative delay between the two pulses allows for investigating ultrafast decays of intermediate states participating in the double ionization of Xe. Observed photoelectron spectra show a biexponential decay within \ensuremath{\sim}100 fs and \ensuremath{\sim}300 ps in addition to constant signals lasting longer than 1 ns. These ultrafast decays reflect the lifetimes of autoionizing Rydberg states converging to electronically excited states of ${\mathrm{Xe}}^{2+}$. The results demonstrate that time-resolved shot-by-shot EUV--free-electron-laser photoelectron spectroscopywith a synchronized optical laser provides a powerful tool for investigating ultrafast electron emission processes.

We have used the FERMI free-electron laser to perform time-resolved photoelectron imaging experiments on a complex group of resonances near 15.38 eV in the absorption spectrum of molecular nitrogen, N2, under jet-cooled conditions. The new data complement and extend the earlier work of Fushitani et al. [Opt. Express 27, 19702–19711 (2019)], who recorded time-resolved photoelectron spectra for this same group of resonances. Time-dependent oscillations are observed in both the photoelectron yields and the photoelectron angular distributions, providing insight into the interactions among the resonant intermediate states. In addition, for most states, we observe an exponential decay of the photoelectron yield that depends on the ionic final state. This observation can be rationalized by the different lifetimes for the intermediate states contributing to a particular ionization channel. Although there are nine resonances within the group, we show that by detecting individual photoelectron final states and their angular dependence, we can identify and differentiate quantum pathways within this complex system.

Ion-coincidence momentum imaging of Coulomb explosion of formaldehyde (H2CO) in femtosecond intense laser fields (800 nm, 1.3 × 1015 W/cm2) is performed with two different laser pulse durations (7 fs and 35 fs). In the 7-fs laser fields, the full fragmentation pathway from H2CO4+ → H+ + H+ + C+ + O+ is identified. The angles between the fragment momenta are well reproduced by a simple Coulomb explosion model from the geometry of neutral formaldehyde, showing that the molecular structure is virtually frozen along the bending coordinates during the multiple ionization. Three-body Coulomb explosion pathways from triply charged states, H2CO3+ → H+ + H+ + CO+ and H+ + CH+ + O+, are observed in both the 7-fs and 35-fs laser fields. Significant changes in the momentum angle distribution and asymmetric energy partitioning between two H+ ions are observed in the 35-fs case, which are attributed to structural deformation prior to the Coulomb explosion in the longer pulse.

The pulse duration of soft X-ray free-electron laser (FEL) pulses of SACLA BL1 (0.2–0.3 nC per bunch, 0.5–0.8 MeV) were characterized by photoelectron sideband measurements. The intensity of the He 1 s−1 photoelectron sidebands generated by a near-infrared femtosecond laser was measured as a function of the time delay between the two pulses using an arrival time monitor. From the width of the cross-correlation trace thus derived, the FEL pulse duration was evaluated to be 28 ± 5 fs full width at half-maximum in the photon energy range between 40 eV and 120 eV.

Coulomb explosion of CO 2 , CO 2 → CO 2 2 + + 2e − → CO + + O + + 2e − , in phase-locked two-color ultrashort intense laser fields (800 nm and 400 nm, ∼10 14 W/cm 2 ) has been investigated by coincidence momentum imaging. The momentum images of the O + and CO + fragments show asymmetric distributions along the laser polarization direction depending on the relative phase of the two-color laser fields. The fragment asymmetry becomes most prominent (∼4%) at the relative phases providing the largest asymmetry of the electric field amplitude, with the O + fragments preferentially ejected to the stronger field side. The mechanism of the asymmetric bond breaking of the two equivalent C O bonds is discussed in terms of the nuclear dynamics in CO 2 2 + .

Two-photon Rabi oscillations are observed in He on a timescale of 10 fs by utilizing the strong-field phenomenon known as Freeman resonance. The importance of ponderomotive shifts of both the Rydberg states and the ionization limit is highlighted. Coherent light–matter interaction provides powerful methods for manipulating quantum systems1,2,3. Rabi oscillation is one such process. As it enables complete population transfer to a target state, it is thus routinely exploited in a variety of applications in photonics, notably quantum information processing4,5. The extension of coherent control techniques to the multiphoton regime offers wider applicability, and access to highly excited or dipole-forbidden transition states. However, the multiphoton Rabi process is often disrupted by other competing nonlinear effects such as the a.c. Stark shift, especially at the high laser-field intensities necessary to achieve ultrafast Rabi oscillations6. Here we demonstrate a new route to drive two-photon Rabi oscillations on timescales as short as tens of femtoseconds, by utilizing the strong-field phenomenon known as Freeman resonance7. The scenario is not specific to atomic helium as investigated in the present study, but broadly applicable to other systems, thus opening new prospects for the ultrafast manipulation of Rydberg states8.

We present applications of extreme ultraviolet (XUV) single-order laser harmonics to gas-phase ultrafast photoelectron spectroscopy. Ultrashort XUV pulses at 80 nm are obtained as the 5th order harmonics of the fundamental laser at 400 nm by using Xe or Kr as the nonlinear medium and separated from other harmonic orders by using an indium foil. The single-order laser harmonics is applied for real-time probing of vibrational wavepacket dynamics of I2 molecules in the bound and dissociating low-lying electronic states and electronic-vibrational wavepacket dynamics of highly excited Rydberg N2 molecules.

Tunneling-ionization imaging of photoexcitation of NO has been demonstrated by using few-cycle near-infrared intense laser pulses (8 fs, 800 nm, 1.1×10^{14} W/cm^{2}). The ion image of N^{+} fragment ions produced by dissociative ionization of NO in the ground state, NO (X^{2}Π,2π)→NO^{+}+e^{-}→N^{+}+O+e^{-}, exhibits a characteristic momentum distribution peaked at 45° with respect to the laser polarization direction. On the other hand, a broad distribution centered at ∼0° appears when the A^{2}Σ^{+} (3sσ) excited state is prepared as the initial state by deep-UV photoexcitation. The observed angular distributions are in good agreement with the corresponding theoretical tunneling ionization yields, showing that the fragment anisotropy reflects changes of the highest-occupied molecular orbital by photoexcitation.

Photoelectron spectroscopy of isolated atoms and molecules using single-order high-harmonics of Ti:Sapphire laser pulses (800 nm, 12 fs/30 fs) is demonstrated. Dielectric multilayer mirrors, SiC/Mg and Mo/Si, are used to isolate the 27th (42 eV) and 59th (91 eV) order harmonics, respectively. The obtained harmonics are characterized by valence and inner-shell photoelectron spectroscopy of Xe. The applications to two-color two-photon ionization of He and pump-probe spectroscopy of ultrafast photodissociation of Br2, Br2(C1Πu) → Br(2P3/2) + Br(2P3/2), are presented.

An electron–ion coincidence momentum imaging apparatus has been developed and applied to dissociative ionization of CS 2 in ultrashort intense laser fields. Photoelectron images of CS 2 in 35 fs intense laser fields (2 × 10 13 W/cm 2 , 800 nm, linearly polarized) recorded in coincidence with the parent ion, CS 2 + , show clear concentric ring patterns due to the above-threshold ionization (ATI) process. On the other hand, broad structureless distributions elongated along the direction of the laser polarization are observed in the coincidence electron images for the CS + and S + fragment ions. The difference in the electron images indicates that the dissociative ionization does not proceed sequentially by the formation and photodissociation of CS 2 + in intense laser fields.

Femtosecond pump–probe 2D (wavelength and delay) optical Kerr effect (OKE) spectroscopy is used to measure laser induced birefringence in parahydrogen and normal hydrogen crystals at 4.2 K. At the probe center wavelength the OKE signal reveals underdamped sinusoidal modulations at frequencies corresponding to the Raman-active transverse optical phonon mode of solid parahydrogen (36.8 cm−1) and normal hydrogen (38.5 cm−1), respectively. For parahydrogen crystals, at small shifts away from the probe center wavelength the OKE signal displays high frequency oscillations (355 cm−1) which correspond to J = 2 rotons with a 94 fs time period.

Three-body Coulomb explosion of formaldehyde (H2CO) in intense 7- and 35-fs laser fields (1.3 × 1015 W/cm2) has been investigated by using ion-coincidence momentum imaging technique. Two types of explosion pathways from the triply charged state, H2CO3+ → (i) H+ + H+ + CO+ and (ii) H+ + CH+ + O+, have been identified. It is shown from the momentum correlation of the fragment ions of pathway (i), that the geometrical structure of the molecule is essentially frozen along the H-C-H bending coordinate for the 7-fs case. On the other hand, for a longer pulse duration (35 fs), structural deformation along the C-H stretching and H-C-H bending coordinates is identified, which is ascribed to the nuclear dynamics in the dication states populated within the laser pulse duration.

Ultrafast three-body Coulomb explosion of formaldehyde (H2CO) in intense laser fields has been studied. The pulse duration dependence of the Newton plot of the fragment ions revealed the ultrafast molecular dynamics in the dication states.

Single-shot photoelectron spectroscopy of nonresonant two-color two-photon ionization of He has been carried out using an intense free-electron laser (FEL) at 59.7 nm and a femtosecond UV laser at 268 nm. By shot-by-shot analysis of photoelectron spectra, the cross section for nonresonant two-color ionization of He is determined to be ${\ensuremath{\sigma}}^{(2)}=4.1(6)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}52}$ cm${}^{4}$ s. The cross-correlation trace derived from the nonresonant signals shows that the temporal resolution of the system is 0.36(3) ps, which is mainly governed by the timing jitter between the FEL and UV laser pulses.

Nonlinear processes of rare gas atoms in intense extreme ultraviolet (EUV) free-electron laser (FEL) fields have been investigated by photoelectron spectroscopy. Simultaneous recording of fluctuating laser spectra from self-amplified spontaneous emission (SASE) FEL and nonlinear responses of target atoms provided a deeper understanding on the multiphoton processes in (i) double ionization of Ar and (ii) double excitation of He, in intense EUV laser fields. Results on two-color time-resolved experiment are also presented.

We report the results of our preliminary investigations into the suitability of condensed-phase parahydrogen as a Raman-shifting medium for infrared cavity ringdown laser absorption spectroscopy. We have observed the conversion of ∼10-ns pulses of 532-nm radiation into first-, second-, and third-order vibrational Stokes radiation in bulk liquid and solid parahydrogen after a single 11-cm pass. Unexpectedly, we find that liquid H2 yields more efficient conversion than solid H2 with certain focal geometries, and that in the case of the solid, a collimated or loosely focused pump geometry is more efficient than a tight focus.

The visualization of ultrafast isomerization of deuterated acetylene dication (C(2)D(2)(2+)) is demonstrated by time-resolved Coulomb explosion imaging with sub-10 fs intense laser pulses (9 fs, 0.13 PW cm(-2), 800 nm). The Coulomb explosion imaging monitoring the three-body explosion process, C(2)D(2)(3+)→ D(+) + C(+) + CD(+), as a function of the delay between the pump and probe pulses revealed that the migration of a deuterium atom proceeds in a recurrent manner; One of the deuterium atoms first shifts from one carbon site to the other in a short timescale (∼90 fs), and then migrates back to the original carbon site by 280 fs, in competition with the molecular dissociation. Correlated motion of the two deuterium atoms associated with the hydrogen migration and structural deformation to non-planar geometry are identified by the time-resolved four-body Coulomb explosion imaging, C(2)D(2)(4+)→ D(+) + C(+) + C(+) + D(+).

Photoelectron spectroscopy has been performed to study the multiphoton double ionization of Ar in an intense extreme ultraviolet laser field (hν ∼ 21 eV, ∼ 5 TW/cm²), by using a free electron laser (FEL). Three distinct peaks identified in the observed photoelectron spectra clearly show that the double ionization proceeds sequentially via the formation of Ar(+): Ar+hν→Ar (+) + e⁻ and Ar²(+) + 2hν→Ar(+) + e⁻. Shot-by-shot recording of the photoelectron spectra allows simultaneous monitoring of FEL spectrum and the multiphoton process for each FEL pulse, revealing that the two-photon ionization from Ar(+) is significantly enhanced by intermediate resonances in Ar(+).

We theoretically investigate the laser-assisted photoionization of He by an extreme ultra violet (XUV) pulse in the presence of a linearly chirped intense laser pulse by solving the time-dependent Schrodinger equation within the single-active-electron approximation. Analysis based on the time-dependent perturbation theory is also carried out to provide more physical insights. A new scheme is shown to be capable of extracting the arrival time of an XUV free-electron laser (FEL) pulse relative to an external laser pulse as well as the XUV pulse duration from the photoelectron sidebands resulting from XUV ionization in the presence of a chirped laser pulse. This scheme is independent of the energy fluctuation and the timing jittering of the FEL pulse. Therefore it can be implemented in a non-invasive way to characterize FEL pulses on a shot-by-shot basis in time-resolved spectroscopy.

We demonstrate ultrafast multiphoton coherent excitation in near-infrared intense laser fields (≤10 TW/cm2) using excited helium in the 1s2p (1P) state as the target. Strong two-photon coupling between the 2p state and the 5f and 6f Rydberg states drives ultrafast Rabi oscillations in tens of femtosecond. Theoretical calculations solving the time-dependent Schrodinger equation were carried out to elucidate the strong field effects.

Dissociative ionization of NO, NO → NO+ + e− → N+ + O + e−, in ω-2ω two-color phase-controlled intense laser fields was investigated by three-dimensional ion momentum imaging. The momentum image of the N+ ion exhibited anisotropic distributions peaked at 35° against the laser polarization, which show clear left-right asymmetry depending on the ω-2ω relative phase. The present study demonstrates that the molecular orbital can be retrieved by distinguishing the difference between the N and O side from the fragment anisotropy by intense laser pulses.

We report the preliminary results of our experiments with stimulated Raman scattering in para-hydrogen crystal aimed at developing a continuously tunable laboratory laser source of mid-infrared radiation. With laser pulses at 532 nm, a conversion efficiency for the first Stokes beam of as much as 20% in the forward direction was observed through a single-pass, 5-cm-long crystal. Generation of mid-infrared pulses at 4.5 microm was achieved by use of the output of a near-infrared pulsed laser (1.6 microm, 3 ns), and an absorption spectrum of gaseous CD4 molecules was successfully recorded. These results suggest use of the solid para-hydrogen Raman shifter as a promising light source for mid-infrared spectroscopy.

Ultrafast multichannel single-photon ionization of Ar is investigated theoretically by a model calculation incorporating correlation between the photoelectron and photoion. It is shown that the coherent hole dynamics in Ar+ associated with a superposition of the spin–orbit states can be observed by using a Fourier-transform limited laser pulse for ionization, while the coherence is degraded or lost by chirped a laser pulse. We demonstrate that the coherent hole dynamics can be retrieved even in the case of ionization by a chirped laser pulse, by labeling the photoion dynamics with the counterpart photoelectron energy.

Dissociative ionization (DI) of NO in few-cycle intense laser fields was investigated by using the 3D momentum imaging method. It was found that the symmetry change in the outermost occupied molecular orbital upon the π – σ electronic transition is clearly reflected in the spatial anisotropy of the fragmention, N+.

Generation of single-order laser harmonics in extreme ultraviolet (EUV) and the application to the time-resolved photoelectron spectroscopy of I(2) are demonstrated. The EUV pulses at 80 nm were generated from Kr as the 5th order harmonics of intense 400 nm laser pulses and then separated from other harmonic orders by a thin indium foil. The pump-probe photoelectron spectroscopy of I(2) in the B (3)Π(0(u)(+)) and B" (1)Π(1(u)) states excited by visible laser pulses at 490 nm showed a rapid increase in the yield of atomic iodine (~400 fs), reflecting the dissociation dynamics evolving simultaneously in the two excited states.

We discuss two novel approaches to visualize ultrafast dynamics of polyatomic molecules using few-cycle intense laser pulses and the high-order harmonics in the soft X-ray region, respectively. First, we present the real-time Coulomb explosion imaging of ultrafast isomerization of C2D22+ by using intense few-cycle laser pulses (

The isomerization of acetylene via hydrogen migration in intense laser fields (8 x 10(14) W/cm2) has been investigated by coincidence momentum imaging of the three-body Coulomb explosion process, C2H2 (3+)-->H+ + C+ + CH+. When ultrashort (9 fs) laser pulses are used, the angle between the momenta of C+ and H+ fragments exhibits a sharp distribution peaked at a small angle ( approximately 20 degrees ), showing that the hydrogen atom remains near the original carbon site in the acetylene configuration. On the other hand, a significantly broad distribution extending to larger momentum angles ( approximately 120 degrees ) is observed when the pulse duration is increased to 35 fs, indicating that the ultrafast isomerization to vinylidene is induced in the longer laser pulse.

Ultrafast hydrogen migration in deuterated acetylene dication (C2D22+) is studied by the pump-probe Coulomb explosion imaging with few-cycle intense laser pulses (9 fs, 0.13 PW/cm2, 800 nm). The temporal evolution of the momenta of the fragment ions produced by the three-body explosion, C2D23+ → D++ C+ + CD+, shows that the migration proceeds in a recurrent manner: The deuterium atom first shifts from one carbon site to the other in a short time scale (~90 fs), and then migrates back to the original carbon site by 280 fs, in competition with the molecular dissociation.