Three-photon Ionization Research Articles

Momentum distributions of symmetric (H2+) and asymmetric (HeH2+) molecular ions in a circularly polarized laser field under different ionization mechanisms

Abstract By numerically solving the two-dimensional (2D) time-dependent Schrödinger equation (TDSE), we present photoelectron momentum distributions (PMDs) and photoelectron angular distributions (PADs) of symmetric ( H 2 + ) and asymmetric (HeH2+) molecular ions in circularly polarized (CP) laser pulses. By adjusting the laser wavelength, two circumstances of resonance excitation and direct ionization were considered. The ionization mechanism of the resonance excitation was mainly investigated. The results show that the PMDs of H 2 + and HeH2+ in the y-direction gradually increase with increasing intensity, and the number of PMDs lobes is in good agreement with the results predicted by the ultrafast ionization model. In the resonance excitation scenario, the PMDs of H 2 + are dominated by two-photon ionization, whereas the PMDs of HeH2+ are dominated by three-photon ionization. Furthermore, the PMDs of HeH2+ are stronger in the resonance excitation scenario than those of H 2 + , which can be explained by the time-dependent population of electrons. In addition, the molecular structure is clearly imprinted onto the PMDs.

Competition of multiphoton ionization pathways in lithium

We study the three-photon ionization of atomic lithium by intense, short light pulses, via numerically solving the time-dependent Schrödinger equation. Two-photon Rabi oscillations are induced between the 2s and 4s states, which are damped due to single-photon ionization to the p continuum. Developing a minimal three-level model, we analyze the spectral features of the Autler–Townes (AT) doublet that is formed upon the resonant coupling with the laser pulse. Furthermore, we show that this 2s→→4s→p continuum pathway is the dominant process, if the duration of the laser pulse exceeds a certain value. For shorter pulses, ionization through the 2p state ( 2s→2p→4d→f continuum ) gradually becomes the dominant process, provided that the pulse is strong enough to induce several Rabi floppings. Here, we trace the competition of these ionization pathways by observing the structural changes in the shape of the AT doublet.

Resonance multiphoton ionization of alkaline Earth Ca, Ba, Sr atoms

In this work, we study the process of three-photon resonant ionization of alkaline earth atoms Ca, Sr, and Ba. To carry out the experiments, a frequency-tunable laser setup was created. An effusive beam of alkali atoms served as an atomic target.

Wavelength- and ellipticity-dependent photoelectron spectra from multiphoton ionization of atoms

We theoretically study the photoelectron momentum distributions from multiphoton ionization of a model lithium atom over a range of laser wavelengths from 500 nm to 700 nm by numerically solving the time-dependent Schrödinger equation. The photoelectron momentum distributions display many ring-like patterns for the three-photon ionization, which vary dramatically with the change of the laser wavelength. We show that the wavelength-dependent photoelectron energy spectrum can be used to effectively identify the resonant and nonresonant ionization pathways. We also find an abnormal ellipticity dependence of the electron yield for the (2+1) resonance-enhanced ionization via the 4d intermediate state, which is relevant to the two-photon excitation probability from the ground state to the 4d state.

Three-dimensional photoelectron holography with trichromatic polarization-tailored laser pulses

We present a three-dimensional (3D) photoelectron wave packet holography scheme based on polarization-tailored trichromatic femtosecond laser pulses for the determination of quantum phases in atomic multiphoton ionization (MPI). Experimentally, we combine supercontinuum polarization pulse shaping with photoelectron tomography for the reconstruction of the 3D photoelectron momentum distribution (PMD). To demonstrate the 3D photoelectron holography scheme, we superimpose a sculptured wave packet encoding a relative continuum phase with a reference wave packet. In particular, we create a sculptured angular momentum superposition wave packet by (2 + 1) resonance-enhanced MPI of potassium atoms using a counter-rotating circularly polarized bichromatic pulse sequence. The sculptured wave packet, consisting of states with different orbital angular momentum quantum numbers, interferes with the reference wave packet generated by direct three-photon ionization with a circularly polarized pulse of the third color. Depending on the circularity of the reference pulse, interference of both wave packets gives rise to 3D photoelectron holograms with c 2 or c 4 rotational symmetry in the laser polarization plane, i.e., in the azimuthal direction. In the polar direction, the azimuthal interference pattern undergoes a phase-shift revealing the relative quantum phase between the p- and f-type continuum partial waves in the sculptured wave packet. We determine the relative continuum phase by fitting the parameters of an analytical model of the hologram to the measured 3D PMD and confirm the result by direct extraction of the continuum phase difference from the polar-angle-dependent azimuthal phase-shift of the photoelectron angular distribution.

Helicity dependent Wigner phase shift for photoionization in a circularly polarized laser field

The sensitivity of strong-field ionization to atomic orbital helicity has attracted much attention from physicists, due to its potential application in attosecond spectroscopy and spintronics. In order to intuitively observe the physical mechanisms of helicity-dependent ionization rates during photoionization, the concept of the Wigner phase can be used to characterize the different interactions between the rotating electrons and the Coulomb potential. Here, we find that in both one- and three-photon ionization schemes, the electrons liberated more easily by the circularly polarized laser field suffer less influence of the Coulomb potential during the propagation and then accumulate less Winger phase. This result indicates that the strength of the interaction between the rotating electrons and the Coulomb potential can explain the helicity-dependent ionization for different ionization mechanisms universally, which is also supported by our classical ensemble analysis. Our work provides an intuitive perspective towards the physics picture of ionization propensity rules.

Phase dependence of resonant and antiresonant two-photon excitations

Measurements of the phase of two-photon matrix elements are presented for resonant and antiresonant two-color ionization of helium. A tunable, narrow-bandwidth, near-infrared (NIR) laser source is used for extreme ultra-violet (XUV) high-harmonic generation (HHG). The 15th harmonic of the laser is used within (1+1') XUV+NIR two-photon ionization, and tuned in and out of resonance with members of the 1s$n$p $^1$P$_1$ ($n=3,4,5$) Rydberg series, covering a broad spectral range with high spectral resolution. The technique allows to observe characteristic rapid changes in the phase of the two-photon matrix elements around the resonances and, previously unobserved, at the antiresonances between the resonances. Similar effects are observed for (1+2') XUV+NIR three-photon ionization. The experimental results are compared to a perturbative model and to numerical solutions of the time-dependent Schr\"odinger equation (TDSE) in the single active electron (SAE) approximation, elucidating the origin and dependences of the observed phenomena.

Separation of manganese isotopes by resonance ionization mass spectrometry for 53Mn half-life determination

We report on the production of ultra-pure samples of the long-lived radioisotope 53Mn for precision measurements of its half-life. Activated samples from a copper beam dump from PSI, which was irradiated with 590 MeV protons, were used for extraction of the manganese fraction. Following initial radiochemical purification, efficient three-photon laser resonance ionization of manganese inside a hot-cavity laser ion source was applied for subsequent isotope selection in a 30 keV high transmission magnetic mass separator. A new ionization scheme was developed and characterized for 53Mn implantation. In this way the isobar 53Cr and the Mn isotopes 54,55Mn are quantitavely removed, with a special focus on the radioactive 54Mn isotope. Microgram quantities of 53Mn were implanted into Al targets with an isotopic and isobaric purity of well above 103. An overall efficiency of the enrichment process of about 15% was demonstrated.

Reaction microscope for investigating ionization dynamics of weakly bound alkali dimers.

We report on the implementation of a far-off-resonant, optical dipole force trap in a reaction microscope combined with a magneto-optical trap. Kinematically complete multi-photon ionization experiments were performed on optically trapped 6Li atoms and photo-associated 6Li2 molecules in their highest vibrational state. The apparatus allows us to distinguish different ionization mechanisms related to the presence of the IR field of the optical dipole trap that can occur during ionization of 6Li and 6Li2 in strong fields. In a series of proof-of-principle experiments, we detect weakly bound dimers via three-photon ionization with femtosecond pulses (τ = 30 fs) at a central wavelength of 780 nm and measure directly the momenta of the photoelectrons in coincidence with recoil ions.

High efficiency laser resonance ionization of plutonium

Three-step resonance photoionization spectra of plutonium have been studied with Ti:Sapphire lasers for the development of efficient laser ionization schemes for ultra-trace analysis of Pu isotopes by resonance ionization mass spectrometry. We observed eighteen intermediate excited states of even parity in the energy range 35568–36701 {text {cm}}^{-1}, thirteen of them have not been previously documented, and a larger number of high-lying excited states and autoionizing states of odd-parity between 48238 and 49510 {text {cm}}^{-1}. Three-color, three-photon ionization schemes via six intermediate states were evaluated under similar ion source operating conditions. This led to a highly efficient three-step scheme with an overall ionization efficiency of 51.1 pm 1.3%, which is an order of magnitude improvement over the previously reported ionization efficiency for Pu.

Controlling the atomic-orbital-resolved photoionization for neon atoms by counter-rotating circularly polarized attosecond pulses.

We theoretically investigate the atomic-orbital-resolved vortex-shaped photoelectron momentum distributions (PMDs) and ionization probabilities by solving the two-dimensional time-dependent Schrödinger equation (2D-TDSE) of neon in a pair of delayed counter-rotating circularly polarized attosecond pulses. We found that the number of spiral arms in vortex patterns is twice the number of absorbed photons when the initial state is the ψm=±1 state, which satisfy a change from c2n+2 to c2n (n is the number of absorbed photons) rotational symmetry of the vortices if the 2p state is replaced by 2p+ or 2p- states. For two- and three-photon ionization, the magnetic quantum number dependence of ionization probabilities is quite weak. Interestingly, single-photon ionization is preferred when the electron and laser field corotate and ionization probabilities of 2p- is much larger than that of 2p+ if the proper time delay and wavelength are used. The relative ratio of ionization probabilities between 2p- and 2p+ is insensitive to laser peak intensity, which can be controlled by changing the wavelength, time delay, relative phase and amplitude ratio of two attosecond pulses.

Three-Photon Ionization with One-Photon Resonance between Excited Levels

Within the framework of a three-level model, the process of three-photon ionization with one-photon resonance between two excited levels (with the lower one being initially unpopulated) is considered using the density matrix method. It is shown that such resonance can result in the appearance of a maximum in the three-photon ionization spectrum when detuning between the resonance wavenumber and the wavenumber of the transition responsible for the lower excited level being populated exceeds the laser radiation linewidth by more than three orders of magnitude.

Coherent control mechanisms in bichromatic multiphoton ionization

Free electron vortices (FEVs) generated by multiphoton ionization (MPI) with ultrashort laser pulses have attracted significant attention due to their varied symmetries and unusual topological properties. We study two physical mechanisms of coherent control in atomic MPI with bichromatic polarization-shaped femtosecond laser pulses which give rise to the rich variety of FEVs. In the experiments, we combine pulse shaping of a carrier-envelope phase-stable supercontinuum with photoelectron tomography to generate and reconstruct three-dimensional photoelectron momentum distributions (PMDs). Simultaneous measurements of energetically separated photoelectrons from intraband and interband interference in a single PMD allow us to compare phase and polarization control of the angular distributions by both mechanisms. We investigate phase control in three scenarios: first, counterrotating circularly polarized pulses are employed to contrast the phase-insensitive angular momentum eigenstate created by intraband interference via frequency mixing with the phase-sensitive c 7 rotationally symmetric FEV from pure interband interference of two single-color ionization pathways. In the second scenario, we use orthogonal linearly polarized pulses to compare the phase control properties of a six-lobed angular momentum wave packet from intraband interference to those of a complex shaped interband PMD in the presence of phase fluctuations. Finally, we demonstrate phase control of a photoelectron hologram from mixed interband interference. In a (3 + 1) resonance enhanced MPI scheme, the red pump pulse induces a bound electron wave packet probed by the time-delayed blue pulse. The latter simultaneously creates a reference wave packet by three-photon ionization to form the photoelectron hologram. Rotation of the hologram with c 1 or c 5 rotational symmetry maps the time evolution of the bound wave packet. To analyze our results, we develop analytical expressions for the wave functions of intraband and interband interference in perturbative non-resonant MPI. The experiments are complemented with two-dimensional TDSE simulations to follow the FEV formation dynamics and to validate the physical pictures.

The bond dissociation energy of VO measured by resonant three-photon ionization spectroscopy.

The predissociation threshold of VO has been measured using resonant three-photon ionization (R3PI) spectroscopy. Given the high density of electronic states in the molecule, it is argued that the molecule dissociates rapidly as soon as the thermochemical bond dissociation energy (BDE) is exceeded, allowing the measured predissociation threshold to be assigned as the BDE. This is the first time a BDE has been measured using the R3PI method. The first photon is provided by an optical parametric oscillator (OPO) laser that promotes VO into a high-energy, discrete vibronic state. A tunable dye laser then excites the molecule further to a resonant state close to the dissociation limit where there is a quasi-continuum of states. A second photon from the same dye laser pulse ionizes the molecule, generating VO+ ions. The dye laser is then scanned to higher energies, and when the energy of one OPO photon plus one dye photon exceeds the BDE, the molecule dissociates before another dye photon can be absorbed to induce ionization. The combined photon energy at the sharp drop in the ion signal is assigned as the BDE. The experiment has been repeated using four different intermediate states, all yielding the same BDE, D0(VO) = 6.545(2) eV. Using thermochemical cycles, a revised value for the BDE of cationic VO is obtained, D0(V+-O) = 6.053(2) eV. The 0 K enthalpy of formation for VO(g) is also derived as ΔfH0K 0VO(g) = 128.6(1.0) kJ mol-1. Previous spectroscopic and thermochemical studies of VO are reviewed.

Development of two-color resonant ionization sputtered neutral mass spectrometry and microarea imaging for Sr

Two-color resonant laser ionization sputtered neutral mass spectrometry offers high elemental selectivity. In this study, two-color resonance ionization in sputtered neutral Sr was confirmed by combining a grating type Ti:sapphire laser system and a time-of-flight secondary ion mass spectrometry (TOF-SIMS) system. The authors compared the ionization efficiencies of Sr of the two-color three-photon ionization scheme 1 (first step: 460.862 nm; second step: 767.519 nm) and the two-color two-photon ionization scheme 2 (first step: 460.862 nm; second step: 405.200 nm). The resonant ionization efficiency of the latter was found to be 50 times larger than that of the former. Finally, the authors mapped the microarea distribution of Sr by two-color resonant ionization sputtered neutral mass spectrometry.

Ionization of helium by an ultrashort extreme-ultraviolet laser pulse

We theoretically study photoelectron angular distributions and related anisotropy parameters for the competition of one- and two-photon ionization of He in an ultrashort extreme-ultraviolet laser pulse, using numerical results from the time-dependent Schrödinger equation. We explore the transition between the two processes for variation of the pulse duration, peak intensity, and central frequency or photoelectron energy. In the results obtained for fixed pulse parameters the transition and interference between the processes can be observed in the even (β2, β4) and odd (β1, β3) parameters, respectively, while the onset of the impact of three-photon ionization is observed via β5 at high peak intensities. Finally, we show that the transition can be observed via the even anisotropy parameters in pulses without carrier-to-envelope stabilization as well as in free-electron laser pulses with fluctuating pulse shape.

Purifying Electron Spectra from Noisy Pulses with Machine Learning Using Synthetic Hamilton Matrices.

Photoelectron spectra obtained with intense pulses generated by free-electron lasers through self-amplified spontaneous emission are intrinsically noisy and vary from shot to shot. We extract the purified spectrum, corresponding to a Fourier-limited pulse, with the help of a deep neural network. It is trained on a huge number of spectra, which was made possible by an extremely efficient propagation of the Schrödinger equation with synthetic Hamilton matrices and random realizations of fluctuating pulses. We show that the trained network is sufficiently generic such that it can purify atomic or molecular spectra, dominated by resonant two- or three-photon ionization, nonlinear processes which are particularly sensitive to pulse fluctuations. This is possible without training on those systems.

Modeling tomographic measurements of photoelectron vortices in counter-rotating circularly polarized laser pulses

Recent experiments [D. Pengel, S. Kerbstadt, L. Englert, T. Bayer, and M. Wollenhaupt, \href{https://journals.aps.org/pra/abstract/10.1103/PhysRevA.96.043426}{{\PRA} {\bf 96} 043426 (2017)}] have measured the photoelectron momentum distribution for three-photon ionization of potassium by counter-rotating circularly polarized 790-nm laser pulses. The distribution displays spiral vortices, arising from the interference of ionizing wavepackets with different magnetic quantum numbers. The high level of multidimensional detail observed in the distribution makes this an ideal case in which to demonstrate the accuracy of emerging theoretical techniques applicable to such problems. We use the \(R\)-matrix with time dependence approach to investigate this process. We calculate the full-dimensional photoelectron momentum distribution, and compare against a set of planar projections of this distribution previously measured in experiment.

High efficiency resonance ionization of thorium

Multi-step resonance ionization spectroscopy of thorium has been performed with Ti:Sapphire lasers and a hot-cavity laser ion source. Resonance ionization schemes involving three-color, three-photon ionization processes are evaluated and a new three-photon scheme is demonstrated with measured overall ionization efficiency of 38.6(5)%. This high efficiency makes it possible to determine the thorium impurities in materials used for ultra-low background neutrino detectors and could also benefit ultra-trace thorium analysis using resonance ionization mass spectrometry for various radiochemical tracer applications.

Investigation of high-lying even-parity levels of atomic samarium with multi-color photoionization technique: Energies and radiative lifetimes

We have investigated high-lying even-parity energy levels of atomic samarium in the energy region 32,156.3–32,886.4 cm−1 using two-color three-step photoionization technique. The experiments have been carried out in an atomic beam coupled to a linear time of flight mass spectrometer. The analysis of the photoionization spectra has resulted in the identification of twenty-five high-lying even-parity energy levels of atomic samarium. These include the confirmation of fifteen energy levels reported earlier while the remaining ten energy levels are new. The observed relative photoionization signal intensities of the corresponding transitions are also reported. The possible total angular momenta of the newly discovered energy levels have been assigned by the total angular momentum selection rules. Further, the radiative lifetimes of twenty high-lying even-parity energy levels of atomic samarium were measured for the first time by delayed three-color three-photon resonance ionization spectroscopy via a pump-probe method.