Two-photon Ionization Research Articles

Angular distribution parameters in two-photon double ionization of helium beyond the dipole approximation

We study nondipole effects in the two-photon double ionization of helium by solving the full-dimensional time-dependent Schr\"odinger equation (TDSE). The angular distributions of the photoelectrons in TDSE calculations are parametrized by several angular distribution parameters. The electron correlation effects are revealed and discussed by analyzing angular distribution parameters of the photoelectrons. Compared with the linearly polarized laser, the values of dipole angular parameters for circularly polarized laser pulses in the nonsequential double-ionization regime are closer to the pure dipole emission of the one-photon single ionization, which indicates a weaker electron correlation for circular pulses. For the nondipole angular parameters, in the sequential double-ionization regime, we find that the parameters show peak structures from the sequential ionization channel over the energy sharing between two electrons and these peak positions are slightly shifted by the electron correlation. In general, due to the nondipole effects, the angular distributions of photoelectrons are shifted towards the direction of laser propagation, due to the transfer of the photon linear momentum.

Non-dipole effects on angular distribution of photoelectrons in sequential two-photon double ionization of Ar atom and K<sup>+</sup> ion

Owing to the development of XUV and X ray of the free-electron lasers, the photoelectron angular distribution in the sequential two-photon double ionization has received increasing attention of theorists and experimentalists, because it provides the valuable information about the electronic structure of atom or molecule systems and allows the obtaining of additional information about mechanisms and pathways of the two-photon double ionization. In this paper, the expression of the sequential two-photon double ionization process of the photoelectron angular distributions, including the non-dipole effects, is obtained based on the multi-configuration Dirac-Fock method and the density matrix theory, and the corresponding calculation code is also developed. Based on the code, the sequential two-photon double ionization process of the 3p and 2p shells of Ar atom and K<sup>+</sup> ion are studied, in which, the dipole and the non-dipole parameters of photoelectron angular distribution are investigated systematically. It is found that the angular distributions of the first- and second-step electrons in sequential two-photon double ionization are similar and the two photoionization processes affect each other. Near the ionization threshold, the photoionization cross-sections and anisotropy parameters for the 3p shell and the 2p shell show a large difference. While away from the threshold, the cross-section and angular anisotropy parameters of the 3p and 2p shells show similar behaviors. At the position of Cooper minimum of the photoionization cross section, the contribution of the electric dipole is suppressed, and the non-dipole effect is obvious. The non-dipole effect leads to a forward-backward asymmetric distribution of photoelectrons relative to the direction of incident light. The results of this paper will be helpful in studying the nonlinear processes of photon and matter interaction in the XUV range.

Two-color resonance enhanced two-photon ionization and mass analyzed threshold ionization spectroscopy of <i>p</i>-chlorobenzonitrile

The vibrational features of <i>p</i>-chlorobenzonitrile in its first electronically excited state S<sub>1</sub> and cationic ground state D<sub>0</sub> have been investigated by two-color resonance enhanced two-photon ionization and mass analyzed threshold ionization spectroscopy. The excitation energy of S<sub>1</sub> ← S<sub>0</sub> and the ionization energy of <sup>35</sup>Cl and <sup>37</sup>Cl isotopomers of <i>p</i>-chlorobenzonitrile are determined to be 35818 ± 2, and 76846 ± 5 cm<sup>–1</sup>, respectively. These two isotopomers have similar vibrational features. Most of the active vibrations in the S<sub>1</sub> and D<sub>0</sub> states are related to the motions of the in-plane ring deformation. The stable structures and vibrational frequencies of <i>p</i>-chlorobenzonitrile are also calculated by the B3LYP/aug-cc-pVDZ method for the S<sub>0</sub> and D<sub>0</sub> states, and TD-B3LYP/aug-cc-pVDZ method for the S<sub>1</sub> state. The changes in the molecular geometry are discussed in the S<sub>1</sub> ← S<sub>0</sub> photoexcitation process and the D<sub>0</sub> ← S<sub>1</sub> photoionization process. The comparisons between the transition energy of <i>p</i>-chlorophenol, <i>p</i>-chloroaniline, <i>p</i>-chloroanisole, and <i>p</i>-chlorobenzonitrile with those of phenol, anisole, aniline, and benzonitrile provide an insight into the substitution effect of Cl atom.

Femtosecond dynamics of stepwise two-photon ionization in solutions as revealed by pump-repump-probe detection with a burst mode of photoexcitation.

Pump-repump-probe spectroscopy with a burst mode of photoexcitation was applied to the direct observation of the photoionization dynamics of perylene in the solution phase. Irradiation of a pump pulse train generated with birefringent crystals effectively accumulated an intermediate S1 state and a repump pulse triggered photoionization in the higher excited state, ensuring sufficiently large signal intensity to probe. Two-photon excitation to the energy level, which is 0.7 eV lower than the ionization potential in the gas phase, results in instantaneous formation of the radical cation of perylene in acetonitrile, unlike aromatic amines in previous reports. In addition, subsequent recombination dynamics between the radical cation and ejected electron was monitored in polar and nonpolar solvents. The ultrafast recombination in nonpolar solvents suggests that the distribution of the distance in the cation-ejected electron pair largely evolves even in acetonitrile in the femtosecond timescale, in which the solvation is not completed and the dielectric constant is still low. The recombination process in acetonitrile was well reproduced with simulations based on the Smoluchowski equation taking account of the transient change in the dielectric constant by solvation.

Two-color resonance enhanced multiphoton ionization spectroscopy of o-hydroxybenzonitrile and Franck-Condon simulation

The cyano group is a typical electron-withdrawing group, which has aroused the interest of relevant researchers. Many papers reported the dispersed fluorescence spectra of o-hydroxybenzonitrile, its dimers, and complexes with small molecules, aiming to study the intermolecule hydrogen bond and the vibration features of the electronic ground state. There are also reports on using fluorescence excitation spectra to study excited state vibrations, but no report on the systematical analyzing of the vibration features of excited state spectra. Compared with fluorescence spectroscopy, resonance enhanced multiphoton ionization (REMPI) spectroscopy detects ions to obtain excited state energy level data, which has mass-resolution capability, and eliminates the interference of impurities with different charge-to-mass ratios. The strong electron-withdrawing ability of cyano group results in higher ionization energy for molecules containing cyano groups. Many REMPI experiments on benzonitrile derivatives require two-color lasers. In this paper, two-color resonance enhanced two-photon ionization experiment is performed by using a home-made linear time-of-flight mass spectrometer, and the vibration-resolved REMPI spectrum of o-hydroxybenzonitrile is obtained for the first time. Combining the high-precision density functional theory calculations with the Franck-Condon spectral simulations, the spectral characteristics are analyzed in detail, and a large number of fundamental, overtone and combined vibrations are found. The spectral assignment is carried out as accurately as possible. Most of the fundamental vibrations located at ring are assigned to the in-plane distortion or swing of the ring, which is related to the expansion of the ring during the molecular excitation. Theoretical and experimental results show that the low-frequency signal of REMPI spectrum is strong, the background is low, the band is less, and the resolution is good. As the vibration frequency increases, the signal changes in the worse direction. This is because the low-frequency spectrum mainly comes from the low-frequency fundamental vibrations and a little contribution from overtones. As the vibration frequency increases, the contributions from overtone and combined vibrations gradually increase, resulting in dense bands and low resolution. Theoretical calculations show that the high-order vibration and combination of multi-mode vibrations usually have a lower Franck-Condon factor, so the signal gradually becomes weak as the frequency increases, and the signal-to-noise ratio becomes worse.

A geometric approach to decoding molecular structure and dynamics from photoionization of isotropic samples.

We propose a geometric approach to the description and analysis of photoelectron angular distributions resulting from isotropic samples in the case of few-photon ionization by electric fields of arbitrary polarization. This approach formulates the standard photoionization observables - the bl,m expansion coefficients of the photoelectron angular distribution, in terms of geometrical properties of the vector field D⃑(k⃑) ≡ 〈k⃑|d⃑|0〉 describing the electronic transition from a bound state |0〉 into a scattering state |k⃑〉 - the photoionization transition dipole. Besides revealing selection rules for the enantio-sensitivity of bl,m coefficients in multiphoton ionization, our approach yields very compact expressions for both chiral and achiral molecules revealing how the molecular rotational invariants couple to the rotational invariants of the setup defined by the electric field polarization and the arrangement of photoelectron detectors. We apply this approach to one-photon ionization and find that the forward-backward asymmetry parameter b1,0, emerging exclusively in chiral molecules and encoded in the field B⃑(k⃑) ≡ iD⃑*(k⃑) × D⃑(k⃑), is sensitive only to the components of D⃑(k⃑) perpendicular to k⃑, while the regular asymmetry parameter b2,0 emerging in chiral and achiral molecules is sensitive only to the component of D⃑(k⃑) parallel to k⃑. Next, we analyze resonantly enhanced two-photon ionization and show that b0,0 and b1,0 can be written in terms of an effectively stretched D⃑(k⃑), and how b1,0 and b3,0 can be used to probe B⃑(k⃑).

Role of nuclear-electronic coupling in attosecond photoionization of H2

The separation of electronic and nuclear dynamics due to differing timescales is a useful concept for understanding ground-state molecular systems. However, coupling between these degrees of freedom is critical to understanding the evolution of most excited-state systems. We measure two-photon ionization delays of ${\mathrm{H}}_{2}$ and compare to calculations of the same measurement in a frozen-nuclei approximation. We find discrepancies between the vibrationally resolved measurement and bond-length-dependent theory, suggesting that nuclear motion affects ${\mathrm{H}}_{2}$ photoionization on attosecond timescales. We ascribe our observation to nuclear-electronic channel coupling between continuum vibrational states. Our results demonstrate that nuclear-electronic coupling cannot be neglected in the sudden ionization of molecules containing light atoms.

Comprehensive Analysis of Analogues of Amine-Related Psychoactive Substances Using Femtosecond Laser Ionization Mass Spectrometry.

Amine-related psychoactive molecules contain N-Cα and Cα-Cβ bonds, which easily dissociate to form various fragment ions in electron ionization mass spectrometry (EIMS). Therefore, observing a molecular ion and then determining the molecular weight of the analyte is difficult. In this study, we examined phenethylamine, 3,4-methylenedioxyphenethylamine, tryptamine, N-methylephedrine, and nicotine as well as analogues of amine-related psychoactive substances using EIMS and femtosecond laser ionization mass spectrometry (fs-LIMS) combined with gas chromatography for comprehensive analysis. A molecular ion was clearly observed in fs-LIMS for all of these compounds, which was in contrast to EIMS providing fragment ions dominantly (no molecular ion was observed for N-methylephedrine). This favorable result was obtained by adjusting the laser wavelength to the optimal value for two-photon ionization to minimize the excess energy remaining in the molecular ion. It therefore appears that fs-LIMS is superior to EIMS in terms of observing a molecular ion and would be potentially useful for identifying a variety of amine-related psychoactive substances, some of which are illegal and are of interest in the field of forensic science.

Detection of atomic bromine (4p5 2PJ; J = 1/2, 3/2) by two-photon laser-induced vacuum ultraviolet emission

Two ultraviolet photons (250–282 nm) excited atomic bromine, Br(4p52PJ;J=1/2,3/2), to the terms built from the 4p45p electronic configuration. Through visible and infrared (VIS–IR) transitions and/or collisions with ambient gases, the terms transfer to the 2,4DJ and 2,4PJ states in the 4p44d and 4p45s electronic configurations. The vacuum ultraviolet (VUV) emission (125–163 nm) from the 4p44d and 4p45s states to the 4p52PJ state was detected. Twenty in 25 allowed two-photon transitions were observed; however, no VUV or VIS–IR emission from the other five transitions was detected. The findings differ from those by the previous reports on the two-photon resonance-enhanced ionization.

Laser-assisted two-color two-photon double ionization of helium atoms

Correlated momentum and kinetic energy distributions of two photoelectrons in laser-assisted two-color two-photon double ionization of helium are investigated by numerically solving a one-plus-one dimensional time-dependent Schrödinger equation (TDSE). We find that the weak assisting laser field can act as an energy transferring field, resulting in burst of double ionization triggered by the intense extreme ultraviolet (XUV) pulse. More importantly, the participation of the laser photon into the double ionization reshapes the correlation patterns in the momentum and kinetic energy distributions. The laser photon can be absorbed by any one of the two electrons, providing two channels that induces destructive interference in the correlated momentum and kinetic energy distributions, which is never found in previous work.

Predissociation measurements of the bond dissociation energies of EuO, TmO, and YbO.

The observation of a sharp predissociation threshold in the resonant two-photon ionization spectra of EuO, TmO, and YbO has been used to measure the bond dissociation energies of these species. The resulting values, D0(EuO) = 4.922(3) eV, D0(TmO) = 5.242(6) eV, and D0(YbO) = 4.083(3) eV, are in good agreement with previous values but are much more precise. In addition, the ionization energy of TmO was measured by the observation of a threshold for one-color two-photon ionization of this species, resulting in IE(TmO) = 6.56(2) eV. The observation of a sharp predissociation threshold for EuO was initially surprising because the half-filled 4f7 subshell of Eu in its ground state generates fewer potential energy curves than in the other molecules we have studied by this method. The observation of a sharp predissociation threshold in YbO was even more surprising, given that the ground state of Yb is nondegenerate (4f146s2, 1Sg) and the lowest excited state of Yb is over 2eV higher in energy. It is suggested that these molecules possess a high density of electronic states at the energy of the ground separated atom limit because ion-pair states drop below the ground limit, providing a sufficient electronic state density to allow predissociation to set in at the thermochemical threshold.

Optical Identification of the Resonance-Stabilized para-Ethynylbenzyl Radical

We report the spectroscopic observation of the jet-cooled para-ethynylbenzyl (PEB) radical, a resonance-stabilized isomer of C9H7. The radical was produced in a discharge of p-ethynyltoluene diluted in argon and probed by resonant two-color two-photon ionization (R2C2PI) spectroscopy. The origin of the D0(2B1)-D1(2B1) transition of PEB appears at 19,506 cm-1. A resonant two-color ion-yield scan reveals an adiabatic ionization energy (AIE) of 7.177(1) eV, which is almost symmetrically bracketed by CBS-QB3 and B3LYP/6-311G++(d,p) calculations. The electronic spectrum exhibits pervasive Fermi resonances, in that most a1 fundamentals are accompanied by similarly intense overtones or combination bands of non-totally symmetric modes that would carry little intensity in the harmonic approximation. Under the same experimental conditions, the m/z = 115 R2C2PI spectrum of the p-ethynyltoluene discharge also exhibits contributions from the m-ethynylbenzyl and 1-phenylpropargyl radicals. The former, like PEB, is observed herein for the first time, and its identity is confirmed by measurement and calculation of its AIE and D0-D1 origin transition energy; the latter is identified by comparison with its known electronic spectrum (J. Am. Chem. Soc., 2008, 130, 3137-3142). Both species are found to co-exist with PEB at levels vastly greater than might be explained by any precursor sample impurity, implying that interconversion of ethynylbenzyl motifs is feasible in energetic environments such as plasmas and flames, wherein resonance-stabilized radicals are persistent.

Esterification of perfluorinated carboxylic acids with bromomethyl aromatic compounds for gas chromatography combined with laser ionization mass spectrometry

Perfluorinated carboxylic acids (PFCAs) were derivatized with two types of aromatic compounds that contained a bromomethyl group, i.e., 2-(bromomethyl)naphthalene (BMN) and benzyl bromide (BB). The conditions for derivatization were optimized in terms of reaction temperature and time and the concentration of derivatizing reagent. Using these optimal conditions, the PFCAs-MN and PFCAs-B derivatives were measured by gas chromatography (GC) combined with mass spectrometry using an ultraviolet femtosecond laser (267 nm) as the ionization source. The efficiency of derivatization for PFCAs-B was higher than that for PFCAs-MN because of the smaller size of the chromophore (benzene). The ionization efficiency of PFCAs-MN, however, was better than PFCAs-B, since a larger sized chromophore (naphthalene) and then a larger molar absorptivity was preferable for resonance-enhanced two-photon ionization. Due to superior GC separation, BB was successfully used as the derivatizing agent for the trace analysis of PFCAs, with detection limits of 6.0, 8.4, and 9.5 ng/mL for perfluoroheptanoic, perfluorooctanoic, and perfluorononanoic acids, respectively. The other bromomethyl aromatic compounds were evaluated for use as a derivatization reagent in future studies.

A compact and cost-effective laser desorption source for molecular beam generation: comparison with simulations

The development of laser-desorption jet-cooling has enabled the study of low vapor pressure molecules in the gas phase. Here, we design and assemble a unique compact laser-desorption source comprising simple parts for sample movement and desorption and attach it to a home-built time-of-flight mass spectrometer for spectroscopic studies of jet-cooled biomolecules. Modeling and visualization of the molecular beam (MB) by the direct simulation Monte Carlo method provides spatial evolution and global features of the flow and new insights into source operation. The system is validated by determining operational parameters from the simulation and comparing them with the resulting resonance-enhanced two-photon ionization (R2PI) signal of tryptamine. The signal measurements in the origin band transitions region provide an R2PI spectrum resembling that previously acquired from heated samples, indicating seven conformers in the MB. Due to the potential of this source, we expect that it will reveal its feasibility through coupling to other systems and various spectroscopies.

Two-photon ionization in solar opacity experiments

The discrepancies between theoretical and experimental opacities reported by experiments performed at the Sandia National Laboratory Z-pinch relevant to the solar interior remain unexplained. The suggestion that two-photon ionization could help resolve the discrepancies was recently examined and found not to account for the higher than predicted measured opacities. That test, however, was limited in scope and is now extended to include excited configurations and different charge states of several elements. Comparisons of one- and two-photon ionization cross-sections show that the latter fail to resolve the aforementioned discrepancies.

Odd-parity autoionizing levels of uranium observed by two-color two-step photoionization optogalvanic spectroscopy

Two-color two-step photoionization optogalvanic spectroscopy was performed using high-repetition-rate titanium sapphire lasers and a uranium hollow cathode lamp to find the two-step resonance ionization schemes of uranium. Many ionization transitions were observed by exciting uranium atoms in a ground state into five, even parity, excited levels with the first-step laser and by scanning the second-step laser wavelengths. By blocking the first-step laser, single-color, two-photon ionization transitions were also identified. From these results, we have found more than 50 odd-parity autoionizing levels of uranium in the energy, ranging from the ionization potential (49958.4 cm−1) to 51 150 cm−1. The determined energy levels are within ∼±1 cm−1 of previously reported values.

Electronic Spectroscopy of cis- and trans-meta-Vinylbenzyl Radicals.

The D0(2A″)-D1(2A″) electronic transition of resonance-stabilized radical C9H9 isomers cis- and trans-meta-vinylbenzyl (MVB) has been investigated using resonant two-color two-photon ionization (R2C2PI) and laser-induced fluorescence. The radicals were produced in a discharge of m-vinyltoluene diluted in Ar and probed under jet-cooled conditions. The origin bands of the cis and trans conformers are at 19 037 and 18 939 cm-1, respectively. Adiabatic ionization energies near 7.17 eV were determined for both conformers from two-color ion-yield scans. Dispersed fluorescence (DF) was used to conclusively identify the cis-conformer: ground-state cis-MVB eigenvalues calculated for a Fourier series fit of a computed vinyl torsion potential are in excellent agreement with torsional transitions in the 19 037 cm-1 DF spectrum. R2C2PI features arising from cis- or trans-MVB were distinguished by optical-optical hole-burning spectroscopy and vibronic assignments were made with guidance from density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. There is a notable absence of mirror symmetry between excitation and emission spectra for several totally symmetric modes, whereby modes that are conspicuous in emission are nearly absent in excitation, and vice versa. This effect is largely ascribed to interference between Franck-Condon and Herzberg-Teller contributions to the electronic transition moment, and its pervasiveness a consequence of the low symmetry (Cs) of the molecule, which permits intensity borrowing from several relatively bright electronic states of A″ symmetry.

Elliptical dichroism in biharmonic ionization of atoms

In multiphoton ionization of atoms, elliptical dichroism may arise in the photoelectron angular distributions due to the interference of the possible ionization pathways. We here consider the interaction of atoms with an elliptically polarized biharmonic ($\ensuremath{\omega} + 2\ensuremath{\omega}$) field which simultaneously allows one- and two-photon ionization of the atoms. The interference between these two ionization pathways introduces contributions to the elliptical dichroism in addition to the dichroism that arises from the two-photon ionization alone. We show that these additional dichroism contributions can lead to a stronger dichroism in comparison to the one arising from two-photon ionization only. We present a relativistic analysis of the corresponding photoelectron angular distributions and discuss individual contributions to the dichroic phenomena. Detailed computations have been performed for biharmonic ionization of neutral helium atoms.

Two-Photon Ionization Induced Stable White Organic Long Persistent Luminescence.

Organic long persistent luminescence (OLPL) materials with afterglow duration in the scale of minutes or even hours are still rare. Most OLPL systems are based on exciplexes, which require complicated multi-component system in order to realize white afterglow but with slightly compromised duration and color stability. In this work, OLPLs lasting from 20 to 40 minutes are realized in a simple binary system based on two-photon ionization mechanism, which can simultaneously harvest excitons from both singlet and triplet excited states, making it potentially one of the most promising candidates to achieve stable white OLPL. Through modulation and optimization of dopant molecules in dibenzo[b,d]thiophen-2-yldiphenyl phosphine oxide host, the emission profiles of afterglow can be readily tuned from cyan (0.19, 0.22), cold white (0.31, 0.35), standard white (0.33, 0.33) to warm white (0.31, 0.46), with excellent color consistency.

Characterization of vacuum and deep ultraviolet pulses via two-photon autocorrelation signals.

Characterization of ultrashort vacuum and deep ultraviolet pulses is important in view of applications of those pulses for spectroscopic and dynamical imaging of atoms, molecules, and materials. We present an extension of the autocorrelation technique, applied for measurement of the pulse duration via a single Gaussian function. Analytic solutions for two-photon ionization of atoms by Gaussian pulses are used along with an expansion of the pulse to be characterized using multiple Gaussians at multi-color central frequencies. This approach allows one to use two-photon autocorrelation signals to characterize isolated ultrashort pulses and pulse trains, i.e., the time-dependent amplitude and phase variation of the electric field. The potential of the method is demonstrated using vacuum and deep ultraviolet pulses and pulse trains obtained from numerical simulations of macroscopic high harmonic spectra.