Resonance-enhanced Multiphoton Ionization Research Articles

Nonresonant Multiphoton Ionization of Stark Decelerated Molecules by Femtosecond Laser Pulses

Nonresonant multiphoton ionization by femtosecond laser pulses can be applied to any molecule virtually, thereby greatly enhancing the scope of Stark decelerated molecules. For comparison, we detect decelerated and trapped ammonia molecules using two different schemes: (i) nonresonant multiphoton ionization using intense femtosecond (fs) pulses in the near infrared, and (ii) resonance-enhanced multiphoton ionization using nanosecond (ns) pulses from a tunable UV laser. The observed number of ions per shot for both schemes is similar. The fs laser detection scheme suffers from an increased background, which can be effectively eliminated by subsequent mass and velocity selection. To determine the detection volume of the ns laser detection scheme, we present measurements in which the decelerated ammonia molecules are bunched to a packet with a longitudinal spread well below ∼100 μm. It is concluded that the detection volume for the ns laser detection scheme is 1.5–2 times larger than that of the fs laser detection scheme.

Angular distribution of near-threshold photoelectrons from resonance-enhanced multiphoton ionization of argon

We experimentally study the angular distribution of near-threshold photoelectrons of argon in the multiphoton-ionization regime. Those near-threshold photoelectrons are released from atoms by a weak 800-nm laser field and a strong 400-nm laser field with parallel polarizations. In the laser polarization direction, the yield of the near-threshold photoelectron oscillates with twice the 800-nm laser frequency, while higher-frequency components for the yield oscillations are found for the electrons emitted perpendicular to the laser polarization direction. By decomposing the photoelectron angular distribution into different partial waves, we found that those near-threshold photoelectrons are generated by the interference of different photon channels via resonant states. Moreover, we observed a large time delay between the near-threshold photoelectrons emitted along the laser polarization direction via the $5p$ and $4f$ resonant states.

NO (A) Rotational State Distributions from Photodissociation of the N2-NO Complex.

We have recorded the resonance-enhanced multiphoton ionization spectrum for NO (A) products from photodissociation of the N2-NO complex. We made measurements at excitation energies ranging from 28 to 758 cm-1 above the threshold to produce NO (A) + N2 (X) products, and the resulting spectra reveal the NO (A) rotational states formed during dissociation, allowing us to determine the rotational state distribution. At the lowest available energies, 28 and 50 cm-1 above threshold, we observed contributions from NO (A) rotational states that exceed the available energy and must originate from excitation due to hotbands of the complex. At all higher energies, we did not observe any energetically disallowed NO (A) rotational states, and for all available energies above 259 cm-1 the observed rotational transitions do not extend to the maximum allowed by energy conservation. Furthermore, the observed distributions were typically biased toward low rotational states, in contrast with expectations from vibrational predissociation. From the rotational state distributions, we determined the average fraction of energy partitioned into NO (A) rotation, fNOrot,ave, to be 0.088 at the highest available energy, and this fraction increased as the available energy decreased. By combining the average NO (A) rotational energy along with the average center-of-mass translational energy from our previous work, we determined the average rotational energy for the undetected N2 (X) photoproduct. The results showed that the N2 fragment has a higher average rotational energy relative to the NO fragment. Finally, we found that the NO (A) rotational state distribution was colder than expected for a statistical dissociation.

Pushing multiphoton resonant ionization of the argon atom to the low-intensity regime

Resonance-enhanced multiphoton ionization process of the argon atom by an 800-nm 30-fs linearly polarized laser field is investigated at intensities range from 1.1 to $4.55\ifmmode\times\else\texttimes\fi{}{10}^{13}\phantom{\rule{0.28em}{0ex}}\mathrm{W}/{\mathrm{cm}}^{2}$. At $4.55\ifmmode\times\else\texttimes\fi{}{10}^{13}\phantom{\rule{0.28em}{0ex}}\mathrm{W}/{\mathrm{cm}}^{2}$ intensity the experimental photoelectron energy spectrum is in a good agreement with the time-dependent Schr\"odinger equation (TDSE) calculation where the double structure originating from dressed $4p\ensuremath{-}4d$ coupled transition is clearly identified. At lower intensity of $1.1\ifmmode\times\else\texttimes\fi{}{10}^{13}\phantom{\rule{0.28em}{0ex}}\mathrm{W}/{\mathrm{cm}}^{2}$, the resonant ionization process via the $4f$ state is observed, however, the expected peak (jet) at ${90}^{\ensuremath{\circ}}$ in the photoelectron angular distribution from the zeroth order above threshold ionization, has vanished completely. Such behavior is attributed to the destructive interference phenomenon in the coherent contributions of different partial waves of the photoelectron, namely, $\ensuremath{\epsilon}d$ and $\ensuremath{\epsilon}g$ states, and has been confirmed in our TDSE calculations.

Resonance-Enhanced Multiphoton Ionization of Molecular Oxygen at the 222 nm KrCl Laser Wavelength

We study the photo-ionization mechanism of molecular oxygen at the 222 nm KrCl laser wavelength within a laser pulse intensity range of 108 – 1010 W/cm2, using 14 ns laser pulses. We experimentally observe (2+1) resonance-enhanced multiphoton ionization (REMPI) of molecular oxygen with the effective ionization cross-section {sigma}_{{mathrm{O}}_2}^{(2)} = (3.2 ± 1.3) · 10−18 cm4 · s−1 · W−2 at an intensity range of 109 – 1010 W/cm2 and linear ionization due to gas impurities at an intensity range of 108 – 109 W/cm2.

Spectroscopy of N-methylpyrrole-RG (RG = Ar, Kr) complexes: First excited neutral and ground cationic states

N-methylpyrrole-RG (RG = Ar, Kr) complexes are investigated using resonance-enhanced multiphoton ionization (REMPI) and zero-electron-kinetic-energy (ZEKE) spectroscopy. The RG atom makes the electronic transition to the S1 state allowed, and the REMPI spectrum is blue-shifted compared to the N-methylpyrrole origin, with no bands associated with vibrational excitation of the N-methylpyrrole moiety. The nature of the electronic structure of the S1 state is discussed. Binding energies are obtained for all three electronic states. Adiabatic ionization energies are obtained from the ZEKE spectra, yielding values of 64077 ± 5 cm−1 and 64029 ± 5 cm−1 for RG = Ar and Kr, respectively.

Determination of atomic multiphoton-ionization phases by trichromatic multichannel wave-packet interferometry

We present the unambiguous determination of quantum phases in the multiphoton ionization (MPI) of potassium atoms by using a multichannel photoelectron interferometry scheme based on trichromatic pulse shaping. The colors of the laser field are chosen to produce three energetically separated photoelectron interferograms in the continuum. While the red pulse is two-photon resonant with the $3d$ state resulting in a $(2+1)$ resonance-enhanced MPI (REMPI), a $(1+2)$ REMPI occurs via the nonresonant intermediate $4p$ state with an initial green or blue pulse. We show that ionization via a nonresonant intermediate state lifts the degeneracy of photoelectron interferograms from pathways consisting of permutations of the colors. The analysis of the interferograms reveals a phase shift of $\ifmmode\pm\else\textpm\fi{}\ensuremath{\pi}/2$ depending on the sign of the detunings in the $(1+2)$ REMPI pathways. In addition, we demonstrate that the photoionization time delay in the resonant $(2+1)$ REMPI pathway gives rise to a linear spectral phase in the photoelectron spectra. Insights into the underlying MPI processes are gained through an analytic perturbative description and numerical simulations of a trichromatic driven three-level system coupled to the continuum.

One-dimensional air temperature measurements by air resonance enhanced multiphoton Ionization thermometry (ART).

In this work, a detailed calibration study is performed to establish non-intrusive one-dimensional (1D) rovibrational temperature measurements in unseeded air, based on air resonance enhanced multiphoton ionization thermometry (ART). ART is generated by REMPI (resonance enhanced multi-photon ionization) of molecular oxygen and subsequent avalanche ionization of molecular nitrogen in a single laser pulse. ART signal, the fluorescence from the first negative band of molecular nitrogen, is directly proportional to the 2-photon transition of molecular oxygen C3Π (v = 2) ← X3Σ (v'=0), which is used to determine temperature. Experimentally, hyperfine structures of the O2 rotational branches with high temperature sensitivity are selectively excited through a frequency-doubled dye laser. Electron-avalanche ionization of N2 results in the fluorescence emissions from the first negative bands of N2 + near 390, 425, and 430nm, which are captured as a 1D line by a gated intensified camera. Post processing of the N2 + fluorescence yields a 1D thermometry line that is representative of the air temperature. It is demonstrated that the technique provides ART fluorescence of ∼5cm in length in the unseeded air, presenting an attractive thermometry solution for high-speed wind tunnels and other ground test facilities.

Air resonance enhanced multiphoton ionization tagging velocimetry.

Air resonance enhanced multiphoton ionization (REMPI) tagging velocimetry (ART) was demonstrated in quiescent and supersonic flows. The ART velocimetry method utilizes a wavelength tunable laser beam to resonantly ionize molecular oxygen in air and generate additional avalanche-type ionization of molecular nitrogen. The fluorescence emissions from the first negative and first positive bands of molecular nitrogen are, thus, produced and used for flow tagging. Detailed characterization of ART was conducted, including the effects of oxygen resonance to fluoresce nitrogen, nitrogen fluorescence spectrum, laser energy deposition into quiescent flow showing minimal perturbations in flow, fluorescence lifetime study at various pressures, and line tagging without breakdown. Pointwise velocity measurements within a supersonic flow from a nominal Mach 1.5 nozzle have been conducted and characterized.

Spin-Conservation Propensity Rule for Three-Body Recombination of Ultracold Rb Atoms.

We explore the physical origin and the general validity of a propensity rule for the conservation of the hyperfine spin state in three-body recombination. This rule was recently discovered for the special case of ^{87}Rb with its nearly equal singlet and triplet scattering lengths. Here, we test the propensity rule for ^{85}Rb for which the scattering properties are very different from ^{87}Rb. The Rb_{2} molecular product distribution is mapped out in a state-to-state fashion using resonance-enhanced multiphoton ionization detection schemes which fully cover all possible molecular spin states. Interestingly, for the experimentally investigated range of binding energies from zero to ∼13 GHz×h we observe that the spin-conservation propensity rule also holds for ^{85}Rb. From these observations and a theoretical analysis we derive an understanding for the conservation of the hyperfine spin state. We identify several criteria to judge whether the propensity rule will also hold for other elements and collision channels.

High-repetition-rate krypton tagging velocimetry in Mach-6 hypersonic flows.

A 100 kHz krypton (Kr) tagging velocimetry (KTV) technique was demonstrated in a Mach-6 Ludwieg tube using a burst-mode laser-pumped optical parametric oscillator system. The single-beam KTV scheme at 212 nm produced an insufficient signal in this large hypersonic wind tunnel because of its low Kr seeding (≤5%), low static pressure (∼2.5torr), and long working distance (∼1m). To overcome these issues, a new scheme using two excitation beams was developed to enhance KTV performance. A 355 nm laser beam was combined with the 212 nm beam to promote efficient two-photon Kr excitation at 212 nm, and increase the probability of 2 + 1 resonant-enhanced multiphoton ionization by adding a 355 nm beam. A signal enhancement of approximately six times was obtained. Using this two-excitation beam approach, strong long-lasting KTV was successfully demonstrated at a 100 kHz repetition rate in a Mach-6 flow.

An efficient method for producing 9Be+ ions using a 2 + 1 resonance-enhanced multiphoton ionization process

We report a method of creating pure 9Be+ ions by a 2 + 1 resonance-enhanced multiphoton ionization for the ionization potential of 75 192.64(6) cm−1 (133 nm). The efficient generation of 9Be+ ions has been realized in a segmented linear ion trap. The average loading rates with a 10 ns, 1 mJ laser at 310 nm and 306 nm are 3.8 and 1.3 ions per pulse, respectively. This method has the advantage of reducing the electron contamination to the ion trap electrodes greatly. It also reduces the requirement of single-photon energy while satisfying the need for ionization probability and can be applied to other atoms with high ionization thresholds.

Generation of Highly Vibrationally Excited CO in Sequential Photodissociation of Iron Carbonyl Complexes

Ultraviolet photochemistry of iron pentacarbonyl, Fe(CO)5, was investigated with resonantly enhanced multiphoton ionization (REMPI) spectroscopy and ion imaging. The REMPI spectrum of CO photofragments, generated by ultraviolet irradiation of Fe(CO)5, showed the generation in the highly vibrationally excited states with v = 11-15. Analysis of the band intensities observed in the 213-235 nm region indicated that the high-v CO generation was maximized at around 220 nm. Generation yields of the coordinatively unsaturated intermediates, Fe(CO)n=1-4, were measured as a function of the photolysis wavelength using a nonresonant detection scheme. The yield spectrum of FeCO was correlated with that of the high-v CO fragments, suggesting high-v CO generation in the photodissociation of FeCO. The density functional theory calculations of the excited states of FeCO showed an intense photoabsorption to the metal-centered state near 220 nm. The theoretical results were consistent with the interpretation of FeCO + hν → Fe + high-v CO, which was experimentally indicated. The momentum distribution obtained from the velocity distributions of Fe, Fe(CO)4, and CO fragments further supported that Fe is the counter-product of the high-v CO fragment. The present results provided selective observation of the photochemistry of the unsaturated iron carbonyl complexes, which has not been well elucidated in laser-based experiments because of the uncontrollable sequential photodissociation producing mixed Fe(CO)n intermediates.

Using Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry to Evaluate the Movement of a Constituent in a Multiple Emulsion.

Herein, we propose a method for evaluating the movement of a constituent in a multiple emulsion while maintaining its original dispersed condition. In this study, an oil-in-water-in-oil (O1/W/O2) emulsion was prepared using a two-step emulsification method with styrene as an analyte species in the inner phase (O1). The emulsion was measured using resonance-enhanced multiphoton ionization time-of-flight mass spectrometry without pretreatment such as centrifugation. From a series of obtained mass spectra, a time profile for the peak areas arising from styrene was constructed. When the emulsion was measured immediately following preparation, a time profile composed of a base, positive, and negative signals confirmed the presence of styrene in the O2, O1, and W phases, respectively. Moreover, while a small amount of styrene was present in the inner O1 phase, almost all of the styrene was found in the outer O2 phase. Furthermore, the results of the obtained time profile were converted into a box plot, and a method for the selection of the base, positive, and negative signals was tentatively determined. Then, the movement of styrene among the phases could be evaluated using the time courses of these signals; the time constant of the movement of styrene from an O1/W droplet to the O2 phase was calculated to be 0.8 h.

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.

Studies of the First Electronically Excited State of 3-Fluoropyridine and Its Ionic Structure by Means of REMPI, Two-Photon MATI, One-Photon VUV-MATI Spectroscopy and Franck–Condon Analysis

3-Fluoropyridine has been investigated by means of resonance-enhanced multi photon ionization, mass-analyzed threshold ionization (MATI) and one-photon VUV-MATI spectroscopy to study the effect of m-fluorine substitution on the involved states.

Measurements of Ortho-to-para Nuclear Spin Conversion of H2 on Low-temperature Carbonaceous Grain Analogs: Diamond-like Carbon and Graphite

Abstract Hydrogen molecules have two nuclear spin isomers: ortho-H2 and para-H2. The ortho-to-para ratio (OPR) is known to affect chemical evolution as well as gas dynamics in space. Therefore, understanding the mechanism of OPR variation in astrophysical environments is important. In this work, the nuclear spin conversion (NSC) processes of H2 molecules on diamond-like carbon and graphite surfaces are investigated experimentally by employing temperature-programmed desorption and resonance-enhanced multiphoton ionization methods. For the diamond-like carbon surface, the NSC time constants were determined at temperatures of 10–18 K and from 3900 ± 800 s at 10 K to 750 ± 40 s at 18 K. Similar NSC time constants and temperature dependence were observed for a graphite surface, indicating that bonding motifs (sp3 or sp2 hybridization) have little effect on the NSC rates.

Resonance-Enhanced Multiphoton Ionization in the X-Ray Regime.

Here, we report on the nonlinear ionization of argon atoms in the short wavelength regime using ultraintense x rays from the European XFEL. After sequential multiphoton ionization, high charge states are obtained. For photon energies that are insufficient to directly ionize a 1s electron, a different mechanism is required to obtain ionization to Ar^{17+}. We propose this occurs through a two-color process where the second harmonic of the FEL pulse resonantly excites the system via a 1s→2p transition followed by ionization by the fundamental FEL pulse, which is a type of x-ray resonance-enhanced multiphoton ionization (REMPI). This resonant phenomenon occurs not only for Ar^{16+}, but also through lower charge states, where multiple ionization competes with decay lifetimes, making x-ray REMPI distinctive from conventional REMPI. With the aid of state-of-the-art theoretical calculations, we explain the effects of x-ray REMPI on the relevant ion yields and spectral profile.

Photodissociation Dynamics of Vinoxy Radical via the B̃2A″ State: The H + CH2CO Product Channel.

Photodissociation dynamics of the jet-cooled vinoxy radical (CH2CHO) via the B̃2A″ state was studied in the near-ultraviolet (near-UV) region of 308-328 nm using high-n Rydberg H atom time-of-flight (HRTOF) and resonance-enhanced multiphoton ionization (REMPI) techniques. The vinoxy radical beam was produced by 193 nm photolysis of ethyl vinyl ether followed by supersonic expansion. The H + CH2CO product channel was observed directly in the H atom TOF spectra. The H atom photofragment yield (PFY) spectra were obtained by integrating the H atom TOF spectra and measuring the H atom REMPI signals, and showed several vibronic bands of the B̃2A″ state. The translational energy distributions of the H + CH2CO products, P(ET)'s, were obtained at several vibronic transitions. The P(ET) distributions were broad, peaking at a low energy of ∼3500 cm-1. The product translational energy release was moderate; the average translational energy release in the maximum available energy, ⟨fT⟩, was in the range of 0.24-0.27. The product angular distributions in this wavelength region were slightly anisotropic, with the β parameter in the range of 0.10-0.24. The near-UV photodissociation mechanism of the H + CH2CO product channel of the vinoxy radical is consistent with unimolecular dissociation on the electronic ground state (X̃2A″) following internal conversion from the B̃2A″ state to the Ã2A' state and then to the X̃2A″ state (although unimolecular dissociation from the first excited Ã2A' may also contribute).

Quantitative Evaluation of the Creaming of Emulsions via Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry.

The creaming behavior of an oil-in-water (O/W) emulsion was quantitatively evaluated via resonance-enhanced multiphoton ionization time-of-flight mass spectrometry. Styrene O/W emulsions were prepared with initial styrene concentrations of 1 and 4 g/L, and the height at the center of the sample was monitored. A peak area of the molecular ion of styrene was set as the signal intensity, for which a time profile was constructed from a series of mass spectra. As a result, the averaged time profiles showed that the signal intensities increased once and then decreased with the onset of creaming. In addition, in order to fit an experimentally obtained time profile, a modified fit function was proposed. Based on the fit results, the ratios of the increases and decreases in signal intensities were different between the two emulsions-higher in the case of an O/W emulsion with a higher initial oil concentration. On the other hand, the duration of the enhancement of the signal intensity with the onset of creaming was independent of the initial oil concentration. The present method offers the possibility to quantitatively evaluate the creaming behavior of an emulsion without pretreatment, and, therefore, would be useful for confirming the stability and quality assurance of emulsions.