Resonance-enhanced Multiphoton Ionization Research Articles

Vacuum Laser Photoionization inside the C-trap of an Orbitrap Mass Spectrometer: Resonance-Enhanced Multiphoton Ionization High-Resolution Mass Spectrometry.

State-of-the-art mass spectrometry with ultraviolet (UV) photoionization is mostly limited to time-of-flight (ToF) mass spectrometers with 1000-10 000 m/Δm mass resolution. However, higher resolution and higher spectral dynamic range mass spectrometry may be indispensable in complex mixture characterization. Here, we present the concept, implementation, and initial evaluation of a compact ultrahigh-resolution mass spectrometer with gas-phase laser ionization. The concept is based on direct laser photoionization in the ion accumulation and ejection trap (C-trap) of an Orbitrap mass spectrometer. Resonance-enhanced multiphoton ionization (REMPI) using 266 nm UV pulses from a frequency-quadrupled Nd:YAG laser was applied for selective and efficient ionization of monocyclic and polycyclic aromatic hydrocarbons. The system is equipped with a gas inlet for volatile compounds and a heated gas chromatography coupling. The former can be employed for rapid system m/z-calibration and performance evaluation, whereas the latter enables analysis of semivolatile and higher-molecular-weight compounds. The capability to evaluate complex mixtures is demonstrated for selected petrochemical materials. In these experiments, several hundred to over a thousand compounds could be attributed with a root-mean-square mass error generally below 1 ppm and a mass resolution of over 140 000 at 200 m/z. Isobaric interferences could be resolved, and narrow mass splits, such as 3.4 mDa (SH4/C3), are determined. Single laser shots provided limits of detection in the 20-ppb range for p-xylene and 1,2,4-trimethylbenzene, similar to compact vacuum REMPI-ToF systems.

Electronic, vibrational, and torsional couplings in N-methylpyrrole: Ground, first excited, and cation states.

The electronic spectrum associated with the S1 ← S0 (Ã1A2←X̃1A1) one-photon transition of jet-cooled N-methylpyrrole is investigated using laser-induced fluorescence (LIF) and (1 + 1) resonance-enhanced multiphoton ionization (REMPI) spectroscopy; in addition, the (2 + 2) REMPI spectrum is considered. Assignment of the observed bands is achieved using a combination of dispersed fluorescence (DF), two-dimensional LIF (2D-LIF), zero-electron-kinetic energy (ZEKE) spectroscopy, and quantum chemical calculations. The spectroscopic studies project the levels of the S1 state onto those of either the S0 state, in DF and 2D-LIF spectroscopy, or the ground state cation (D0 +) state, in ZEKE spectroscopy. The assignments of the spectra provide information on the vibrational, vibration-torsion (vibtor), and torsional levels in those states and those of the S1 levels. The spectra are indicative of vibronic (including torsional) interactions between the S1 state and other excited electronic states, deduced both in terms of the vibrational activity observed and shifts from expected vibrational wavenumbers in the S1 state, attributed to the resulting altered shape of the S1 surface. Many of the ZEKE spectra are consistent with the largely Rydberg nature of the S1 state near the Franck-Condon region; however, there is also some activity that is less straightforward to explain. Comments are made regarding the photodynamics of the S1 state.

Quantum control of entangled photon-pair generation in electron-atom collisions driven by laser-synthesized free-electron wave packets

We propose an extension of coherent control using laser-synthesized free-electron matter waves. In contrast to coherent control schemes exploiting optical coherences to steer the dynamics of matter waves, we analyze the opposite and investigate the control of quantum light emission driven by laser-sculpted coherent free-electron matter waves. We apply this concept to the control of entangled photon-pair emission in electron-atom collisions, in which the incident electron wave packet, colliding with a target atom $B$, is engineered by interferometric resonantly-enhanced multiphoton ionization of a parent atom $A$. Each ionization pathway leads to electron wave packets that coherently interfere during temporal evolution in the continuum. Their mutual coherence can be controlled by adjusting the relative phases or time delays of the frequency components of the ionizing field contributing to the interfering pathways. We report coherent control of entangled photon-pair generation in radiative photo-cascade emission upon decay of the target atom after inelastic excitation triggered by the collision with the synthesized electron wave packet.

Calculation of multiphoton ionization amplitudes and cross sections of few-electron atoms

We present a theoretical method for calculating multiphoton ionization amplitudes and cross sections of few-electron atoms. The present approach is based on an extraction of partial wave amplitudes from a scattering wave function, which is calculated by solving a system of driven Schroedinger equations. The extraction relies on a description of partial waves in terms of a small number of Coulomb waves with fixed wave numbers. The method can be used for photon energies below and above the ionization threshold and to treat resonance-enhanced multiphoton ionization. We use it to calculate two-, three-, and four-photon ionization cross sections of hydrogen and helium atoms for a wide range of photon energies and to determine the asymmetry parameters of photoelectron angular distributions for two-, three-, and four-photon ionization of the helium atom.

Correction to “Using Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry to Quantitatively Analyze the Creaming of an Emulsion”

[This corrects the article DOI: 10.1021/acsomega.9b02930.].

High-resolution UV spectroscopy of 1-indanol.

We report on rotationally resolved laser induced fluorescence (LIF) and vibrationally resolved resonance-enhanced multiphoton ionization (REMPI) spectroscopy of the chiral molecule 1-indanol. Spectra of the S1← S0 electronic transition are recorded in a jet-cooled, pulsed molecular beam. Using two time-delayed pulsed lasers, the lifetimes of the S1 state of the two most stable conformers, referred to as eq1 and ax2, have been determined. The S1← S0 origin bands of these conformers as well as the transition to a vibrationally excited level in the S1 state of eq1 are recorded with full rotational resolution (25 MHz observed linewidth) by measuring the LIF intensity following excitation with a tuneable, narrowband cw laser. On selected rotationally resolved electronic transitions, Lamb-dips are measured to confirm the Lorentzian lifetime-contribution to the observed lineshapes. The rotationally resolved S1← S0 origin band of a neon-complex of eq1 is measured via LIF as well. The fit of the rotationally resolved LIF spectra of the origin bands to those of an asymmetric rotor yields a standard deviation of about 6 MHz. The resulting spectroscopic parameters are tabulated and compared to the outcome of ab initio calculations. For both conformers as well as for the Ne-eq1 complex, the geometric structures in the S0 and S1 states are discussed. For all systems, the transition dipole moment is mainly along the a-axis, the contributions along the b- and c-axes being about one order of magnitude smaller.

Nuclear spin conservation enables state-to-state control of ultracold molecular reactions.

Quantum-state control of reactive systems has enabled microscopic probes of underlying interaction potentials and the alteration of reaction rates using quantum statistics. However, extending such control to the quantum states of reaction outcomes remains challenging. Here, we realize this goal by utilizing the conservation of nuclear spins throughout the reaction. Using resonance-enhanced multiphoton ionization spectroscopy to investigate the products formed in bimolecular reactions between ultracold KRb molecules we find that the system retains a near-perfect memory of the reactants' nuclear spins, manifested as a strong parity preference for the rotational states of the products. We leverage this effect to alter the occupation of these product states by changing the coherent superposition of initial nuclear spin states with an external magnetic field. In this way, we are able to control both the inputs and outputs of a reaction with quantum-state resolution. The techniques demonstrated here open up the possibilities to study quantum entanglement between reaction products and ultracold reaction dynamics at the state-to-state level.

Primary and Secondary Loss of CO and NO Ligands in the Ultraviolet Photodissociation of the Heteroleptic Co(CO)3NO Complex.

The photodissociation dynamics of the heteroleptic Co(CO)3NO complex were investigated in the metal-to-carbonyl (CO) ligand charge-transfer band to compare the reactivity of the CO and nitrosyl (NO) ligands. The final state distributions of both the CO and NO fragments were measured using resonance-enhanced multiphoton ionization (REMPI) spectroscopy and velocity-map ion-imaging. The primary CO photofragment was differentiated from the secondary fragments of the subsequent unimolecular decomposition of coordinatively unsaturated intermediates by comparing the momentum distributions. The internal energy of the Co(CO)2NO intermediate was sufficiently high (≥348 kJ/mol) to be generated in the electronic excited state, indicating the occurrence of the primary CO elimination on an excited state. The NO fragments exhibited two velocity components. The analysis of the final state distributions suggested that the higher- and lower-kinetic-energy components originated from the direct primary elimination and sequential elimination, respectively. The direct photoelimination through a transiently bent ligand conformation was illustrated on the basis of a two-dimensional REMPI approach and time-dependent density functional theory calculations. The present results of both ligands demonstrate the correlation between elimination mechanisms and possible ligand conformations in the electronic excited state.

Exploiting Photoionization Reflectron Time-of-Flight Mass Spectrometry to Explore Molecular Mass Growth Processes to Complex Organic Molecules in Interstellar and Solar System Ice Analogs.

ConspectusThis Account presents recent advances in our understanding on the formation pathways of complex organic molecules (COMs) within interstellar analog ices on ice-coated interstellar nanoparticles upon interaction with ionizing radiation exploiting reflectron time-of-flight mass spectrometry (ReTOF-MS) coupled with tunable vacuum ultraviolet (VUV) single photon ionization (PI) and resonance enhanced multiphoton ionization (REMPI) of the subliming molecules during the temperature-programmed desorption (TPD) phase. Laboratory simulation experiments provided compelling evidence that key classes of complex organics (aromatic hydrocarbons, alcohols, ethers, aldehydes, enols, ketones, and carboxylic acids) can be synthesized upon exposure of astrophysically relevant model ices to ionizing radiation within and throughout the ices at temperatures as low as 5 K.Molecular mass growth processes can be initiated by suprathermal or electronically excited reactants along with barrierless radical-radical recombination if both radicals hold a proper recombination geometry. Methyl (CH3), amino (NH2), hydroxyl (OH), ethyl (C2H5), vinyl (C2H3), ethynyl (C2H), formyl (HCO), hydroxycarbonyl (HOCO), hydroxymethyl (CH2OH), methoxy (CH3O), and acetyl (CH3CO) represent readily available reactants for radical-radical recombination within the ices. Reactive singlet species were found to insert without barrier into carbon-hydrogen and carbon-carbon single bonds (carbene) leading to an extension of the carbon chain and may add to carbon-carbon double bonds (carbene, atomic oxygen) forming cyclic reaction products. These galactic cosmic ray-triggered nonequilibrium pathways overcome previous obstacles of hypothesized thermal grain-surface processes and operate throughout the ice at 5 K. Our investigations discriminate between multiple structural isomers such as alcohols/ethers, aldehydes/enols, and cyclic/acyclic carbonyls. These data provide quantitative, isomer selective input parameters for a cosmic ray-dictated formation of complex organics in interstellar ices and are fully able to replicate the astronomical observations of complex organics over typical lifetimes of molecular clouds of a few 106 to 107 years. Overall, PI-ReTOF-MS revealed that the processing of astrophysically relevant ices can lead to multifaceted mixtures of organics reaching molecular weights of up to 200 amu. Further advances in laboratory techniques beyond the FTIR-QMS limit are clearly desired not only to confidently assign detection in laboratory ice analog experiments of increasingly more complex molecules of interest but also from the viewpoint of future astronomical searches in the age of the Atacama Large Millimeter/submillimeter Array (ALMA).

Characteristic Signal Behaviors for Water-in-Oil and Oil-in-Water Emulsions Measured by Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry.

Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) was used to study the characteristic signal behaviors obtained from two types of emulsions: water-in-oil (W/O) and oil-in-water (O/W). All emulsions were prepared using phase inversion emulsification, i.e., a solution for an aqueous phase was added dropwise to an oil phase with constant stirring to obtain an emulsion. Toluene served as a detection component. When using REMPI-TOFMS to measure an emulsion, a time profile for the target component can be constructed by plotting peak areas for the corresponding component on a series of mass spectra. In the case of a W/O emulsion at a water volume fraction (fw) of 0.005, the concentration of toluene was instantaneously decreased due to the existence of water droplets, and therefore, several negative spikes were detected on the time profile while establishing a baseline. In the case of a W/O emulsion at fw = 0.3, negative peaks consisting of several plots appeared on the time profile because of the formation of aggregates of water droplets while the emulsion was flowed through a capillary column for sample introduction. An O/W emulsion at fw = 0.995 was analyzed following phase inversion, and positive peaks were detected due to the aggregates of many oil droplets. In this manner, the direct mass analysis of emulsions before and after phase inversion was achieved, and the resultant signal inversion was confirmed via REMPI-TOFMS.

Photostimulated desorption of OH radicals from amorphous solid water: Evidence for the interaction of visible light with an OH-ice complex

Using a combination of photostimulated desorption and resonance-enhanced multiphoton ionization techniques, OH radicals photodesorbed from amorphous solid water at low temperatures are detected. It was found that the OH photodesorption can be caused by a one-photon process on the surface even at 532 nm, where both isolated OH and ${\mathrm{H}}_{2}\mathrm{O}$ are transparent. Quantum chemical calculations reveal that the electronic excitation of OH dramatically changes depending on the adsorption sites and the number of surrounding ${\mathrm{H}}_{2}\mathrm{O}$ molecules, and that OH having three hydrogen bonds with neighboring ${\mathrm{H}}_{2}\mathrm{O}$ molecules can absorb photons of around 532 nm, which supports the experimental findings.

Resonant dual-pulse laser ignition technique based on oxygen REMPI pre-ionization

This contribution investigates a novel laser ignition method based on a dual-pulse resonant pre-ionization scheme. The first laser pulse efficiently creates initial gas ionization (seed electrons) through a 2 + 1 resonantly-enhanced multiphoton ionization (REMPI) scheme targeting molecular oxygen (λ ~ 287.6 nm). This pulse is followed by a second non-resonant near-infrared pulse (λ = 1064 nm) for energy addition into the gas via inverse bremsstrahlung absorption. The sequence of two pulses creates a laser induced plasma that exhibits high peak electron number density and temperature (ne ~ 8 × 1017 cm-3 at t = 100 ns and T ~ 8000 K at t = 10 μs, respectively). These plasma parameters are similar to those attained for typical single-pulse near-infrared laser plasmas but with the advantage of substantially lower pulse energy (by factor of ~ 2.5) in the dual-pulse REMPI case. A combustion study focusing on ignition of propane/air mixtures shows that the dual-pulse REMPI method leads to an extension of the lean flammability limit, and an increase in combustion efficiency near the lean limit, as compared to laser ignition with a single NIR pulse. The measurement results and observed gas dynamics are discussed in the context of their impact on combustion applications.

The effect of the electric trapping field on state-selective loading of molecules into rf ion traps

Trapped molecular ions in pure rovibronic states are desirable in experiments ranging from cold chemistry to searches for physics beyond the Standard Model. Resonance-enhanced multiphoton ionisation (REMPI) can be used to prepare molecular ions in specific internal states with high fidelities. However, in the presence of electric fields, ionisation spectra exhibit frequency shifts and the ionisation thresholds are broadened. For this reason, REMPI studies are normally conducted in low and highly homogeneous electric fields, whereas the operating principle of rf ion traps requires electric fields that vary in space and time. In order to investigate the impact of this on the state-selectivity of REMPI in ion traps, we have simulated the expected broadening of the ionisation threshold under various operating conditions of a typical linear Paul trap. In many cases, the width of the ionisation threshold exceeds the separation between rotational energy levels, preventing state-selective ionisation. Careful choice of the trapping and laser parameters during loading can reduce this broadening, enabling state-selective ionisation in some instances. Where this strategy is not sufficient, the broadening can be reduced further by rapidly switching the trapping voltages off and on again during loading. This has been demonstrated experimentally for a Coulomb crystal of ^{40}hbox {Ca}^+ ions without descrystallising it.

Disentangling the H2 E, F(1Σ g +) (v′=0−18)←X(1Σ g +)(v″=3−9)(2+1) REMPI spectrum via 2D velocity-mapped imaging

We have measured the two-photon Resonance-Enhanced Multiphoton Ionization (REMPI) spectrum of H by producing the hydrogen molecule via photolysis of HCO. H is produced with rovibrational energies up to 30,000 cm, at a maximum observed of (9,5). In the well-resolved jet-cooled HCO spectrum, ortho and para H are selectively produced with near 100% selectivity. Over 470 REMPI transitions were identified in the EF−X band system, many of which have not been seen previously, including transitions to EF levels not yet accurately measured. Speed distributions were obtained for each REMPI transition using Velocity-mapped imaging, aiding in the assignment by providing a precise measurement of the internal energy of the H molecule.

Far-IR Absorption of Neutral Polycyclic Aromatic Hydrocarbons (PAHs): Light on the Mechanism of IR-UV Ion Dip Spectroscopy.

Gas-phase IR–UV double-resonance laser spectroscopy is an IR absorption technique that bridges the gap between experimental IR spectroscopy and theory. The IR experiments are used to directly evaluate predicted frequencies and potential energy surfaces as well as to probe the structure of isolated molecules. However, a detailed understanding of the underlying mechanisms is, especially in the far-IR regime, still far from complete, even though this is crucial for properly interpreting the recorded IR absorption spectra. Here, events occurring upon excitation to vibrational levels of polycyclic aromatic hydrocarbons by far-IR radiation from the FELIX free electron laser are followed using resonance-enhanced multiphoton ionization spectroscopy. These studies provide detailed insight into how ladder climbing and anharmonicity influence IR–UV spectroscopy and therefore the resulting IR signatures in the far-IR region. Moreover, the potential energy surfaces of these low-frequency delocalized modes are investigated and shown to have a strong harmonic character.

Diagnostics of CO concentration in gaseous mixtures at elevated pressures by resonance enhanced multi-photon ionization and microwave scattering

In this work, a novel diagnostic technique for carbon monoxide (CO) number density measurements in a nitrogen buffer mixture at elevated pressures up to 5 bar was developed and tested. The technique utilizes 2 + 1 resonance enhanced multi-photon ionization (REMPI) of CO induced by a femtosecond laser pulse at 230.1 nm, followed by detection of the number of REMPI-induced electrons using the microwave scattering (MS) method (REMPI-MS technique). Dependences of the number of REMPI-generated electrons on CO number density and laser energy were measured and analyzed in conjunction with a four energy level model of the CO molecule. The number of REMPI-induced electrons scaled linearly with CO number density up to about 5 × 1018 cm−3 and was independent of the buffer gas pressure up to 5 bar. Higher CO number densities caused saturation onset associated with laser beam energy loss while travelling through the gaseous mixture due to two-photon absorption and photoionization. The number of REMPI-induced electrons was found to scale cubically with the laser pulse energy for the tested energy range of 8–20 μJ (intensity in the focal region about 7–18 GW/cm2), which is consistent with the operation regime where the number density of excited CO molecules increases throughout the laser pulse duration and does not saturate in time. The linear scaling region of the REMPI-MS signal can be used for a CO number density diagnostic after appropriate calibration of the system.

Experimental and Theoretical Investigation of the 3sp(d) Rydberg States of Fenchone by Polarized Laser Resonance-Enhanced-Multiphoton-Ionization and Fourier Transform VUV Absorption Spectroscopy.

The VUV absorption spectrum of fenchone is re-examined using synchrotron radiation Fourier transform spectrometry, revealing new vibrational structure. Picosecond laser (2+1) resonance enhanced multiphoton ionization (REMPI) spectroscopy complements this, providing an alternative view of the 3spd Rydberg excitation region. These spectra display broadly similar appearance, with minor differences that are largely explained by referring to calculated one- and two-photon electronic excitation cross-sections. Both show good agreement with Franck-Condon simulations of the relevant vibrational structures. Parent ion REMPI ionization yields with both femtosecond and picosecond excitation laser pulses are studied as a function of laser polarization and intensity, the latter providing insight into the relative two-photon excitation and one-photon ionization rates. The experimental circular-linear dichroism observed in the parent ion yields varies strongly between the 3s and 3p Rydberg states, in good overall agreement with the calculated two-photon excitation circular-linear dichroism, while corroborating other evidence that the 3pz sub-state plays no more than a very minor role in the (2+1) REMPI spectrum. Vibrationally resolved photoelectron spectra are recorded with picosecond pulse duration (2+1) REMPI at selected intermediate vibrational excitations. The 3s intermediate state displays a very strong Δv=0 propensity on ionization, but the 3p intermediate evidences more complex vibronic dynamics, and we infer some 3p→3s internal conversion prior to ionization.

External trap-and-release membrane inlet for photoionization mass spectrometry: Towards fast direct analysis of aromatic pollutants in aquatic systems.

Fast and sensitive detection of aromatic hydrocarbons (AHs) in water is of high importance because of their significant impact on human health and the environment. For this, resonance-enhanced multiphoton ionization (REMPI) coupled to trap-and-release membrane-introduction mass spectrometry (T&R-MIMS) offers the possibility of sensitive on-line water analysis with a time resolution of minutes. REMPI is a versatile tool for sensitive gas-phase analysis, in which AHs are selectively ionized in complex gas mixtures by the subsequent absorption of at least two photons. In T&R-MIMS, selective extraction and enrichment of analytes from water can be achieved using semipermeable membranes. By the subsequent stimulated desorption of enriched compounds, mass spectrometric detection is enabled. We present an external T&R inlet for hollow-fiber membranes coupled to REMPI time-of-flight mass spectrometry, which enables direct and sensitive detection of semi-volatile AHs in water. In laboratory experiments, spiked water samples were analyzed. For the investigated compounds, limits of detection (LODs) in the range 1-47 ng/L were determined. The LODs are approximately one order of magnitude lower than in a previously reported continuous membrane-introduction approach using a planar membrane. Further improvement of LOD may be realized by extending the trapping time and by increasing the release temperature. Furthermore, the system was applied to investigate different fuels suspended in water and real water samples. The obtained data are in good agreement with findings of a former study. In the framework of the present study, we demonstrate the high potential of the combination of REMPI and T&R-MIMS in the form of a newly developed external hollow-fiber membrane inlet. With the developed system, semi-volatile AHs can be directly detected down to ng/L levels on a minute time scale. The approach thus may pave the way to future ship application in marine sciences, natural resources exploration or pollutant and hazard detection.

Direct measurement of fast ortho-para conversion of molecularly chemisorbed H2 on Pd(210)

Ortho-para conversion of molecularly chemisorbed ${\mathrm{H}}_{2}$ on a Pd(210) surface at a surface temperature of 50 K is reported. A combination of a pulsed molecular beam, photostimulated desorption, and resonance-enhanced multiphoton ionization techniques was used for probing the change in the rotational states of molecularly chemisorbed ${\mathrm{H}}_{2}$ on the surface. Our result shows that fast ortho-para conversion of chemisorbed ${\mathrm{H}}_{2}$ occurs. The conversion time was experimentally determined to be about 2 s, which is in good agreement with a previous theoretical calculation. This agreement supports that the ortho-para conversion mechanism of the molecularly chemisorbed ${\mathrm{H}}_{2}$ on Pd(210) is a two-step process based on the hyperfine-Coulomb excitation.

Clustering and multiphoton effects in velocity map imaging of methyl chloride

We have investigated different effects caused by clustering and multiphoton processes in the photodissociation of CHCl using velocity map imaging (VMI). Single-photon dissociation of CHCl at 193.3 nm yields CH and Cl fragments probed subsequently by resonance enhanced multiphoton ionisation (REMPI) at 333.52 nm and 235.31 nm, respectively. In the clusters, the CH fragments are strongly ‘caged’ losing most of their kinetic energy. Consequently, the VMI is dominated by a sharp central peak. On the other hand, the Cl fragments lose a broad range of energies in the cluster, yielding a blurred isotropic ‘central blob’ in VMI. At an increased 193 nm photon flux, another central feature appears in the CH images for isolated CHCl molecules. This ‘hour-glass’ shaped image corresponds to the CHCl multiphoton ionisation at 193 nm and subsequent CHCl ion photodissociation at 333 nm. The ion photodissociation is a parallel process with the anisotropy β-parameter values between +1.3 and +2.0. The total kinetic energy release (TKER) distribution suggests a high CH vibrational excitation. The CHCl ion photodissociation is discussed and compared to the photodissociation of similar CHBr ion.