Multiphoton Ionization Research Articles

Gas-phase vibrational spectroscopy of the dysprosium monoxide molecule and its cation.

Rotationally resolved vibrational spectra of DyO and DyO+ in a molecular beam are obtained by IR excitation from the X8 ground state and from high-n Rydberg states of DyO using an infrared free electron laser. Vibrational excitation is detected either by resonance enhanced multiphoton ionisation from X8(v = 1) or by autoionisation of Rydberg states converging to DyO+(v = 1). For most heavy molecules, the large spectral width of an infrared free electron laser does not allow for rotational resolution. In DyO and DyO+ the P, Q, and R transitions can be resolved due to the high angular momentum in their ground states. For 164DyO a vibrational constant of ωe = 847.5(2) cm-1 and a vibrational anharmonicity of ωeχe = 2.9(1) cm-1 are deduced. For the 161DyO+ cation a transition frequency of ΔG1/2 = 907(1) cm-1 is found.

Selective ionization of marker molecules in fuels by laser-based ion mobility spectrometry (LIMS).

Careful quality control of complex matrices such as fuels and food is necessary due to the prevalence of counterfeit and pirated goods in global trade. The addition of taggants (indicator substances) to products or their packaging helps to ensure traceability. In order to prevent the mixing of different liquid products, such as different taxed fuels, invisible labelling (marker) can be used to detect illegal activities. This study investigates the qualitative and quantitative analysis of markers in complex fuel matrices using Resonance-Enhanced Multiphoton Ionisation (REMPI) Ion Mobility Spectrometry (IMS). The potential of REMPI as a selective ionisation technique for the detection of markers is highlighted, particularly with respect to minimizing matrix background and the possibility of detection without chromatographic pre-separation. Finding a suitable marker-wavelength combination that provides a suitable marker-to-matrix ratio allows selective ionization of markers while minimising matrix background. Matrix analysis shows that higher excitation wavelengths result in reduced matrix signals, with the low intensities observed at 355 nm for diesel and petrol matrices. Several candidate markers are evaluated based on the criteria of intense signal at 355 nm and non-leachability for the low tax labelling. The analytical performance of selected markers is evaluated, with a focus on the charge transfer reaction (CTR) between markers and matrix components. Our findings demonstrate the potential of REMPI-IMS for marker analysis in fuels without the need for chromatographic pre-separation, providing a promising approach for detecting illegal or fraudulent activities in the supply chain.

A multiphoton ionisation photoelectron imaging study of thiophene.

Thiophene is a prototype for the excited state photophysics that lies at the heart of many technologies within the field of organic electronics. Here, we report a multiphoton ionisation photoelectron imaging study of gas-phase thiophene using a range of photon energies to excite transitions from the ground electronic state to the first two electronically excited singlet states, from the onset of absorption to the absorption maximum. Analysis of the photoelectron spectra and angular distributions reveal features arising from direct photoionisation from the ground electronic state, and resonance-enhanced photoionisation via the electronically excited singlet states. The first two ionisation energies from the ground electronic state were confirmed to be 8.8 eV (adiabatic) and 9.6 eV (vertical). The ionisation energies from the first two electronically excited singlet states were found to be 3.7 eV (adiabatic) and 4.4 eV (vertical).

The tautomer-specific excited state dynamics of 2,6-diaminopurine using resonance-enhanced multiphoton ionization and quantum chemical calculations.

2,6-Diaminopurine (2,6-dAP) is an alternative nucleobase that potentially played a role in prebiotic chemistry. We studied its excited state dynamics in the gas phase by REMPI, IR-UV hole burning, and ps pump-probe spectroscopy and performed quantum chemical calculations at the SCS-ADC(2) level of theory to interpret the experimental results. We found the 9H tautomer to have a small barrier to ultrafast relaxation via puckering of its 6-membered ring. The 7H tautomer has a larger barrier to reach a conical intersection and also has a sizable triplet yield. These results are discussed relative to other purines, for which 9H tautomerization appears to be more photostable than 7H and homosubstituted purines appear to be less photostable than heterosubstituted or singly substituted purines.

Roaming in the Unimolecular Decay of syn-Methyl-Substituted Criegee Intermediates.

Alkene ozonolysis generates transient carbonyl oxide species, known as Criegee intermediates, which are a significant nonphotolytic source of OH radicals in the troposphere. This study demonstrates that unimolecular decay of syn-methyl-substituted Criegee intermediates proceeds via 1,4 H atom transfer to vinyl hydroperoxides, resulting in OH fission to O-O products or, alternatively, OH roaming to hydroxycarbonyl products. Newly generated Criegee intermediates are shown to yield hydroxycarbonyls with sufficient internal excitation to dissociate via C-C fission to acyl and hydroxymethyl (CH2OH) radicals. The stabilized Criegee intermediates and unimolecular products are rapidly cooled in a pulsed supersonic expansion for photoionization detection with time-of-flight mass spectrometry. CH2OH products are identified by 2 + 1 resonance-enhanced multiphoton ionization via the 3pz Rydberg state upon unimolecular decay of CH3CHOO, (CH3)2COO, (CH3)(CH3CH2)COO, and (CH3)(CH2═CH)COO (methyl vinyl ketone oxide). The stabilized Criegee intermediates are separately detected using 10.5 eV photoionization. This study provides the first experimental evidence of roaming in the unimolecular decay of isoprene-derived methyl vinyl ketone oxide and extends earlier studies that reported stabilized hydroxycarbonyl products.

Laser-Pulse-Length Effects in Ultrafast Laser Desorption.

Shortening the laser pulse length opens up new opportunities for laser desorption (LD) of molecules, with benefits for mass spectrometry (MS) sampling and ionization. The capability to ablate any material without the need for an absorbing matrix and the decrease of thermal damage and molecular fragmentation has promoted various applications with very different parameters and postionization techniques. However, the key issues of the optimum laser pulse length and intensity to achieve efficient and gentle desorption of molecules for postionization in MS are not resolved, although these parameters determine the costs and complexity of the required laser system. Here, we address this research gap with a systematic study on the effect of the pulse length on the LD of molecules. Keeping all other optical and ionization parameters constant, we directly compared the pulses in the femtosecond, picosecond, and nanosecond range with respect to LD-induced fragmentation and desorption efficiency. To represent real-world applications, we investigated the LD of over-the-counter medicaments naproxen and ibuprofen directly from tablets as well as the LD of retene and ship emission aerosols from a quartz filter. With our study design, we excluded interfering effects on fragmentation and LD efficiency from, for example, collisional cooling or postionization by performing the experiments in vacuum with resonance-enhanced multiphoton ionization as the postionization technique. Regarding LD-induced fragmentation, we already found benefits for the picosecond pulses. However, the efficiency of LD was found to continuously increase with decreasing pulse length, pointing to the application potential of ultrashort pulses in trace analytics. Because many interfering effects beyond the LD pulse length could be excluded in the experiment, our results may be directly transferable to the LD applied in other techniques.

Low temperature reaction kinetics inside an extended Laval nozzle: REMPI characterization and detection by broadband rotational spectroscopy.

Chirped-Pulse Fourier-Transform millimeter wave (CP-FTmmW) spectroscopy is a powerful method that enables detection of quantum state specific reactants and products in mixtures. We have successfully coupled this technique with a pulsed uniform Laval flow system to study photodissociation and reactions at low temperature, which we refer to as CPUF ("Chirped-Pulse/Uniform flow"). Detection by CPUF requires monitoring the free induction decay (FID) of the rotational coherence. However, the high collision frequency in high-density uniform supersonic flows can interfere with the FID and attenuate the signal. One way to overcome this is to sample the flow, but this can cause interference from shocks in the sampling region. This led us to develop an extended Laval nozzle that creates a uniform flow within the nozzle itself, after which the gas undergoes a shock-free secondary expansion to cold, low pressure conditions ideal for CP-FTmmW detection. Impact pressure measurements, commonly used to characterize Laval flows, cannot be used to monitor the flow within the nozzle. Therefore, we implemented a REMPI (resonance-enhanced multiphoton ionization) detection scheme that allows the interrogation of the conditions of the flow directly inside the extended nozzle, confirming the fluid dynamics simulations of the flow environment. We describe the development of the new 20K extended flow, along with its characterization using REMPI and computational fluid dynamics. Finally, we demonstrate its application to the first low temperature measurement of the reaction kinetics of HCO with O2 and obtain a rate coefficient at 20K of 6.66 ± 0.47 × 10-11cm3 molec-1s-1.

The importance of molecular axis alignment and symmetry-breaking in photoelectron elliptical dichroism.

Photoelectron angular distributions (PADs) produced from the photoionization of chiral molecules using elliptically polarized light exhibit a forward/backward asymmetry with respect to the optical propagation direction. By recording these distributions using the velocity-map imaging (VMI) technique, the resulting photoelectron elliptical dichroism (PEELD) has previously been demonstrated as a promising spectroscopic tool for studying chiral molecules in the gas phase. The use of elliptically polarized laser pulses, however, produces PADs (and consequently, PEELD distributions) that do not exhibit cylindrical symmetry about the propagation axis. This leads to significant limitations and challenges when employing conventional VMI acquisition and data processing strategies. Using novel photoelectron image analysis methods based around Hankel transform reconstruction tomography and machine learning, however, we have quantified-for the first time-significant symmetry-breaking contributions to PEELD signals that are of a comparable magnitude to the symmetric terms in the multiphoton ionization of (1R,4R)-(+)- and (1S,4S)-(-)-camphor. This contradicts any assumptions that symmetry-breaking can be ignored when reconstructing VMI data. Furthermore, these same symmetry-breaking terms are expected to appear in any experiment where circular and linear laser fields are used together. This ionization scheme is particularly relevant for investigating dynamics in chiral molecules, but it is not limited to them. Developing a full understanding of these terms and the role they play in the photoionization of chiral molecules is of clear importance if the potential of PEELD and related effects for future practical applications is to be fully realized.

Multichromatic supercontinuum polarization shaping applied to photoelectron holography

We present a supercontinuum pulse shaping method specifically designed for the generation of polarization-tailored multichromatic femtosecond laser fields. By combining a 4f-polarization pulse shaper with a custom-made polarizer kit, we independently modulate different spectral bands of a white-light supercontinuum in amplitude, phase, and polarization. The scheme is highly modular, scalable to any number of bands supported by the input spectrum and aims at the physically motivated design of specific laser fields tailored to the relevant transitions and dynamics of the quantum system. The power and versatility of the scheme is showcased in three different scenarios based on atomic multiphoton ionization employing polarization-tailored trichromatic pulse sequences. (1) We demonstrate the creation of an -type free electron wave packet and reconstruct its 3D momentum distribution by a waveplate-free shaper-based photoelectron tomography technique. (2) We utilize the holographic properties of the wave packet to study time-resolved and phase-sensitive ultrafast dynamics of bound states. (3) We investigate the field-free time-evolution of a photoelectron wave packet in the continuum. Our results on an atomic model system demonstrate the great potential of the modular shaping scheme for a wide range of applications on more complex quantum systems, including polyatomic molecules, nanoscopic structures and solids.

Temporal evolution of laser-induced ionization and recombination processes in argon-helium mixture

Preparation of metastable atoms (1s5) through laser-induced preionization holds the potential to mitigate the electromagnetic interference (EMI) issues associated with the large volume, atmospheric pressure discharge of traditional optically pumped rare-gas metastable laser (OPRGL). In this work, we conducted experimental investigations into the temporal evolution of the Ar 763.5 nm (2p6→1s5) spectral line in Ar-He mixture. These experiments unveiled the intricate interaction mechanism involving the laser, Ar atoms, He atoms, and free electrons within the laser-induced plasma. Our findings highlight the dual contributions of the multiphoton ionization and the inverse bremsstrahlung process to the initial plasma formation. Notably, the time-resolved atomic emission spectrum at 763.5 nm reveals two distinct regimes, namely Regime1 and Regime2. Regime1 primarily arises from the “excitation + radiation + collisional relaxation” process, wherein excited states Ar atoms, populated via multiphoton excitation and electron impact excitation, accumulate on the 2p6 level. Conversely, Regime2 is predominantly a result of the “ion-electron recombination” process. In this regime, highly excited states Ar atoms are generated through the recombination of ion and electron, subsequently populating the 2p6 level through a combination of radiation and collisional relaxation channels. The differences in the temporal evolution between 763.5 nm and 811.5 nm spectral lines can be attributed to the distinct radiation and collisional relaxation channels in the two aforementioned processes.

Ultrafast Multistage Lattice Strain via Laser‐Excited Phonons in Lithium Niobate

AbstractUltrafast laser‐excitation of lithium niobate (LiNbO3) crystal has triggered numerous photonic applications through the structural transitions in LiNbO3. However, the explanations for ultrafast laser‐induced modification of LiNbO3 have remained phenomenological, lacking a convincing in‐depth understanding of the fundamental laser‐lattice interaction process. Based on ab initio simulations, it is demonstrated that photoexcited anharmonic phonons play a significant role in influencing the lattice structure of LiNbO3. Harnessing the real‐time time‐dependent density functional theory, it is revealed that the excitation of TO4 phonons via electric‐phonon coupling triggers displacement‐induced lattice oscillations during multiphoton ionization. These oscillations give rise to multistage structural strains, resulting in alterations of the refractive index. Significantly, these modifications exhibit sensitivity to the incident laser energy. Experimentally, using the waveguide technique and micro‐Raman spectroscopy, the correlation between local refractive index, lattice volume density, and phonon vibrational modes has been established, exhibiting good consistency with theoretical predictions. This work provides an effective means to understand the ultrafast excitation of phonons and relaxation processes of the lattice in dielectric crystals.

Molecular beam laser spectroscopic studies of the photoactive properties of resveratrol

Resonance Enhanced MultiPhoton Ionization spectroscopic techniques coupled with laser desorption and supersonic cooling have been employed to elucidate the photoactive properties of resveratrol. The observed excitation spectra give evidence for an internal-energy dependent trans–cis isomerisation pathway in the electronically excited state, while pump-probe studies show dynamics that are in line with what is known for the parent compound, trans-stilbene. Similar studies have been performed on a derivative of resveratrol with methoxy instead of hydroxy groups, a compound aimed to reduce previously observed photodegradation pathways of resveratrol. Time-resolved studies of the latter compound under solution conditions have given further insight into its excited-state dynamics and support the isolated-molecule conclusions on the topology of the potential energy surface of the electronically excited state. Spectroscopic studies under prolonged irradiation conditions show that both compounds suffer from photodegradation, although in the alkylated compound other pathways appear to be involved than in resveratrol.Graphical abstract

Multiphoton excitation and ionization of hydrogen atoms in two-color laser fields

Multiphoton excitation and ionization of hydrogen atoms in two-color laser fields

Characterizing the origin band spectrum of isoquinoline with resonance enhanced multiphoton ionization and electronic structure calculations.

We report the experimental resonance enhanced multiphoton ionization spectrum of isoquinoline between 315 and 310nm, along with correlated electronic structure calculations on the ground and excited states of this species. This spectral region spans the origin transitions to a π-π* excited state, which previous work has suggested to be vibronically coupled with a lower lying singlet n-π* state. Our computational results corroborate previous density functional theory calculations that predict the vertical excitation energy for the n-π* state to be higher than the π-π* state; however, we find an increase in the C-N-C angle brings the n-π* state below the energy of the π-π* state. The calculations find two out-of-plane vibrational modes of the n-π* state, which may be brought into near resonance with the π-π* state as the C-N-C bond angle increases. Therefore, the C-N-C bond angle may be important in activating vibronic coupling between the states. We fit the experimental rotational contour with a genetic algorithm to determine the excited state rotational constants and orientation of the transition dipole moment. The fits show a mostly in-plane polarized transition, and the projection of the transition dipole moment in the a-b plane is about 84° away from the a axis. These results are consistent with the prediction of our electronic structure calculations for the transition dipole moment of the π-π* excited state.

MALDI-2 Mass Spectrometry for Synthetic Polymer Analysis.

Synthetic polymers are ubiquitous in daily life, and their properties offer diverse benefits in numerous applications. However, synthetic polymers also present an increasing environmental burden through their improper disposal and subsequent degradation into secondary micro- and nanoparticles (MNPs). These MNPs accumulate in soil and water environments and can ultimately end up in the food chain, resulting in potential health risks. Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) has the potential to study localized biological or toxicological changes in organisms exposed to MNPs. Here, we investigate whether MALDI-2 postionization can provide a sensitivity enhancement in polymer analysis that could contribute to the study of MNPs. We evaluated the effect of MALDI-2 by comparing MALDI and MALDI-2 ion yields from polyethyleneglycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTHF), nylon-6, and polystyrene (PS). MALDI-2 caused a signal enhancement of the protonated species for PEG, PPG, PTHF, and nylon-6. PS, by contrast, preferentially formed radical ions, which we attribute to direct resonance-enhanced multiphoton ionization (REMPI). REMPI of PS led to an improvement in sensitivity by several orders of magnitude, even without cationizing salts. The improved sensitivity demonstrated by MALDI-2 for all polymers tested highlights its potential for studying the distribution of certain classes of polymers in biological systems.

Influence of Electron Collisions on Electromagnetic Modes of Plasma Produced by Multi-Photon Ionization of an Inert Gas

Collective electromagnetic modes in weakly ionized plasma formed by multiphoton ionization of inert gas atoms, in which the Ramsauer–Townsend effect takes place, are studied. It is shown that at a relatively low energy of photoelectrons of the order of 1 eV, typical for multiphoton ionization, amplification of electromagnetic waves is possible. Amplification is possible both in the case of rare collisions of photoelectrons with neutral atoms and for collision frequencies higher than electron plasma frequency. At photoelectron energies somewhat higher than 1 eV, aperiodic instability can develop with growth rate whose value is comparable to electron plasma frequency. Detailed analytical and numerical analysis of the effect of collisions of photoelectrons with neutral atoms on the dispersion law of electromagnetic wave and the growth rates of instabilities is presented.

Influence of Electron Collisions on Electromagnetic Modes of Plasma Produced by Multi-Photon Ionization of an Inert Gas

Influence of Electron Collisions on Electromagnetic Modes of Plasma Produced by Multi-Photon Ionization of an Inert Gas

Ultraviolet electronic spectroscopy of heavily substituted naphthalene derivatives

Context. The so-called bump spectral signature observable on interstellar extinction curves, peaking at 217.5 nm, is commonly assigned to π* ← π transitions from carbonaceous carriers, but the exact nature of the carbonaceous carriers remains debated. Aims. To constrain the chemical structures associated with the bump carriers, we record and compare the UV spectra of a large variety of carbonaceous molecules to this interstellar feature. Methods. Large carbonaceous molecules, such as polycyclic aromatic hydrocarbons (PAHs), were produced by a combustion process stabilized at low pressure under rich flame conditions. Species were extracted and probed through resonance enhanced multiphoton ionization spectroscopy coupled to a time-of-flight mass spectrometer. Masses and absorption profiles of the carbonaceous molecules were measured, and their spectra were compared to the bump feature. Results. Species showing a specific mass progression starting at mass 128 u visible up to mass 394 u with a characteristic progression of +14 u present a common electronic absorption band profile peaking asymptotically around 220 nm. The first masses were assigned to a naphthalene C10H8 molecule and two of its derivatives: C10H7CH3 and C10H7C2H5. The mass progression of +14 u is explained by successive H atom substitutions by CH3 functional groups. This mass distribution was thus assigned to naphthalene derivatives with large aliphatic carbon substitution. This derivative family shows an electronic band assigned to S3 ← S0 transitions involving electron promotion within the π aromatic orbitals of the naphathlene chromophore. More importantly, after a few substitutions, the position of the band converges asymptotically to a value close to the interstellar bump signature, independent of the molecule size. Conclusions. Based on the asymptotic behavior of the larger members in the species distribution, a similar band position is expected from double aromatic ring substructures within hydrogenated amorphous carbons (HACs). Similar to the conclusions of previous works, we find substituted naphthalene units as substructures of interstellar HACs to be good candidates as carriers of the bump feature.

Excited-state dynamics of deuterated indigo

Indigo, a rich blue dye, is an incredibly photostable molecule that has survived in ancient art for centuries. It is also unique in that it can undergo both an excited-state hydrogen and proton transfer on the picosecond timescale followed by a ground-state back transfer. Previously, we performed gas phase excited-state lifetime studies on indigo to study these processes in a solvent-free environment, combined with excited-state calculations. We found two decay pathways, a fast sub-nanosecond decay and a slow decay on the order of 10 ns. Calculations of the excited-state potential energy surface found that both hydrogen and proton transfer are nearly isoenergetic separated by a 0.1 eV barrier. To further elucidate these dynamics, we now report a study with deuterated indigo, using resonance-enhanced multi-photon ionization and pump-probe spectroscopy with mass spectrometric isotopomer selection. From new calculations of the excited-state potential energy surface, we find sequential double-proton or hydrogen transfer, whereby the trajectory to the second transfer passes a second barrier and then encounters a conical intersection that leads back to the ground state. We find that deuteration only increases the excited-state lifetimes of the fast decay channel, suggesting tunneling through the first barrier, while the slower channel is not affected and may involve a different intermediate state.Graphical abstract

When Phenyl and Cyclopropyl Rings Meet: Spectroscopic Shifts and Conformational Questions.

The electronic and vibrational spectra of cyclopropylbenzene (CPB) and 1,3-bromocyclopropylbenzene (BrCPB) in the gas phase were investigated using quantum chemical calculations in combination with resonance-enhanced multi-photon ionization REMPI techniques including 1c-R2PI, UV-UV holeburning, and IR-UV ion depletion in the CH stretch region. The electronic spectra revealed the presence of a single conformer for both species, with the absence of any perpendicular conformer attributed to low computed barriers to conformer interconversion. Assignment of CPB to the bisected conformer was made through interpreting distinctive CH stretch bands in the IR-UV spectrum in conjunction with quantum chemical calculations. A local anharmonic model based on DFT calculations was adapted to reproduce the cyclopropyl CH stretch spectrum successfully. It was not feasible to definitively assign which bisected conformer of BrCPB was observed using vibrational information alone due to the close similarity of their predicted IR spectra. However, conformational sensitivity of the S1 ← S0 transition dipole moment (TDM) alignments leads to simulated rotational contours that display stark differences, which prompted assignment to the "B1" bisecting conformer with the cyclopropyl ring directed away from the bromine atom. The absence of the energetically comparable "B2" conformer is unexpected. The analysis of the convolution of aromatic and aliphatic modes serves as a basis for assignment in constrained aliphatic systems.