Multiphoton Spectroscopy Research Articles

TOLUENIUM AND OTHER GASEOUS METHYLBENZENIUM IONS: COMPLEX INTERPLAY OF PROTONATED ARENES AND CYCLO‐OLEFINS

The development of the current knowledge of the gas-phase chemistry of protonated methylbenzenes, such as toluenium, xylenium and mesitylenium ions, their higher congeners as well as of their mostly cyclo-olefinic isomers by mass spectrometric methodology is presented. Starting from the observation of the characteristic expulsion of dihydrogen from metastable C7 H9 + ions, which is associated with the release of large amounts of kinetic energy, and the composite C- and H-scrambling prior to the loss of methane, in particular, insights into the isomerization scenario of various isomeric C7 H9 + , C8 H11 + , and C9 H13 + ions, based on a large variety of independent techniques, are discussed. Besides isotope labeling and metastable ion methodology, these include flowing afterglow mass spectrometry, gas-phase titration and infrared spectroscopy of mass-selected ions. The particularly complex energy hypersurface of isomerizing and fragmenting toluenium ions, which has been elaborated in various reports over the years, is presented in a combined way to assess the role of protonated cycloheptatriene, norbornadiene, and 6-methylfulvene as well as a number of further C7 H9 + isomers. The formation and nature of C7 H9 + ions generated by fragmentation of various hydrocarbon precursors, such as monoterpenes and adamantane, is also addressed. The contribution of infrared multiphoton dissociation spectroscopy (IRMPD)and tagged-ion infrared photodissociation (IRPD) of the gaseous C7 H9 + ions as compared to the wealth of previous understanding of their chemistry is commented on as well. Finally, remarkable parallels of the gas-phase chemistry of methylbenzenium ions and the role of such species within the cavities of acidic zeolite catalysts in the course of the industrially important methanol-to-hydrocarbon reaction are discussed. © 2020 John Wiley & Sons Ltd. Mass Spec Rev.

Above-threshold multiphoton photoemission from noble metal surfaces

Exciting solids with intense femtosecond laser pulses prompts electrons of the interrogated material to respond in a highly nonlinear manner, as is evident in the emission of high-order harmonic radiation and photoelectrons with kinetic energies well above that of the driving photons. Such high-field interactions can be resolved, for example, in above-threshold multiphoton photoemission (ATP) spectroscopy. In this work, we interrogate the nonlinear photoelectric responses of the pristine copper, silver, and gold noble metal surfaces in (111) and (100) crystal orientations in the perturbative regime. Using multiphoton photoemission spectroscopy (mPP) excited by finely tuned optical fields, we characterize enhancement of the mPP and ATP yields from (111) surfaces in selected ${k}_{||}$-momentum ranges when the occupied Shockley surface (SS) states are (near-)resonantly coupled by multiphoton transitions to image potential (IP) intermediate states in the excitation process. The ATP signal from the IP states of (111) surfaces is largely defined by their formation through polarization of SS electrons; this observation is contrasted with ATP experiments from the Ag(100) surface, for which the SS becomes an unoccupied resonance and the IP states can only be excited from bands with significantly more bulk character. In addition, based on the optical power and nonlinear order-dependent mPP spectra, we provide evidence for ATP being a one-step, rather than a sequential process, as previously postulated.

Translation of two-photon microscopy to the clinic: multimodal multiphoton CARS tomography of in vivo human skin.

.Two-photon microscopes have been successfully translated into clinical imaging tools to obtain high-resolution optical biopsies for in vivo histology. We report on clinical multiphoton coherent anti-Stokes Raman spectroscopy (CARS) tomography based on two tunable ultrashort near-infrared laser beams for label-free in vivo multimodal skin imaging. The multiphoton biopsies were obtained with the compact tomograph “MPTflex-CARS” using a photonic crystal fiber, an optomechanical articulated arm, and a four-detector-360 deg measurement head. The multiphoton tomograph has been employed to patients in a hospital with diseased skin. The clinical study involved 16 subjects, 8 patients with atopic dermatitis, 4 patients with psoriasis vulgaris, and 4 volunteers served as control. Two-photon cellular autofluorescence lifetime, second harmonic generation (SHG) of collagen, and CARS of intratissue lipids/proteins have been detected with single-photon sensitivity, submicron spatial resolution, and picosecond temporal resolution. The most important signal was the autofluorescence from nicotinamide adenine dinucleotide [NAD(P)H]. The SHG signal from collagen was mainly used to detect the epidermal–dermal junction and to calculate the ratio elastin/collagen. The CARS/Raman signal provided add-on information. Based on this view on the disease-affected skin on a subcellular level, skin areas affected by dermatitis and by psoriasis could be clearly identified. Multimodal multiphoton tomographs may become important label-free clinical high-resolution imaging tools for in vivo skin histology to realize rapid early diagnosis as well as treatment control.

Femtochemistry under scrutiny: Clocking state-resolved channels in the photodissociation of CH3I in the A-band.

Clocking of electronically and vibrationally state-resolved channels of the fast photodissociation of CH3I in the A-band is re-examined in a combined experimental and theoretical study. Experimentally, a femtosecond pump-probe scheme is employed in the modality of resonant probing by resonance enhanced multiphoton ionization (REMPI) of the methyl fragment in different vibrational states and detection through fragment velocity map ion (VMI) imaging as a function of the time delay. We revisit excitation to the center of the A-band at 268 nm and report new results for excitation to the blue of the band center at 243 nm. Theoretically, two approaches have been employed to shed light into the observations: first, a reduced dimensionality 4D nonadiabatic wavepacket calculation using the potential energy surfaces by Xie et al. [J. Phys. Chem. A 104, 1009 (2000)]; and second, a full dimension 9D trajectory surface-hopping calculation on the same potential energy surfaces, including the quantization of vibrational states of the methyl product. In addition, high level ab initio electronic structure calculations have been carried out to describe the CH3 3pz Rydberg state involved in the (2 + 1) REMPI probing process, as a function of the carbon-iodine (C-I) distance. A general qualitative agreement is obtained between experiment and theory, but the effect of methyl vibrational excitation in the umbrella mode on the clocking times is not well reproduced. The theoretical results reveal that no significant effect on the state-resolved appearance times is exerted by the nonadiabatic crossing through the conical intersection present in the first absorption band. The vibrationally state resolved clocking times observed experimentally can be rationalized when the (2 + 1) REMPI probing process is considered. None of the other probing methods applied thus far, i.e., multiphoton ionization photoelectron spectroscopy, soft X-ray inner-shell photoelectron spectroscopy, VUV single-photon ionization, and XUV core-to-valence transient absorption spectroscopy, have been able to provide quantum state-resolved (vibrational) clocking times. More experiments would be needed to disentangle the fine details in the clocking times and dissociation dynamics arising from the detection of specific quantum-states of the molecular fragments.

Entropy- and purity-tailored broadband entanglement from vectorial four-wave mixing: Insights from pulse modes and classical-field dynamics

We present a time-domain Schmidt-mode analysis of a broadband continuous-variable entanglement of photon pairs generated via a vectorial four-wave mixing (FWM) of ultrashort laser pulses in a highly nonlinear birefringent optical fiber. We demonstrate that the time-domain eigenmodes of high-purity two-photon states generated through vectorial FWM can be steered, by varying the pump wavelength and FWM polarization geometry, from a high-purity entangled ket to a high-entropy entangled state in a space of a very high dimensionality. Moreover, this pulse-mode analysis is shown to provide a clear physical perspective on how the entanglement structure of two-photon states builds up as a result of short-pulse FWM dynamics. This insight reveals a correspondence-type relation between the quantum and classical pictures of photon-pair generation. With an eye on practical applications, a clear understanding of the temporal profile of pulse modes representing high-purity two-photon states is central to a meaningful shaping of ultrashort photon-packet waveforms for super-resolving microscopy and multiphoton spectroscopy using quantum states of light.

Design and characterization of a recirculating liquid-microjet photoelectron spectrometer for multiphoton ultraviolet photoelectron spectroscopy.

A new recirculating liquid-microjet photoelectron spectrometer for multiphoton ultraviolet photoelectron spectroscopy is described. A recirculating system is essential for studying samples that are only available in relatively small quantities. The reduction in background pressure when using the recirculating system compared to a liquid-nitrogen cold-trap results in a significant improvement in the quality of the photoelectron spectra. Moreover, the recirculating system results in a negligible streaming potential. The instrument design, operation, and characterization are described in detail, and its performance is illustrated by comparing a photoelectron spectrum of aqueous phenol recorded using the recirculating system with one recorded using a liquid nitrogen cold-trap.

Imaging of π-conjugated polymer/fullerene blends used in organic photovoltaics by nonlinear photoluminescence emission

A number of image microscopies have been applied to films of π-conjugated polymers and their fullerene blends used in photovoltaic applications; however, they seldom are able to map the polymer/fullerene grain interfaces and detect microscopic defects in the blend films. We have conducted multiphoton microscopy using a 65-fs mode-locked laser at 1.56 μm for spectroscopy and mapping of films of two prototype π-conjugated polymers, namely MEH-PPV and P3HT combined with their blends of PCBM fullerene molecules. The pristine polymer films have shown third harmonic generation and three-photon photoluminescence emission bands that are used for mapping the film topography with micrometer spatial resolution. Since the nonlinear photoluminescence band of the photogenerated charge transfer excitons (CTE) at the polymer/fullerene interfaces in films of polymer/fullerene blends is substantially redshifted compared to that of the excitons in pristine polymers, we could readily map the polymer/fullerene grain interfaces using the nonlinear CTE photoluminescence emission. From the multiphoton imaging of the polymer/fullerene films, we show that the polymer super-grains in MEH-PPV/PCBM are substantially larger than those in P3HT/PCBM, which may be detrimental to charge transport and, in turn, to photovoltaic applications, in agreement with smaller power conversion efficiencies obtained for solar cells based on the former blend. In addition, we also found second harmonic generation emission bands in the MEH-PPV/PCBM blend that result from micron-size embedded defects that do not possess inversion symmetry that forms during the film deposition process at ambient conditions. Multiphoton microscopy and spectroscopy are valuable additions to the tools of organic semiconductor films and devices for investigating the properties and growth of polymer/fullerene blends used for photovoltaic applications with micron spatial resolution.

Coherent Two-Dimensional Multiphoton Photoelectron Spectroscopy of Metal Surfaces

Light interacting with metals elicits an ultrafast coherent many-body screening response on sub- to few-femtosecond time-scales, which makes its experimental observation challenging. Here, we describe the coherent two-dimensional (2D) multi-photon photoemission study of the Shockley surface state (SS) of Ag(111) as a benchmark for spectroscopy of the coherent nonlinear response of metals to an optical field in the perturbative regime. Employing interferometrically time-resolved multi-photon photoemission spectroscopy (ITR-mPP), we correlate the coherent polarizations and populations excited in the sample with final photoelectron distributions where the interaction terminates. By measuring the non-resonant 3- and 4-photon photoemission of the SS state, as well as its replica structures in the above-threshold photoemission (ATP), we record the coherent response of the Ag(111) surface by 2D photoemission spectroscopy and relate it to its band structure. We interpret the mPP process by an optical Bloch equation (OBE) model, which reproduces the main features of the surface state coherent polarization dynamics recorded in ITR-mPP experiments: The spectroscopic components of the 2D photoelectron spectra are shown to depend on the nonlinear orders of the coherent photoemission process m as well as on the induced coherence n.

Nanowire Superinductance Fluxonium Qubit.

We characterize a fluxonium qubit consisting of a Josephson junction inductively shunted with a NbTiN nanowire superinductance. We explain the measured energy spectrum by means of a multimode theory accounting for the distributed nature of the superinductance and the effect of the circuit nonlinearity to all orders in the Josephson potential. Using multiphoton Raman spectroscopy, we address multiple fluxonium transitions, observe multilevel Autler-Townes splitting and measure an excited state lifetime of T_{1}=20 μs. By measuring T_{1} at different magnetic flux values, we find a crossover in the lifetime limiting mechanism from capacitive to inductive losses.

Selective cellular imaging with lanthanide-based upconversion nanoparticles.

Upconversion nanoparticles (UCNPs) with sodium yttrium fluoride, NaYF4 (host lattice) doped with Yb3+ (sensitizer) and Er3+ (activator) were synthesized via hydrothermal route incorporating polyethyleneimine (PEI) for their long‐term stability in water. The cationic PEI‐modified UCNPs with diameter 20 ± 4 nm showed a zeta potential value of +36.5 mV and showed an intense, visible red luminescence and low‐intensity green emission with 976 nm laser excitation. The particles proven to be nontoxic to endothelial cells, with a 3‐(4,5‐dimethylthiazol‐2yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay, showing 90% to 100% cell viability, across a wide range of UCNP concentrations (0.3 ng/mL‐0.3 mg/mL) were used in multiphoton imaging. Multiphoton cellular imaging and emission spectroscopy data reported here prove that the UCNPs dispersed in cell culture media are predominantly concentrated in the cytoplasm than the cell nucleus. The energy transfer from PEI‐coated UCNPs to surrounding media for red luminescence in the biological system is also highlighted with spectroscopic measurements. Results of this study propose that UCNPs can, therefore, be used for cytoplasm selective imaging together with multiphoton dyes (eg, 4′,6‐diamidino‐2‐phenylindole (DAPI)) that are selective to cell nucleus.

The detection of petroleum contaminants in soil based on multiphoton electron extraction spectroscopy

The fast detection of petroleum contaminants in soil is very important and urgent for environmental monitoring.

Multiphoton fluorescence excitation and detection with a single negative curvature hollow core fibre

In this letter, we propose a single fiber-based sensor setup allowing for simultaneous excitation and detection of multiphoton fluorescence. Presented sensor’s key element is the negative curvature hollow core fiber (NCHCF) with three transmission bands in the visible spectral range (414–423 nm, 510–552 nm and 680–784 nm), allowing for nearly dispersion-free guidance of 160 fs-long laser pulses at 730 nm photon wavelength. Total temporal broadening of a laser pulse propagating in the proposed sensor setup is only (7 ± 1) fs. The NCHCF output beam was additionally focused with a microlensed, multimode fiber tip, increasing the efficiency of multiphoton absorption. The usefulness of the sensor for the multiphoton spectroscopy experiments is tested on the solutions of fluorescein and flavin adenine dinucleotide. This optical fiber sensor combines simplicity, minimal size, and good optical properties, and can be found an interesing solution for the non-linear optical methods used in chemistry, biology and medicine.

Combining Hollow Core Photonic Crystal Fibers with Multimode, Solid Core Fiber Couplers through Arc Fusion Splicing for the Miniaturization of Nonlinear Spectroscopy Sensing Devices

The presence of fiber optic devices, such as couplers or wavelength division multiplexers, based on hollow-core fibers (HCFs) is still rather uncommon, while such devices can be imagined to greatly increase the potential of HCFs for different applications, such as sensing, nonlinear optics, etc. In this paper, we present a combination of a standard, multimode fiber (MMF) optic coupler with a hollow core photonic bandgap fiber through arc fusion splicing and its application for the purpose of multiphoton spectroscopy. The presented splicing method is of high affordability due to the low cost of arc fusion splicers, and the measured splicing loss (SL) of the HCF-MMF splice is as low as (0.32 ± 0.1) dB, while the splice itself is durable enough to withstand a bending radius (rbend) of 1.8 cm. This resulted in a hybrid between the hollow core photonic bandgap fiber (HCPBF) and MMF coupler, delivering 20 mW of average power and 250-fs short laser pulses to the sample, which was good enough to test the proposed sensor setup in a simple, proof-of-concept multiphoton fluorescence excitation-detection experiment, allowing the successful measurement of the fluorescence emission spectrum of 10−5 M fluorescein solution. In our opinion, the presented results indicate the possibility of creating multi-purpose HCF setups, which would excel in various types of sensing applications.

Quantitative and sensitive mapping of imidacloprid on plants using multiphoton electron extraction spectroscopy

Neonicotinoids, including imidacloprid, are extensively used for plant protection against insects. Unfortunately, these effective pesticides are one of the reasons for the decline of the bee population in recent decades. Ensuring application of minimal pesticide quantity and preventing excess requires a fast method for monitoring the coverage on plants. We present a new, method based on multiphoton electron extraction spectroscopy (MEES), for detecting, quantifying and mapping of imidacloprid coverage on plants. Imaging and quantitative analyses were demonstrated on several plant surfaces including olive and mint leaves and orange peel. Method provides both low detection limits (down to nanogram level) and good trueness. This method is fast and can be directly performed with no sample pre-treatment, thus, it is a good candidate for field analyses.

Coherent Electron Transfer at the Ag/Graphite Heterojunction Interface

Charge transfer in transduction of light to electrical or chemical energy at heterojunctions of metals with semiconductors or semimetals is believed to occur by photogenerated hot electrons in metal undergoing incoherent internal photoemission through the heterojunction interface. Charge transfer, however, can also occur coherently by dipole coupling of electronic bands at the heterojunction interface. Microscopic physical insights into how transfer occurs can be elucidated by following the coherent polarization of the donor and acceptor states on the time scale of electronic dephasing. By time-resolved multiphoton photoemission spectroscopy (MPP), we investigate the coherent electron transfer from an interface state that forms upon chemisorption of Ag nanoclusters onto graphite to a σ symmetry interlayer band of graphite. Multidimensional MPP spectroscopy reveals a resonant two-photon transition, which dephases within 10fs completing the coherent transfer.

Laboratory Gas-phase Infrared Spectra of Two Astronomically Relevant PAH Cations: Diindenoperylene, and Dicoronylene,

Abstract The first gas-phase infrared spectra of two isolated astronomically relevant and large polycyclic aromatic hydrocarbon (PAH) cations—diindenoperylene (DIP) and dicoronylene (DC)—in the 530–1800 cm−1 (18.9−5.6 μm) range—are presented. Vibrational band positions are determined for comparison to the aromatic infrared bands. The spectra are obtained via infrared multiphoton dissociation spectroscopy of ions stored in a quadrupole ion trap using the intense and tunable radiation of the free electron laser for infrared experiments (FELIX). DIP+ shows its main absorption peaks at 737 (13.57), 800 (12.50), 1001 (9.99), 1070 (9.35), 1115 (8.97), 1152 (8.68), 1278 (7.83), 1420 (7.04), and 1550 (6.45) cm−1(μm), in good agreement with density functional theory (DFT) calculations that are uniformly scaled to take anharmonicities into account. DC+ has its main absorption peaks at 853 (11.72), 876 (11.42), 1032 (9.69), 1168 (8.56), 1300 (7.69), 1427 (7.01), and 1566 (6.39) cm−1(μm), which also agree well with the scaled DFT results presented here. The DIP+ and DC+ spectra are compared with the prominent infrared features observed toward NGC 7023. This results both in matches and clear deviations. Moreover, in the 11.0–14.0 μm region, specific bands can be linked to CH out-of-plane (oop) bending modes of different CH edge structures in large PAHs. The molecular origin of these findings and their astronomical relevance are discussed.

Infrared multiphoton dissociation spectroscopy with free electron lasers: On the road from small molecules to biomolecules

Infrared multiphoton dissociation spectroscopy with free electron lasers: On the road from small molecules to biomolecules

Infrared multiphoton dissociation spectroscopy with free electron lasers: On the road from small molecules to biomolecules

Infrared multiphoton dissociation spectroscopy with free electron lasers: On the road from small molecules to biomolecules

Multiphoton spectroscopy: An optical window into molecular electrostatics

Quantitative knowledge about static molecular electric dipole moments is essential for understanding of intramolecular charge transfer as well as nanometer-scale static electric interactions. However, measuring or determining the molecular electrostatic properties with sufficient accuracy remains a challenging task. In our experiments, we measure the femtosecond two-photon absorption spectra- and cross sections of a range of organic- and organometallic chromophores in solution and use these data to determine the electric dipole moment change in corresponding lowest-energy dipole-allowed transition. Good correspondence of our experimental dipole moments with the quantum-chemical calculations as well as reports by other groups using conventional dipole moment measurement methods suggests that quantitative multiphoton spectroscopy may offer all-optical alternative to the traditional techniques such as Stark effect and electrochromism.

Reassigning the CaH+ 11Σ → 21Σ vibronic transition with CaD.

We observe vibronic transitions in CaD+ between the 11Σ and 21Σ electronic states by resonance enhanced multiphoton photodissociation spectroscopy in a Coulomb crystal. The vibronic transitions are compared with previous measurements on CaH+. The result is a revised assignment of the CaH+ vibronic levels and a disagreement with multi-state-complete-active-space second-order perturbation theory theoretical calculations by approximately 700 cm-1. Updated high-level coupled-cluster calculations that include core-valence correlations reduce the disagreement between theory and experiment to 300 cm-1.