Multiple Photon Absorption Research Articles

The Sequence of Coronene Hydrogenation Revealed by Gas-phase IR Spectroscopy

Abstract Gas-phase coronene cations ( ) can be sequentially hydrogenated with up to 24 additional H atoms, inducing a gradual transition from a planar, aromatic molecule toward a corrugated, aliphatic species. The mass spectra of hydrogenated coronene cations show that molecules with odd numbers of additional hydrogen atoms (n H) are dominant, with particularly high relative intensity for “magic numbers” n H = 5, 11, and 17, for which hydrogen atoms have the highest binding energies. Reaction barriers and binding energies strongly affect the hydrogenation sequence and its site specificity. In this contribution, we monitor this sequence experimentally by the evolution of infrared multiple-photon dissociation (IRMPD) spectra of gaseous with n H = 3–11, obtained using an infrared free electron laser coupled to a Fourier transform ion cyclotron mass spectrometer. For weakly hydrogenated systems (n H = 3, 5) multiple-photon absorption mainly leads to loss of H atoms (and/or H2). With increasing n H, C2H2 loss becomes more relevant. For n H = 9, 11, the carbon skeleton is substantially weakened and fragmentation is distributed over a large number of channels. A comparison of our IRMPD spectra with density functional theory calculations clearly shows that only one or two hydrogenation isomers contribute to each n H. This confirms the concept of hydrogenation occurring along very specific sequences. Moreover, the atomic sites participating in the first 11 steps of this hydrogenation sequence are clearly identified.

Rare-earth free sensitizer in NaLuCrF4:Er upconversion material

Upconversion phosphors are known as a material system that can convert near-infrared light into visible/ultraviolet emissions by sequentially absorbing multiple photons. The studies on upconversion materials often use two rare earth (RE) ions as a sensitizer-activator pair. We investigated the influences on luminescence intensity depending on Cr-doping content (x) of hexagonal NaLu0.98–xCrxF4Er0.02 (x = 0–0.9) upconversion material by substituting Lu3+ ions with Cr3+in the absence of Gd3+. The change in upconversion luminescence intensity appears with saddle-like shape. We suggest that Cr3+ ions play the dual role as a constituent in host lattice and a sensitizer in the upconversion process. Optimal conditions for gaining the strongest upconversion emission correspond to x = 0.3–0.5, where there are effective energy transfers between Cr3+ and Er3+ ions and CrEr dimers. Apart from these values, the emission intensity decreases rapidly which can be ascribed to the absence of multiple-photon absorption for the case of low Cr3+ contents, and to the coupling between Cr3+ and/or Er3+ ions for the case of high Cr3+ contents. Magnetization and electron-spin-resonant measurements were performed to understand the correlation between the optical and magnetic properties.

Measurement of Electron Density from Stark-Broadened Spectral Lines Appearing in Silver Nanomaterial Plasma

This work communicates results from optical emission spectroscopy following laser-induced optical breakdown at or near nanomaterial. Selected atomic lines of silver are evaluated for a consistent determination of electron density. Comparisons are presented with Balmer series hydrogen results. Measurements free of self-absorption effects are of particular interest. For several silver lines, asymmetries are observed in the recorded line profiles. Electron densities of interest range from 0.5 to 3 × 1017 cm−3 for five nanosecond Q-switched Nd:YAG radiation at wavelengths of 1064 nm, 532 nm, and 355 nm and for selected silver emission lines including 328.06 nm, 338.28 nm, 768.7 nm, and 827.3 nm and the hydrogen alpha Balmer series line at 656.3 nm. Line asymmetries are presented for the 328.06-nm and 338.28-nm Ag I lines that are measured following generation of the plasma due to multiple photon absorption. This work explores electron density variations for different irradiance levels and reports spectral line asymmetry of resonance lines for different laser fluence levels.

Photochemistry and spectroscopy of small hydrated magnesium clusters Mg+(H2O)n, n = 1-5.

Hydrated singly charged magnesium ions Mg+(H2O)n, n ≤ 5, in the gas phase are ideal model systems to study photochemical hydrogen evolution since atomic hydrogen is formed over a wide range of wavelengths, with a strong cluster size dependence. Mass selected clusters are stored in the cell of an Fourier transform ion cyclotron resonance mass spectrometer at a temperature of 130 K for several seconds, which allows thermal equilibration via blackbody radiation. Tunable laser light is used for photodissociation. Strong transitions to D1–3 states (correlating with the 3s-3px,y,z transitions of Mg+) are observed for all cluster sizes, as well as a second absorption band at 4–5 eV for n = 3-5. Due to the lifted degeneracy of the 3px,y,z energy levels of Mg+, the absorptions are broad and red shifted with increasing coordination number of the Mg+ center, from 4.5 eV for n = 1 to 1.8 eV for n = 5. In all cases, H atom formation is the dominant photochemical reaction channel. Quantum chemical calculations using the full range of methods for excited state calculations reproduce the experimental spectra and explain all observed features. In particular, they show that H atom formation occurs in excited states, where the potential energy surface becomes repulsive along the O⋅⋅⋅H coordinate at relatively small distances. The loss of H2O, although thermochemically favorable, is a minor channel because, at least for the clusters n = 1-3, the conical intersection through which the system could relax to the electronic ground state is too high in energy. In some absorption bands, sequential absorption of multiple photons is required for photodissociation. For n = 1, these multiphoton spectra can be modeled on the basis of quantum chemical calculations.

Hot-carrier-mediated impact excitation of Er3+ ions in SiO2 sensitized by Si Nanocrystals

Past research has shown that indirect excitation of Er3+ ions in SiO2 solid-state matrix with Si nanocrystals can be achieved by different pathways. Here, we investigate the impact excitation mechanisms in detail by means of time-resolved photoluminescence spectroscopy. We explicitly demonstrate that the free carrier impact excitation mechanism is activated as soon as the carriers obtain sufficient excess energy. The “hot” carriers with the above-threshold energy can be created upon optical pumping in two ways: either upon absorption of (i) a single photon with an energy exceeding a certain threshold hν > Eth or (ii) following absorption of multiple photons of lower energy in a single nanocrystal, hν < Eth, followed by an Auger recombination of the generated multiple e-h pairs. In addition, we show that the impact excitation dynamics by hot carriers are similar, regardless of the mode in which they have been created.

Radiation-Induced Chemical Dynamics in Ar Clusters Exposed to Strong X-Ray Pulses

We show that electron and ion spectroscopy reveals the details of the oligomer formation in Ar clusters exposed to an x-ray free electron laser (XFEL) pulse, i.e., chemical dynamics triggered by x rays. With guidance from a dedicated molecular dynamics simulation tool, we find that van der Waals bonding, the oligomer formation mechanism, and charge transfer among the cluster constituents significantly affect ionization dynamics induced by an XFEL pulse of moderate fluence. Our results clearly demonstrate that XFEL pulses can be used not only to "damage and destroy" molecular assemblies but also to modify and transform their molecular structure. The accuracy of the predictions obtained makes it possible to apply the cluster spectroscopy, in connection with the respective simulations, for estimation of the XFEL pulse fluence in the fluence regime below single-atom multiple-photon absorption, which is hardly accessible with other diagnostic tools.

(Invited) Luminescent Rare Earth Doped Nanoparticles

In recent years, rare earth doped nanoparticles have been proposed for a number of exciting applications in a wide-range of fields including nanomedicine, nanoelectronics, biosensing, bioimaging, photovoltaics, photocatalysis, etc. This is due, primarily, to their interesting and versatile optical properties including their inherent ability to convert low-energy near-infrared (NIR) light to higher energies spanning the UV, visible, and NIR regions of the spectrum via a process known as upconversion. Upconversion, inherent to the rare earths, results from the multitude of 4f electronic energy states, many of which are spaced equally and long-lived, that facilitate the absorption of multiple low energy photons to populate the higher energy emitting states. Thus, upconversion is a multiphoton process, but unlike other two-photon excited materials, the need for expensive ultrafast lasers is eliminated since the simultaneous absorption of multiple photons is not required; due to the long lifetimes of the rare earth ion excited states, sequential absorption occurs efficiently. Moreover, following NIR excitation, these nanoparticles can also undergo conventional luminescence and emit in the three NIR biological windows where tissues are optically transparent. Here, we will discuss the luminescence properties of rare earth doped nanoparticles and present a perspective on both their applicability as well as drawbacks for use in various applications. Finally, we will demonstrate that the intelligent combination of diverse materials, with different properties, will allow for the engineering of novel multifunctional nanostructures, which can usher in a new era for rare earth doped nanoparticles.

Giant multiphoton absorption for THz resonances in silicon hydrogenic donors

The absorption of multiple photons when there is no resonant intermediate state is a well-known nonlinear process in atomic vapours, dyes and semiconductors. The N-photon absorption (NPA) rate for donors in semiconductors scales proportionally from hydrogenic atoms in vacuum with the dielectric constant and inversely with the effective mass, factors that carry exponents 6N and 4N, respectively, suggesting that extremely large enhancements are possible. We observed 1PA, 2PA and 3PA in Si:P with a terahertz free-electron laser. The 2PA coefficient for 1s–2s at 4.25 THz was 400,000,000 GM (=4 × 10−42 cm4 s), many orders of magnitude larger than is available in other systems. Such high cross-sections allow us to enter a regime where the NPA cross-section exceeds that of 1PA—that is, when the intensity approaches the binding energy per Bohr radius squared divided by the uncertainty time (only 3.84 MW cm−2 in silicon)—and will enable new kinds of terahertz quantum control.

CO2 LASER-DRIVEN REACTIONS IN PURE ACETYLENE FLOW

We show that multiple-photon absorption of radiation from a 10.56 μm cw CO2 laser by intermediates (ethylene, vinylidene) generated in pure acetylene flow makes them decompose to carbon dimers and excited hydrogen. The latter associates with downstream acetylene to feedback those laser absorbing intermediates thus making the reactions self-sustained in the absence of oxygen. This process is different from acetylene self-decomposition that may occur at higher temperature and pressure. The results of our work may be useful for understanding the generation of various carbon allotropes and interstellar dust from acetylene.

Visible Multiphoton Dissociation of Chromophore-Tagged Peptides

The visible photodissociation mechanisms of QSY7-tagged peptides of increasing size have been investigated by coupling a mass spectrometer and an optical parametric oscillator laser beam. The experiments herein consist of energy resolved collision- and laser-induced dissociation measurements on the chromophore-tagged peptides. The results show that fragmentation occurs by similar channels in both activation methods, but that the branching ratios are vastly different. Observation of a size-dependent minimum laser pulse energy required to induce fragmentation, and collisional cooling rates in time resolved experiments show that laser-induced dissociation occurs through the absorption of multiple photons by the chromophore and the subsequent heating through vibrational energy redistribution. The differences in branching ratio between collision- and laser-induced dissociation can then be understood by the highly anisotropic energy distribution following absorption of a photon.Graphical ᅟ

Photodissociation spectroscopy of protonated leucine enkephalin.

Protonated leucine enkephalin (YGGFL) was studied by ultraviolet photodissociation (UVPD) from 225 to 300 nm utilizing an optical parametric oscillator tunable wavelength laser system (OPO). Fragments were identified by absolute mass measurement in a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). Bond cleavage was preferred in the vicinity of the two aromatic residues, resulting in high ion abundances for a4, a1, b3, y2 and y1 fragments. a, b and y ions dominated the mass spectrum, and full sequence coverage was achieved for those types. Photodissociation was most effective at the short wavelength end of the studied range, which is assigned to the onset of the La π-π* transition of the tyrosine chromophore, but worked well also at the Lb π-π* chromophore absorption maxima in the 35 000-39 000 cm-1 region. Several side-chain and internal fragments were observed. H atom loss is observed only above 41 000 cm-1, consistent with the requirement of a curve crossing to a repulsive 1πσ* state. It is suggested that the photochemically generated mobile H atom plays a role in further backbone cleavages, similar to the mechanism for electron capture dissociation. The b4 fragment is most intense at the Lb chromophore absorptions, undergoing additional fragmentation at higher photon energies. The high resolution of the FT-ICR MS revealed that out of all x and z-type fragments only x3 and x4 were formed, with low intensity. Other previously reported x- and z-fragments were re-assigned to internal fragments, based on exact mass measurement.

Cisplatin and transplatin interaction with methionine: bonding motifs assayed by vibrational spectroscopy in the isolated ionic complexes.

Cisplatin and transplatin (cis- and trans-[PtCl2(NH3)2]) have been allowed to react with methionine (Met) in water solution in a study aimed to characterize the monofunctional complex primarily formed. The thioether function of methionine is known to have a very high affinity for square planar platinum(ii) and sulfur-containing biomolecules have been proposed as a cisplatin drug reservoir on the way to platination at DNA. Both cisplatin and transplatin yield [PtCl(NH3)2Met]+ complexes, delivered by electrospray ionization in the gas phase and sampled as isolated species using tools based on mass spectrometry. The collision induced dissociation spectra of both cis-[PtCl(NH3)2Met]+ and trans-[PtCl(NH3)2Met]+ are quite similar and also the transport properties assayed by ion mobility mass spectrometry do not allow any appreciable discrimination. However, the vibrational spectra obtained by IR multiple photon absorption (IRMPD) spectroscopy show distinct features. Their analysis, supported by quantum chemical calculations, has revealed that while cisplatin attack is mainly directed to the sulfur atom of Met, transplatin shows a more balanced partition between sulfur and nitrogen binding. Among the vibrational signatures characterizing cis-[PtCl(NH3)2Met]+ and trans-[PtCl(NH3)2Met]+ complexes, the asymmetric NH2 stretching of the α-amino group of the amino acid at ca. 3440 cm-1 is peculiar and diagnostic of S-platination. IRMPD kinetics evaluated at this frequency support the prevailing S-attack by cisplatin while approximately a 1 : 2 ratio of S- versus N-coordination is observed by transplatin, to be possibly related to the trans effect at the platinum center.

Cisplatin Primary Complex with l-Histidine Target Revealed by IR Multiple Photon Dissociation (IRMPD) Spectroscopy.

The primary complex obtained from cisplatin and l-histidine in water has been detected and isolated by electrospray ionization. The so-obtained cis-[PtCl(NH3 )2 (histidine)]+ complex has been characterized in detail by high-resolution mass spectrometry (MS), tandem MS, IR multiple photon dissociation (IRMPD) spectroscopy, and by quantum chemical calculations. The structural features revealed by IRMPD spectroscopy indicate that platinum binds to the imidazole group, which presents tautomeric forms. Thus, depending on the position of the amino acid pendant on the imidazole ring, isomeric complexes are formed that are remarkably different with respect to the ease with which they undergo fragmentation when activated either by energetic collisions or by multiple IR photon absorption. It is shown here how IRMPD kinetics can allow their relative proportions to be estimated.

Multiple absorption of laser photons by atoms for 40 years and more

Multiple absorption of laser photons by atoms for 40 years and more

Infrared Action Spectroscopy of Low-Temperature Neutral Gas-Phase Molecules of Arbitrary Structure.

We demonstrate a technique for IR action spectroscopy that enables measuring IR spectra in a background-free fashion for low-temperature neutral gas-phase molecules of arbitrary structure. The method is exemplified experimentally for N-methylacetamide molecules in the mid-IR spectral range of 1000-1800 cm^{-1}, utilizing the free electron laser FELIX. The technique involves the resonant absorption of multiple mid-IR photons, which induces molecular dissociation. The dissociation products are probed with 10.49eV vacuum ultraviolet photons and analyzed with a mass spectrometer. We also demonstrate the capability of this method to record, with unprecedented ease, mid-IR spectra for the molecular associates, such as clusters and oligomers, present in a molecular beam. In this way the mass-selected spectra of low-temperature gas-phase dimers and trimers of N-methylacetamide are measured in the full amide I-III range.

Metal-Organic Frameworks Modulated by Doping Er(3+) for Up-Conversion Luminescence.

Here we present metal-organic frameworks prepared by a one-step synthesis method, possessing both architectural properties of MOF building and up-conversion luminescence of rare earth Er(3+) (hereafter denoted as Up-MOFs). Up-MOFs have characteristic up-conversion emissions at 520, 540, and 651 nm under the excitation of 980 nm owing to the multiple photon absorption. The up-conversion mechanism of these Up-MOFs has been discussed, and it can be attributed to the excited state absorption process. The design and synthesis of Up-MOF materials possessing near-infrared region excitation and up-conversion luminescence are fully expected to be candidates for the advancement of applications in bioimaging, sensors, optoelectronics, and energy conversion/storage devices.

Femtosecond charge and molecular dynamics of I-containing organic molecules induced by intense X-ray free-electron laser pulses.

We studied the electronic and nuclear dynamics of I-containing organic molecules induced by intense hard X-ray pulses at the XFEL facility SACLA in Japan. The interaction with the intense XFEL pulse causes absorption of multiple X-ray photons by the iodine atom, which results in the creation of many electronic vacancies (positive charges) via the sequential electronic relaxation in the iodine, followed by intramolecular charge redistribution. In a previous study we investigated the subsequent fragmentation by Coulomb explosion of the simplest I-substituted hydrocarbon, iodomethane (CH3I). We carried out three-dimensional momentum correlation measurements of the atomic ions created via Coulomb explosion of the molecule and found that a classical Coulomb explosion model including charge evolution (CCE-CE model), which accounts for the concerted dynamics of nuclear motion and charge creation/charge redistribution, reproduces well the observed momentum correlation maps of fragment ions emitted after XFEL irradiation. Then we extended the study to 5-iodouracil (C4H3IN2O2, 5-IU), which is a more complex molecule of biological relevance, and confirmed that, in both CH3I and 5-IU, the charge build-up takes about 10 fs, while the charge is redistributed among atoms within only a few fs. We also adopted a self-consistent charge density-functional based tight-binding (SCC-DFTB) method to treat the fragmentations of highly charged 5-IU ions created by XFEL pulses. Our SCC-DFTB modeling reproduces well the experimental and CCE-CE results. We have also investigated the influence of the nuclear dynamics on the charge redistribution (charge transfer) using nonadiabatic quantum-mechanical molecular dynamics (NAQMD) simulation. The time scale of the charge transfer from the iodine atomic site to the uracil ring induced by nuclear motion turned out to be only ∼5 fs, indicating that, besides the molecular Auger decay in which molecular orbitals delocalized over the iodine site and the uracil ring are involved, the nuclear dynamics also play a role for ultrafast charge redistribution. The present study illustrates that the CCE-CE model as well as the SCC-DFTB method can be used for reconstructing the positions of atoms in motion, in combination with the momentum correlation measurement of the atomic ions created via XFEL-induced Coulomb explosion of molecules.

Laser-nucleus interactions: The quasi-adiabatic regime

The interaction between nuclei and a strong zeptosecond laser pulse with coherent MeV photons is investigated theoretically. We provide a first semi-quantitative study of the quasiadiabatic regime where the photon absorption rate is comparable to the nuclear equilibration rate. In that regime, multiple photon absorption leads to the formation of a compound nucleus in the so-far unexplored regime of excitation energies several hundred MeV above the yrast line. The temporal dynamics of the process is investigated by means of a set of master equations that account for dipole absorption, stimulated dipole emission, neutron decay and induced fission in a chain of nuclei. That set is solved numerically by means of state-of-the-art matrix exponential methods also used in nuclear fuel burnup and radioactivity transport calculations. Our quantitative estimates predict the excitation path and range of nuclei reached by neutron decay and provide relevant information for the layout of future experiments.

Multiple-photon absorption in cooled molecular beams of acenes compounds at 266 and 355 nm laser radiation

SynopsisThe cooled molecular beams of acenes compounds as naphthalene C10H8, anthracene C14H10, and ben- zantracene C18H12, were produced by adiabatic expansion in high vacuum chamber, 10-8 torr. Molecular beams interacted with laser radiation of 266 and 355 nm, from a Ng:YAG laser at intensities up to 1010 W·cm-2 At higher intensities the multiple photon absorption was possible. The number of photons was calculated using Keldysh approach. The dominant photophysics of photon-molecule interactions were photodissociation and photoionization processes depending on the wavelength used during the experiment.

Laser-pointer-induced self-focusing effect in hybrid-aligned dye-doped liquid crystals.

Nonlinear optics deals with phenomena where “light controls light”; e.g., there is mediation by an intensity-dependent medium through which light propagates. This field has attracted much attention for its immense potential in applications dependent on nonlinear processes, such as frequency conversion, multiple-photon absorption, self-phase modulation, and so on. However, such nonlinearities are typically only observed at very high light intensities and thus they require costly lasers. Here, we report on a self-focusing effect induced with a 1 mW handheld laser pointer. We prepared polymer-stabilized dye-doped liquid crystals, in which the molecular director orientation gradually changes from homeotropic at one surface to homogeneous at the other. This is referred to as hybrid alignment. In such films, the threshold intensity needed to form diffraction rings was reduced by a factor of 8.5 compared to that in conventional homeotropic cells, which enabled the induction of the self-focusing effect with a laser pointer.